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By F. E. Werner, B. L. Averbach, Morris Cohen

THAT bainite formed near the M, temperature bears a striking r esemblance to martensite tempered at the same temperature has been shown by the electron microscope.' By means of electron diffraction,' it has been established that carbide and cementite are present in bainite formed at 500°F (260°C); these carbides are also found in martensite tempered at 500°F (260°C).' The investigation reported here is concerned with an X-ray study of the matrix phases in lower bainite and tempered martensite. These phases have turned out to be dissimilar in structure; the matrix of bainite is body-centered-cubic while that of tempered martensite is body-centered-tetragonal. A vacuum-melted Fe-C alloy containing 1.43 pct C was studied. Specimens of 16 in. diam were sealed in evacuated silica tubing and austenitized at 2300°F (1260°C) for 24 hr. One specimen was quenched into a salt bath at 410°+7 °F (210°+4°C), held for 16 hr, and cooled to room temperature. The structure consisted of about 90 to 95 pct bainite, the re: mainder being martensite and retained austenite. A second specimen was quenched from the austen-itizing temperature into iced brine and then into liquid nitrogen. It consisted of about 90 pct martensite and 10 pct retained austenite. The latter specimen was tempered for 10 hr at 410°+2°F (210°+1°C). The specimens were then fractured along prior austenite grain boundaries (grain size about 2 mm diam) by light tapping with a hammer. Single aus-tenite grains, mostly transformed, were etched to about 0.5 mm diam and mounted in a Unicam single crystal goniometer, which allowed both rotation and oscillation of the sample. Lattice parameters were measured by the technique of Kurdjumov and Lyssak. This method takes advantage of the fact that martensite and lower bainite are related to austenite by the Kurdjumov-sachs orientation relationships Thus, the (002) and the (200) (020) reflections can be recorded separately, permitting the c and a parameters to be determined without interference from overlapping reflections. According to these findings, the matrix phase in bainite is body-centered-cubic and, within experimental error, has the same lattice parameter as ferrite (2.866A). On the other hand, martensite, tempered as above, retains some tetragonality, with a c/a ratio of 1.005t0.002. Most workers in the past have assumed that bainite is generated from austenite as a supersaturated phase, but the nature of this product has not been established. The question arises as to whether bainite initially has a tetragonal structure and then tempers to cubic, or if it forms directly as a cubic structure. If it forms with a tetragonal lattice, it might well be expected to temper to the cubic phase at about the same rate as tetragonal martensite. The martensitic specimen used here was given approximately the same tempering exposure, 10 hr at 410°F, as suffered by the greater part of the bainite during the isothermal transformation. About 50 pct bainite was formed in 6 hr at 410°F. On tempering at this temperature, martensite reduces its tetragonality within a few minutes to a value corresponding to 0.30 pct C.' Further decomposition proceeds slowly, and after 10 hr the c/a ratio is still appreciable, i.e., 1.005. Thus, even if the bainite were to form as a tetragonal phase with a tetragonality corresponding to only 0.30 pct C, which might be assumed to coexist with e carbide, it would not be expected to become cubic in this time. It seems very likely, therefore, that bainite forms irom austenite as a body-centered-cubic phase and does not pass through a tetragonal transition. The carbon content of the cubic phase has not been determined, but it could easily be as high as 0.1 pct, within the experimental uncertainty of the lattice-parameter measurements. It has been postulated that retained austenite decomposes on tempering into the same product as martensite tempered at the same temperature. There is now considerable doubt on this point. The isothermal transformation product of both primary and retained austenite at the temperature in question here is bainite," and the present findings show that bainite and tempered martensite do not have the same matrix. Acknowledgments The authors would like to acknowledge the financial support of the Instrumentation Laboratory, Massachusetts Institute of Technology, and the United States Air Force.

Jan 1, 1957

By Glenn S. Wyman

CHUQUICAMATA, located in northern Chile in the Province of Antofagasta, is on the western slope of the Andes at an elevation of 9500 ft. Because of its position on the eastern edge of the Atacama Desert, the climate is extremely arid with practically no precipitation, either rain or snow. All primary blasting in the open-pit mine at Chuquicamata is done by the churn drill, blasthole method. Since 1915; when the first tonnages of importance were removed from the open pit, there have been many changes in the blasting practice, but no clear-cut rules of method and procedure have been devised for application to the mine as a whole. One general fact stands out: both the ore and waste rock at Chuquicamata are difficult to break satisfactorily for the most efficient operation of power shovels. Numerous experiments have been made in an effort to improve the breakage and thereby increase the shovel efficiency. Holes of different diameter have been drilled, the length of toe and spacing of holes have been varied, and several types of explosives have been used. Early blasting was done by the tunnel method. The banks were high, generally 30 m, requiring the use of large charges of black powder, detonated by electric blasting caps: Large tonnages were broken at comparatively low cost, but the method left such a large proportion of oversize material for secondary blasting that satisfactory shovel operation was practically impossible: Railroad-type steam and electric shovels then in service proved unequal to the task of efficiently handling the large proportion of oversize material produced. The clean-up of high banks proved to be dangerous and expensive as large quantities of explosive were consumed in dressing these banks, and from time to time the shovels were damaged by rock slides. As early as 1923 the high benches were divided, and a standard height of 12 m was selected for the development of new benches. The recently acquired Bucyrus-Erie 550-B shovel, with its greater radius of operation compared to the Bucyrus-Erie 320-B formerly used for bench development, allowed the bench height to be increased to 16 m. Churn drill, blasthole shooting proved to be successful, and tunnel blasts were limited to certain locations where development existed or natural ground conditions made the method more attractive than the use of churn-drill holes. Liquid oxygen explosive and black powder were used along with dynamite of various grades in blasthole loading up to early 1937. Liquid oxygen and black powder were discontinued because they were more difficult to handle due to their sensitivity to fire or sparks in the extremely dry climate. At present ammonium nitrate dynamite is favored because of its superior handling qualities and its adaptability to the dry condition found in 90 pct of the mine. In wet holes, which are found only in the lowest bench of the pit and account for the remaining 10 pct of the ground to be broken, Nitramon in 8x24-in. cans, or ammonium nitrate dynamite packed in 8x24-in. paper cartridges, is being used. This latter explosive, which is protected by a special antiwetting agent that makes the cartridges resistant to water for about 24 hr, currently is considered the best available for the work and is preferred over Nitramon. Early churn drill hole shots detonated' by electric blasting caps, one in each hole, gave trouble because of misfires caused by the improper balance of resistance in the electrical circuits. Primarily, it was of vital importance to effect an absolute balance of resistance in these circuits, the undertaking and completion of which invariably caused delays in the shooting schedule. Misfires resulting from the improper balance of electrical circuits, or from any other cause, were extremely hazardous, since holes had to be unloaded or fired by the insertion of another detonator. The advent of cordeau, later followed by primacord, corrected this particular difficulty and therefore reduced the possibility of missed holes. After much experimentation, the blasting practice evolved into single row, multihole shots, with the holes spaced 4.5 to 5 m center to center in a row 7.5 to 8 m back from the toe. Such shots were fired from either end .by electric blasting caps attached to the main trunk lines of cordeau or primacord. The detonating speed of cordeau or primacord gave the practical effect of firing all holes instantaneously. Double row and multirow blasts, fired instantaneously with cordeau or primacord, proved to be unsatisfactory in the type of rock found at Chuquica-

Jan 1, 1952

By A. S. Grove, C. T. Sah, E. H. Snow, B. E. Deal

A summary of- several recent investigations in to the properties of the metal-oxide-silicon system is presented. A major portion of these studies makes use of the MOS capacitance-z)oltage method of' analysis. The particular areas of investigation which are reported include: 1) a general survey of the electvical properties of thermally oxidized silicon surjbccs; 2) a study of ion migration through silicon dioxide films ; 3) measurements of electron and hole mobilities in surface inversion layers; 4) a study of impurity redistribution due to thermal o.ridatiotz; and 5) measurements of the rates of oxidation oj-heavily doper7. silicon. THE importance of the metal-oxide-semiconductor (MOS) system in the semiconductor industry is well-known. In addition to its importance in the "planar" device technology,' the MOS structure is now also used in the fabrication of active solid-state devices. Consequently, extensive efforts have been made recently to obtain a better understanding of the characteristics of this system. A summary of some studies of the MOS system conducted in our laboratories during the past year is presented. For the most part these studies used silicon as the semiconductor, along with silicon dioxide and aluminum as the other two components of the system. Since the MOS capacitance-voltage method of analysis was used extensively in these studies, we will first briefly describe its nature and consider some of the possible causes of deviation of experimental observations from the simple theory. We will then outline the various related areas of investigation carried out in our laboratories and will briefly indicate some of the results. It should be noted that the purpose of this paper is merely to provide a brief summary of MOS studies. More detailed discussions of the various areas of investigation are given in the references cited. PRINCIPLES OF THE MOS C-V METHOD OF ANALYSIS' A sketch of the MOS structure is shown in the upper portion of Fig. 1. In this case the insulating film is Si02 and the semiconductor p-type silicon. If a large negative bias is applied to the metal field plate, holes are attracted to the silicon surface. The silicon then behaves much like a metal and the capacitance measured is that of the oxide layer alone, Co. If a small positive bias is applied to the aluminum, holes are repelled and a region depleted of majority carriers is formed at the silicon surface. This depletion I-egion adds to the width of the dielectric and the measured capacitance begins to drop. With increasing positive bias, the width of the electrical depletion region increases. At some large positive bias an inzevsion regiotr is formed at the surface and additional charges induced in the silicon appear in the form of electrons in this narrow inversion region. Thus the depletion-region width approaches a maximum value and, consequently, the capacitance reaches a minimum value and then either levels off or rises again depending on the measurement frequency and the rate of equilibration of the minority carriers in the inversion layer.3 Band diagrams, along with the corresponding charge distributions, are shown in Fig. 1 for the above bias conditions. If minority carriers cannot accumulate at the surface to form an inversion region, the depletion-region width continues to increase with increased positive bias and the capacitance drops toward zero as in a reverse biased p-n junction. The effect of a work-function difference $hs between the metal and the silicon, and of surface charges per unit area Qss located at the oxide-silicon interface, is simply to attract charges in the silicon much like the applied bias. It can be shown that this results in a parallel shift of the capacitance-voltage characteristic along the voltage axis by an amount corresponding to AV = -$bIs + Qss/Co. Theoretical curves have been calculated4 giving the capacitance of the MOS structure C normalized to the oxide capacitance Co vs the quantity VG here VG is the voltage applied to the metal field plate. In Fig. 2 such calculations are shown as points for a particular oxide thickness and bulk impurity concentration for a p-type semiconductor. (For an n-type semiconductor the curves would be mirror images of these.) All three cases, i.e., low frequency. high frequency, and depletion, are indicated. Also shown in the figure are recorder tracings of the characteristics of actual devices. These characteristics have been shifted along the voltage axis to compensate the effect of surface charges and work-function difference. It is evident that agreement between experiment and theory is good. The nature of this shift along the voltage axis is

Jan 1, 1965

By John C. Sawyer

The mechanism of catastrophic oxidation of chromium and 446 stainless steel is examined. Data are presented to show that accelerated oxidation of these two materials, as caused by lead oxide, can occur in the absence of a liquid layer contrary to presently accepted theory. An alternate theory is proposed in which the rate of accelerated oxidation is a function of the rate at which lead oxide destroys the protective oxide formed on the base metal. An example of the application of the theory is given for the catastrophic oxidation of chromium in the presence of lead oxide. WHEN stainless iron-, nickel-, or cobalt-base alloys are heated in air to moderate temperatures in the presence of certain metallic oxides, oxidation will proceed at an accelerated rate. This phenomenon, often called "catastrophic oxidation", is most pronounced for the stainless steels. With these alloys the condition is so severe that large masses of oxide will form on the surface of the alloy in 1 hr or less at temperatures of 1200o to 1700oF. While a number of oxides are known to cause this effect, PbO, V2O5, and Moo3 are the most familiar, having been the subject of one or more investigations which have appeared in the literature.1-7 In presenting the results of these investigations, many of the authors have offered possible explanations to account for the more rapid rate of oxidation observed; however, the liquid layer theory as proposed by Rathenau and Meijering 2 has been the most commonly accepted mechanism. The liquid layer theory proposes that a low-melting oxide layer is formed on the surface of the alloy as the result of the interaction of the alloy oxide and the contaminating oxide. When the temperature of oxidation is above the melting point of the oxide on the surface, a liquid layer will form and oxidation will proceed at an accelerated rate. At temperatures below the melting point of the surface oxide, oxidation will proceed more slowly in the normal manner. It is argued that the rates of diffusion of oxygen and metal ions through the liquid layer are extremely rapid thereby accounting for the high rate of oxidation. Various experimental data have been presented to show that the temperature at which accelerated oxidation first becomes apparent coincides with the melting point of the eutectic oxide which would be present on the surface. Some exceptions have been observed, e.g., silver will oxidize in the presence of Moo3 at temperatures below the lowest melting eutectic; on the other hand, stainless steel will not be catastrophically oxidized at 1500oF in a molten bath of PbO and SiO2. In reviewing the various theories which have been used to explain catastrophic oxidation, Kubaschewski and Hopkins 8 favor the liquid layer theory, but note that, ".. .as experimental observations are not altogether in agreement with this theory (liquid layer theory), one should consider it a necessary but not a sufficient condition." In contemplating the liquid layer theory, it appears that sufficient evidence has not been presented to establish the theory beyond question. As a means of further clarification, a program of research was undertaken to determine in greater detail the mechanism of accelerated oxidation as caused by lead oxide. The first part of the program deals with a comparison of the oxidation of both AISI 446 stainless steel and chromium metal in the presence of lead oxide, vs the oxidation of these two materials in air alone. These comparisons are made at a number of different temperatures, most of which are below the melting point of the surface oxides. The second part of the program is concerned with a presentation of an alternate theory of accelerated oxidation exemplified by the system Cr-PbO-Air. PROCEDURE AND RESULTS Several experimental methods are commonly used to follow the progress of oxidation. One of these, the weight-gain method, was chosen for this work. This procedure requires that a specimen of the alloy be weighed, oxidized for a given period of time at an elevated temperature, and reweighed—the difference between the two weights being noted. The weight gain of the specimen represents the amount of oxygen acquired from the atmosphere to transform a portion of the specimen to oxide. In those cases where there is a tendency for the specimen or oxide to volatilize at the testing temperature, additional data must be collected so that a correction factor can be determined. This factor must be applied to the weight change in order to ascertain the actual amount of oxidation which has taken place. The specimens used for this work were 1 1/2 in.

Jan 1, 1963

By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By Jeff Steinhoff

INTRODUCTION The Henderson mine utilizes a highly mechanized, continuous, panel-caving, mining system to extract ore from a deep, massive, molybdenite deposit. The mine is located 80.5 km (50 miles) west of Denver, Colorado. The mine surface facilities are located 3,170 m (10,400 feet) above sea level in a steep valley on the eastern side of the Continental Divide. Milling facilities are 24 km (15 miles) west on the western side of the divide at an elevation of 2,804 m (9,200 feet) above sea level. The ore- body is located approximately 3,000 feet south of the valley under Red Mountain. Access to the ore for men and materials is through a 915 m (3,000-foot) deep, 8.5 m (28-foot) diameter, vertical, concrete-lined, service shaft. Access from the mill is through a 15.5 km (9.6-mile) rail haulage tunnel. The mine is ventilated through an additional intake shaft and two exhaust shafts. Mine production at this time is 27,255 mtpd (30,000 stpd). The mine ventilation system supplies 1,038 cubic meters per second (2.2 million cfm) through approximately 60 miles of drifting or 2.7 tons of air per ton of ore mined. There are 130 fans in the mine in fixed locations and in vent lines with 6,900 connected horsepower in the mine. MINING METHOD AND LAYOUT The orebody is divided vertically into two major zones. The upper zone is the 8100-level production area. The bottom zone is the 7700- level production area which is in the early development stage. The rail haulage level at 7500 feet is common to both production zones. Each mine production zone consists of five associated sublevels. The cave undercut level is 16.8 m (55 feet) above the production level. Two boundary cutoff levels are located 44.2 m (145 feet) and 62.5 m (205 feet) respectively above the production level. The fresh-air level is positioned 15.2 m (50 feet) below the production level, and the exhaust vent level is 19.8 m (65 feet) below the production level. Horizontally, each production zone is divided into three panels each, 224 m (800 feet) wide. These panels are caved from south to north. As the caving in one panel nears completion, caving in the adjacent panel is initiated. Development for the caving panels is continuous so that the sublevels above the production level and the production level itself have a combination of development drifting and production-related activities. UNDERGROUND VENTILATION NETWORK The ventilation system is zoned in the same manner as the orebody itself. One major split of 600 cubic meters per second (1,270,000 cfm) ventilates the 8100-level production zone; one split of 100 cubic meters per second (210,000 cfm) ventilates the development of the 7700- level production zone; and one split of 165 cubic meters per second (350,000 cfm) ventilates the 7500 rail haulage level. The haulage tunnel requires an additional 188 cubic meters per second (400,000 cfm) of air. Development-drift ventilation is accomplished by hanging 1.0 m (3.5-foot) diameter steel ducting in the drifts with 40-horsepower, 0.96 m (38-inch) diameter fans supplying 9.4 cubic meters per second (20.000 cfm). The normal maximum length for these systems is 300 m (1,000 feet). The 8100-level production-area ventilation system is especially suited to a high level of mucking activity confined in a small area. Approximately 93 per cent of the mine's total production is transferred from the drawpoints to ore passes in 10 production drifts. The active area in each drift is 300 m (1,000 feet). Twelve 5-cubic-yard LHD units with Cat turbo- charged 170-horsepower engines are assigned to the area. Under these conditions, more than one LHD is assigned to a particular production drift. Adequate ventilation is maintained by making an air change every 97 m (320 feet) along the production drifts. Fresh air is brought into the production drifts from the fresh-air level through 1.37 m (4.5-foot) diameter raises. Air travels south along the production drift to the ore pass where it is exhausted down the ore pass to the exhaust level. The ore pass is followed by another intake which is followed by an ore-pass exhaust. At the south end of the production area, a series of exhaust fans maintain a southerly air- flow through the production level.

Jan 1, 1981

By R. M. Waterstrat

The phases occurring in the V-Mn system were studied by means of X-yay diffraction and metallo-paphic techniques, using are-melted alloy specimens annealed in the temperature range 800° to 1150°C and quenched. The bcc solid solution extends at 1250°C all the way from vanadium to 6-manganese. Below 1050°C the a-phase is formed, and the terminal a-manganese phase is stabilized up to about 900°C by vanadium in solid solution. IN the only previous general survey of the V-Mn system Cornelius, Bungardt and Schiedtl reported the existence of three intermediate phases corresponding to the approximate compositions VMn,, VMn, and V5Mn. The phase VMn8 has recently been identified as a o phase2 but the alloy VMn was found to have a bcc structure2 corresponding apparently to the vanadium solid solution rather than to the large cubic unit cell reported by Cornelius et al. 1 Subsequent work by Rostoker and Yamamoto3 has shown that the vanadium-base bcc solid solution extends to at least 15 pct Mn at 900°C. An alloy corresponding to the composition VMn, was examined by Elliott,4 who reported that the as-cast sample as well as samples annealed at 1200o and 1300°C had bcc structures, but that annealing at 1000°, 800") and 600°C produced two phases. One of these phases was apparently the bcc solid solution and the other resembled the o phase structure. Hellawell and Hume-Rothery5 established the phase relationships in manganese-rich alloys above 1000°C, and showed that the o phase in this system is replaced by the 6 Mn (bcc) solid solution at temperatures above 1050°C. These results suggest that a continuous bcc solid solution may exist above 1050°C between vanadium and 6 Mn. The present investigation was undertaken in order to develop more complete information in regard to this system. EXPERIMENTAL METHODS The alloys used in the present work were prepared by arc-melting electrolytic manganese having a minimum purity of 99.9 pct and vanadium lumps with a purity of 99.7 pct. The major impurities present in these metals were carbon, nitrogen, and oxygen and this would account for the small percentage of nonmetallic inclusions observed metal-lographically. The arc-melting was at first performed under a helium atmosphere and it was necessary to keep the melting times as short as possible in order to minimize the loss of manganese by vaporization. It was later found that the evaporation of manganese was considerably reduced when the melting was done under argon atmosphere. The final composition of each alloy was calculated by assuming that the total weight loss during melting was due to evaporation of manganese. Compositions which were calculated in this manner agreed reasonably well with the results of chemical analysis, as shown in Table I. Spectrographic analysis revealed the presence of contamination by tungsten, but in no case was the percentage of tungsten greater then 0.4 at. pct. The specimens were in each case broken in half and the fractured section was examined visually and microscopically for evidence of inhomogeneity. Each specimen was homogenized at temperatures near l100°C, as shown in Table I. After this treatment most specimens consisted of large columnar grains of the bcc vanadium solid solution. The etchant used in most of the metallographic work consisted of 20 pct nitric acid, 20 pct hydro-flouric acid, and 60 pct glycerine. It was found that this etchant would clearly delineate the phases present in these alloys although it does not produce any striking contrast between the phases. For certain manganese-rich alloys, a 1 pct aqueous solution of nitric acid was used. This etchant gave a brown color to the a-manganese phase, whereas the o phase was virtually unattacked and appeared very light as shown in Fig. 1. The etchants used by Cornelius et a1.l were found to produce spurious effects in some of these alloys. In particular, the vanadium-rich alloys etched in hot sulfuric acid often appeared to consist of two phases when both X-ray diffraction and etching with the glycerine-acid mixture indicated the presence of single phase bcc solid solution. A few percent of what appears to be an oxide or nitride phase was found at the grain boundaries and in the interior of the grains, especially in the vanadium-rich alloys. All alloys were annealed in sealed silica tubes containing 1 atm of pure argon and these tubes were then quenched in cold water. Although some manganese loss occurred during annealing, the loss seemed to be confined to the surface of the speci-

Jan 1, 1962

By E. N. Doyle

Since the mid-1930's a number of plants, using the principles of heavy media separation, have been installed throughout the world. In cases involving lead, zinc or lead-zinc ores the reasons for the choice of this type of beneficiation process have fallen into four major categories: A) The economic recovery of additional distinctly separate products, such as dolomite limestone at the Mascot Plant (1) of the American Zinc Co., and the ferrosilicon produced by St. Joseph Lead Company. (2) B) The elimination of a large portion of run-of-the-mine ore prior to grinding and flotation, to allow increased throughput with low capital cost. Examples of this approach are the Levante and Ponente plants of the Montevecchio Company in Italy (3) and the frequent choice of the Sink-Float process by the Penarroya Company of Paris. C) The processing of a sedimentary deposit, in which the valuable mineral is contained in the matrix separating the boulders, as was the case at the St. Joseph Lead Company plant at Haydon Creek (4) and also at Bunker Hill Mining and Smelting, Kellogg, Idaho. D) The simplification of Around support programs in mines by allowing greater freedom of action in the extractive pattern. An example of this choice is Cominco’s Sullivan plant which came into being as part of an extensive proposal to update the mining, crushing, transportation, grinding and beneficiation processes. (5)

Jan 1, 1970

It is claimed that the first mining of copper by Americans in Arizona was done at Ajo, near the Mexican border, in 1854,* a year after this region had been added to the United States, under the terms of the Gadsden purchase. A group of adventurers, organized at Los Angeles under the name of the Arizona Mining & Trading Company, came, to the district. This party of prospectors consisted of 20 men, led by Major B. Allen, J. D. Wilson, and William Blanding. † They went first to Yuma, where the party divided, some of them going southward into Mexico while the remainder took the trail to Tinaja Alta, where they heard of the copper deposits of Ajo, which is 85 miles southeast from Yuma.‡ They found attractive outcrops of copper ore, and set to work energetically, but their operations suffered many interruptions, because that part of the country was still controlled by the Mexicans, who were uncertain about the exact position of the new international boundary. The Mexicans tried to expel them, but they held their ground. The first shipment of ore, consisting of native copper and cuprite, came from what is now the western end of of the New Cornelia workings; it was hauled in ox-carts to San Diego, 400 miles across the desert. § Later shipments were hauled to Yuma and floated on barges down the Colorado river to the Gulf of California, whence the ore was loaded on

Jan 1, 1932

By R. T. Mishler

I wish to express my keen appreciation of the article on the above subject by Coe and C1evenger.l It has been doubly interesting to me, for the reason that the experience recorded and the principles evolved practically parallel the results of similar investigations made by myself and others at The Lucky Tiger Mine, El Tigre, Sonora, Mex. An outline of the work at El Tigre may aid in confirming the principles expressed by Coe and Clevenger. El Tigre has the unenviable distinction of possessing a slime with a much lower settling rate than any recorded in the article discussed. Under most favorable conditions the settling rate is about one-third that reported for the Liberty Bell mill, and one-tenth that reported for the Nipissing, Golden Cycle, and Presidio mills. This slow settling characteristic of Tigre ore has necessitated careful investigation of settling phenomena throughout the various evolutions of the plant. Previous Settling Investigation at Tigre During construction work at the mill, the metallurgical engineer in charge, D. L. H. Forbes, ran a series of experiments on settling. His tests proved that deep settling tanks were not ordinarily necessary. The use of tanks 2 or 3 ft. in depth was suggested.2 Later experiments demonstrated that the following principles of settling applied to Tigre pulp.3 1. In settling dilute pulp, settling rates are independent of pulp depth. 2. In settling thick pulp, settling rates are approximately proportional to pulp depth.4

Jan 1, 1918

The income of the Institute is derived mainly from dues, advertising in MINING AND METALLURGY and sale of publications. These sources fortunately are supplemented by the interest from invested funds now amounting to over $500,000, a considerable portion constituting endowments for special purposes. Aside from the medal funds the principal endowments are the James Douglas Fund for support of the Library, the Charles Hayden Memorial Fund, designated to further the education of Student Associates, the Rocky Mountain Fund, and the Seeley W. Mudd Memorial Fund. The income from the two last named is available for the support of research and a variety of other purposes. It is allocated by the Board of Directors upon recommendation of standing committees in each case. An active effort is being made to increase the endowment funds of the Institute through a standing, committee, of which H. T. Hamilton is chairman, and of which the other members are: W. H. Aldridge, George D. Barron, Cleveland E. Dodge, Henry Krumb and J. V. W. Reynders. This committee feels that there exists a tremendous opportunity for the Institute to be of ever-growing service to the public, to the mineral industries, and to the profession. It welcomes suggestions as to names of men of means who are vitally interested in the mineral industries, and to whom the opportunity to make a contribution or bequest might appeal favorably if presented in the proper light by the committee.

Jan 1, 1940

By J. W. Gwinn

THE underground haulage system in the lead-silver mine of the-Bunker Hill & Sullivan Co., situated at Kellogg, Idaho, is the most extensive in the Coeur d'Alène district, comprising about 35,000 ft. of tunnels, drifts, and cross-cuts where locomotive haulage is in use. The main working adit, known as the Kellogg tunnel, or No. 9 level, is approximately 10,000 ft. in length from the portal to the main working shaft and extends beyond that about 4,500 ft. in each of two directions. On this level all the ore from the Bunker Hill & Sullivan, the Sierra Nevada Consolidated, and the Caledonia Mining Co. an average of 44,600 tons per month-is hauled to the mills, located a short distance from the portal. Electric haulage by the trolley-type locomotive is used on this level throughout. Below this level, at intervals of 200 ft. vertically, are five other working levels (Nos. 10, 11, 12, 13, and 14); and the total haulage distance on these, where electric locomotives are used, is approximately 16,000 ft. No. 13 level has but recently been opened up and is not working-to capacity; while the main cross-cut on No. 14 has just been started, and has no need of power haulage. Of the four levels equipped with electric haulage, Nos. 11, 12, and 13 have storage-battery locomotives, and No. 10 still retains the trolley type by reason of the small and decreasing tonnage produced.

Jan 2, 1915

By R. T. Mishler

I WISH to express my keen appreciation of the article on the above subject by Coe and Clevenger.1 It has been doubly interesting to me, for the reason that the experience recorded and the principles evolved practically parallel the results of similar investigations made by myself and others at The Lucky Tiger Mine, El Tigre, Sonora, Mex. An outline of the work at El Tigre may aid in confirming the principles expressed by Coe and Clevenger. El Tigre has the unenviable distinction of possessing a slime with a much lower settling rate than any recorded in the article discussed. Under most favorable conditions the settling rate is about one-third that reported for the Liberty Bell mill, and one-tenth that reported for the Nipissing, Golden Cycle, and Presidio mills. This slow settling characteristic of Tigre ore has necessitated careful investigation of settling phenomena throughout the various evolutions of the plant. PREVIOUS SETTLING INVESTIGATION AT TIGRE During construction work at the mill, the Metallurgical Engineer in charge, D. L. H. Forbes, ran a series of experiments on settling. His tests proved that deep settling tanks were not ordinarily necessary. The use of tanks 2 or 3 ft. in depth was suggested.2 Later experiments demonstrated that the following principles of settling applied to Tigre pulp.3 1. In settling dilute pulp, settling rates are independent of pulp depth. 2. In settling thick pulp, settling rates are approximately proportional to pulp depth.4

Jan 3, 1917

By Sidney Fischler

Large striation-free single crystals of bismuth have been grown from the melt by rapid freezing. Zone-refined bismuth, together with doping impurities if desired, is placed in a shallow flat-bottomed graphite boat and melted in air with a propane hand torch. The torch is then withdrawn in a manner which causes the melt to freeze direction-ally. Crystallization, which resuires only a few minutes, usually results in the formation of a single crystal even when a seed crystal is not used. Crys -tals of any desired orientation may be grown by using oriented seeds. Undoped crystals grown by this method have residual resistivity ratios greater than 200. THE growth of large single crystals of bismuth by either the Czochralski or horizontal zoning technique is not entirely satisfactory. Specifically, difficulties are encountered in producing single crystals of the required dimensions in all desired orientations, and striations caused by low-angle polysynthetic twins are frequently present in the crystals. In addition, both methods are time-consuming and require special apparatus of some complexity. A simpler method has now been developed for growing large striation-free bismuth single crystals of desired orientation in a short time. Fig. 1 shows a typical setup consisting of a rectangular graphite boat which contains zone-refined bismuth, a 1/8-in.-thick flat quartz plate which covers the entire inner bottom of the boat, and three additional quartz plates about 1/4 in. thick which are used to separate the bismuth from the graphite everywhere except at a small area at the left of the boat. The graphite boat is 1 in. high, and its sides and bottom are about 1/8 in. thick. The quartz plates should be smooth and clean. The graphite boat is heated from the right with a propane torch, as shown in Fig. 1, until the bismuth is completely melted. The melt has the shape of a triangle with a narrow neck at the apex farthest from the torch. The melt is frozen direc-tionally by gradually moving the torch toward the right, away from the boat. The bismuth in contact with the graphite, at the left end of the neck, freezes first. The freezing interface then moves down the neck into the main bulk of material, where it develops a convex shape ideal for the continuation of single-crystal growth. The interface continues to move through the melt until the entire bulk is solid. The entire procedure may be completed, in air, in a matter of minutes. The technique described almost always yields a single crystal whose basal plane is nearly perpendi,cular to the bottom of the graphite boat. In earlier experiments, in which the bottom of the melt was in direct contact with the graphite boat, single crystals were grown with basal planes parallel, perpendicular, or at some intermediate angle to the bottom of the boat. At times the orientation of the bulk of the material differed from the orientation of the material in the narrow neck. In these cases, a nucleation site initiated the growth of a differently oriented crystal, and the thermal conditions favored the new orientation over the initial one. The thermal conditions depend on a number of factors, including the heating technique, the placement, shape, and thickness of the quartz plates, the thickness of the walls and bottom of the graphite boat, and the quantity of bulk bismuth employed. All of these factors, plus the initial orientation and the presence and effectiveness of nucleation sites, will determine the orientation of the final large single-crystal slab. When a crystal of specific orientation is desired, an oriented section of a rapid-freeze crystal is shaped by spark cutting and grinding for use as a seed. To grow a doped crystal, the desired impurity is placed in the graphite boat together with the bismuth chunks and seed. Crystals doped with mercury, cadmium, lead, and selenium have been grown. The rate of freezing is so great that the distribution coefficient of any impurity approximates unity. On a gross scale, therefore, impurities should be more homogeneously distributed in rapid-freeze crystals than in Czochralski or zoned crystals. Because of the possibility of constitutional supercooling, however, it is quite possible that impurities are not homogeneously distributed on a microscopic scale in the rapid-freeze crystals. Generally the single crystal slabs which have been prepared are initially 5 to 7 mm thick. Thicker crystals may be obtained by using one of these slabs as a seed. The slab is placed in a graphite boat resting on a large aluminum block, either air- or

Jan 1, 1964

By Leonard Klein

Reduction of oxygen-containing copper has always heretofore been brought about with wood poles. This paper reveals the first successful, economical, and Practical substitute for poles: a gaseous reductant, of which the production and plant use are detailed herein. THE art of fire refining of copper, consisting of melting, oxidation, slag removal, and finally reduction with wood poles, has been practiced for many centuries. An authentic record, discussed in detail in De Re Metallica,* mentions that as early as 1200 A.D. workers in this field of metallurgy were already acquainted with and practiced the basic principles of copper purification. Undoubtedly, the art was well developed marly centuries before the first written records began to appear. Notwithstanding the many advantages gained by application of mechanical con. trivances and by the tremendous increase in size of operations over the centuries, the reduction phase of the process has persisted essentially the same to the present time except for a very recent breakthrough. Numerous articles have been published and many patents have been issued on the subject of substitutes for wood poling in the past half century. They have dealt with a variety of gaseous, solid, and liquid reducing agents. But to the knowledge of the writer, no procedure has ever been prosecuted to a complete success on a large operating plant scale with the single exception of gaseous reduction of oxygen-containing copper revealed in detail herein. A natural gas-air reformer with ample capacity for

Jan 1, 1962

By P. H. Royster

IN a study of the blast-furnace process, the Bureau of Mines has made many experiments for the purpose of determining the exact nature of the combustion of coke in the neighborhood of the tuyeres. Two papers1 presented at a meeting of this Institute discussed somewhat the practical aspects of coke combustibility in its relation to the operation of the blast furnace. In a later paper,2 Sherman and Kinney discussed the possible effect of variations in the combustibility of cokes on the furnace operation, and find that the "reoxidation theory" of Koppers and the "heat concentration theory" of Brassert3 are insufficient to explain the variation in the conduct of different cokes that has been observed by furnace operators. In their report to the D-5 Committee of the American Society for Testing Materials, with which the Bureau of Mines has been cooperating, Perrott and Fieldner4 seem to agree with Sherman and Kinney that, for practical purposes, the nature of the combustion of coke at the tuyeres of any furnace is constant and is affected neither by the physical properties of the coke nor by the nature of the furnace operation. They omit as unimportant any tests on the combustibility of coke from their proposed methods for standard tests on coke. In the last two papers, it is pointed out that performance tests, in which all other factors except coke quality are kept constant, are to be desired and

Jan 3, 1924

By Irving B. Cadoff, Ernest Levine

The crack formation and propagation in the single -phase Cu-4 pct Ag alloys were studied. The alloys were loaded in mercury to various stress levels, the mercury was removed, and the specimen examined for cracks. Cracks were found to develop below the fracture stress; the frequency of such cracks increased with increasing stress level. Some cracks were nmpropagative. Fracture in mercury was found to occur by the link-up of cracks formed at various stress levels rather than by the growth and propagation of a single crack. If the mercury environment is removed prior to a critical amount of crack formation, then continued loading results in ductile fracture. The appearance of the cracks at selected grain boundaries is related to the relative orientation of the boundaries, as are the propaga-tive characteristics of the crack. The mercury interaction appears to be one of lowering the strength of the metal-metal bonds in the high-stress area of the grain boundary. GRIFFITH'S microcrack theory1 proposed a critical crack size above which a crack in an elastic material grows with decreasing energy at a stress of From his theory it was proposed that the presence of a liquid tends to lower the surface energy of the microcrack faces2 leading to a decrease in the critical crack size necessary for spontaneous fracture propagation. stroh3 proposed that the stress concentration at a grain boundary due to pile-up may initiate a microcrack at the grain boundary. petch4 and Stroh5 evaluated the stress distribution at the head of a pile-up in a polycrystal-line material and deduced that the critical crack size and hence of is dependent on the grain size. Experimental verification of this dependence was found by petch6 for hydrogen embrittlement of steel. Studies in stress-corrosion cracking7 have provided a picture of fracture which shows that initial separations occur in a scattered, independent fashion in regions of high tensile stress. A minimum or threshold stress is necessary to produce a sufficient stress concentration to initiate frac- ture. These separations join up to form a crack. The extension of fracture is largely discontinuous and consists of a joining up of cracks. In recent worka evidence of this scattered crack network was found in a Cu-Ag alloy embrittled by mercury. For the Cu alloy-Hg couple, the crack path has also been found to be dependent on the orientation of adjacent grains, and with the addition of zinc to mercury a reduction in embrittlement along with a change in fracture morphology was found.9 In this present study, a mercury-dewetting method was used to observe crack initiation and fracture morphology when a Cu-4 pct Ag alloy is deformed in mercury and Hg-Zn solutions. PROCEDURE Specimens of Cu-4 pct Ag were prepared as in previous crack-path studies.' The specimens were heated at 770°C for 24 hr and water-quenched Tension tests using a table-model Instron were carried out in mercury and in various concentrations of Hg-Zn. Loading was in steps up to the fracture stress, with the load being removed and the specimen examined for surface cracks at each step. The specimens were dewetted after each load to permit examination of the surface structure and rewetted prior to continued loading. The specimens were wetted by electro polish ing in phosphoric acid, rinsing in alcohol, and then immersing in a pool of mercury. Dewetting was accomplished by flame heating the specimen for 30 sec in a vacuum. Some surface contamination was found, but not enough to obscure crack configurations and grain boundaries. RESULTS Fracture Characteristics in Mercury. Fig. 1 is a stress-strain curve showing the progressive step-wise loading of the specimen. As may be seen from the graph, the first position stopped at a is at a stress 5000 psi below the expected fracture stress of 25,000 psi. Examination of the specimen after removal of mercury showed only one crack. The appearance of this crack at a stress far below the fracture stress of this alloy in mercury did not affect the stress-strain curve in any manner. The specimen was then recoated with mercury and deformation was continued (curve b, Fig. 1) raising the stress by 4000 psi, and the same procedure re~eated. The initial crack was located and appeared as in Fig. 2 (crack lb). In this figure the crack is

Jan 1, 1964

By Frank Nicholson

Copper ore was first noticed in Ste. Genevieve County in 1563. The diswvery mas made by a German farmer named Simon Grass, who had occasion to make a road from his farm down the hill into the neighboring valley, and while so engaged noticed pieces of a green-colored mineral, some of which he collected. Not knowing the character of the ore he had found, and supposing it to be valua ble for its brilliant green color only, he carried a piece with him into the town of Ste. Genevieve and showed it around the various bar rooms as a curiosity. No special attention was paid to the matter until nine years later, when Mr. 0. D. Harris sent a specimen of the ore to Dr. Theodore Fay, of St. Louis, for analysis. This analysis, which was the first ever made of Ste. Genevieve copper ore, showed the specimen to contain : Copper,. .........17.75 per cent. Zinc,..........3.21 " Iron........... 24.50 " Sulphur ..........1.09 " Organic matter, silica, carbon, and oxygen,. .. 53.45 " 100.00 " From this analysis it is evident that the sample was taken from near the surface, and was probably recognized by its green color. The almost entire absence of sulphur proves it to be an oxidized form. There is on file, at the office of the Ste. Genevieve Copper Works, a paper* giving three arsays of the ore made in 1875 by Henry B.

Jan 1, 1882

By P. H. Royster, T. L. Joseph

In a study of the blast-furnace process, the Bureau of Mines has made many experiments for the purpose of determining the exact nature of the combustion of coke in the neighborhood of the tuyeres. Two papers1 presented at a meeting of this Institute discussed somewhat the practical aspects of coke combustibility in its relation to the operation of the blast furnace. In a later paper,2 Sherman and Kinney discussed the possible effect of variations in the combustibility of cokes on the furnace operation, and find that the "reoxidation theory" of Koppers and the "heat concentration theory" of Brassert³ are insuffcient to explain the variation in the conduct of different cokes that has been observed by furnace operators. In their report to the D-5 Committee of the American Society for Testing Materials, with which the Bureau of Mines has been cooperating, Perrott and Fieldner4 seem to agree with Sherman and Kinney that, for practical purposes, the nature of the combustion of coke at the tuyeres of any furnace is constant and is affected neither by the physical properties of the coke nor by the nature of the furnace operation. They omit as unimportant any tests on the combustibility of coke from their proposed methods for standard tests on coke. In the last two papers, it is pointed out that performance tests, in which all other factors except coke quality are kept constant, are to be desired and

Jan 1, 1924

By E. J. Roberts

Prior to 1916, thickening was an art, and any accurate decision as to what size of machine to install to handle a given tonnage of a specific ore must have been one of those intuitive conclusions, based on both intimate and extensive acquaintance with thick-ners and ore pulps. Then in 1916 "knowledge of acquaintance," became "knowledge about" with the publication of the Coe and Clevenger paper.' The unit operation of thickening had graduated to the status of an engineering science. The fundamental similitude relationships for the two major phases of the operation were defined so clearly that batch tests on models as small as liter cylinders could serve to specify protypes as large as 325 ft in diameter. It is quite apparent from reading the literature that Coe and Clevenger's contribution is not generally appreciated. In so far as the basic engineering relationships are concerned, the only real advance which has occurred in the 30 odd years which have elapsed since the Coe and Clevenger paper is the recognition of the effect of the rakes on the thickening process. Bull and Darby2 noted this in 1926, and the extensive use of the "gluten type" thickener, in which the effect is magni-fied, bears witness to its importance. Comings3 further verified this effect of the rakes. As a matter of fact, a number of papers show an apparent regression from the Coe paper in that the area determinations are made on the basis of a single test from One concentration of solids. Coe and Clevenger amply demonstrated that this is unsafe, since the controlling zone may be one other than that of the feed dilution. Comings3 neatly demonstrated this without apparently realizing it. Of course there have been significant advances in the application of the operation to industry. Open tray thickeners were introduced to save area; balanced tray thickeners, washing thickeners, and multifeed clarifiers were developed with all of their special hydraulic and mechanical problems. Combinations of all kinds have been introduced, such as combination agitators and thickeners, combination flocculators and clarifiers, combination thickeners and filters. With the establishment of the operation on a firm engineering foundation, installation was facilitated and expansion proceeded. There are still problems, of course, functional as well as mechanical. Sometimes the moisture in the underflow obtained in practice is not as low as is expected on the basis of the test data. Sometimes the underflow is so "thick " that its discharge and subsequent handling requires special attention. Island formation plagues some operators. The use of the thickener as a surge basin and blending tank in the cement industry poses unusual problems. Design of rakes and the drive mechanism must be continually im-proved. Corrosion problems must he overcome. Power requirements for raking the settled solids occasionally is the controlling factor as it was in the case of the all American Canal desilting installation. Other similitude relationships and design problems come into the picture when we enter the field of clarification or nonline settlement. We have an energy dissipation problem in introducing the feed and any models must satisfy the Froude model relationships. Autoflocculation requires detention which involves the same similitude laws that we encounter in the compression zone. Approach to an Exact Science The next step beyond having control of the similitude relationships is to understand the why of these relationships right back up the line to first principles. The ultimate might be that, if given the mineralogical composition of the solids and their size distribution together with an analysis of the suspending liquid, we could calculate the entire thickening behavior of the system. Then we could say we had reduced the operation to an exact science. True it might be more trouble getting this basic analytical data than to make our empirical determinations for area and volume, and we would need an ENIAC to calculate the results, but that does not detract from the desirability of such understanding. Considerable work has been done by the chemical engineers with this end in view. Comings,3 Egolf,4 Work,5 Kam-mermeyer,6 Steinour,7 and others have studied the problem. The writer has no final answer to the thickening story but would like to propose a picture of the mechanics of the two phases of thickening which has been found useful in understanding the subject and which leads to some convenient relationship in treating the compression step and arriving at the compression depth.

Jan 1, 1950