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By N. J. Grant, D. S. Bloom

N recent reports, Sully' and Beck and coworkers' I have advanced hypotheses concerning the formation of the phase. Both of these hypotheses are based on Pauling's theories of the electronic configuration of the elements of the first transition group. Sully considered that the number of electrons which can be absorbed in filling electron "holes" is the factor which determines whether or not the structure can form. Beck suggested that the presence of a certain concentration of electron "holes" is the controlling value. It can be shown that a similar criterion can be developed without making reference to Pauling's theories. Table I shows the elements of the first transition group and the incidence of the a structure in the binary systems of these elements according to the data presently available. Also appended is the number of electrons considered to exist in the 3d-4s levels of these elements. If the atomic percentages for the phase are listed as shown in Table 11, and if the number of electrons in the 3d-4s levels per atom is calculated for the a boundary values, the results are as shown in the last column. It can be seen that the numerical values are all in the vicinity of 7 electrons per atom. This is true also for the ternary Cr-Mo-Ni IT phase, which occurs in a system in which none of the binary compositions are known to develop the phase. In the Fe-Mo binary, the high temperature a phase, which occurs at a composition of 50 atomic pct of each element, also yields a ,;1 e of 7 electrons per atom. From inspection of Tables I and 11, it develops that any series of sequential numbers which is assigned to the elements under consideration will result in the numbers pertaining to a compositions grouping themselves around one specific number. It does not follow, however, that this random number necessarily has physical significance. Such a point has already been discussed by Hume-Rothery." One interesting point develops from this study, however, and that is the position of manganese with reference to the other elements and to the phase. In the system used here, the formation of phase is associated approximately with the value of 7 electrons per atom, which is also the number of electrons per atom that manganese has. Manganese, it will be recalled, exists in three different crystal forms, none of which are the usual, simpler metallic forms; on the other hand, elements just to the left of manganese (in Table I) generally have lower coordination-number structures (body-centered cubic) than do elements to the right of manganese (face-centered cubic). The contribution to a complex crystal structure by the interalloying of elements from opposite sides of manganese is significant in that the a phase is formed in binary systems including one element from each side of manganese, with manganese capable of participating with both sides. It is indeed an interesting coincidence that manganese, with 7 electrons per atom, solidifies in complex crystal forms, and that when alloys of the transition elements are made which have seven 3d-4s electrons per atom, they, too, tend to assume a complex crystal form. From the above, it might be deduced that the study of the a phase might be advanced by a critical examination of the element manganese and how its structure is affected by small additions of elements which change the 3d-4s electrons per atom number. The role of atom size would also be of interest in formation. References ' A. H. Sully: The Sigma Phase in Binary Alloys of the Transition Elements. Journal Inst. Metals (1951) 80, Part 4, p. 173. 2 S. Rideout, W. D. Manly, E. L. Kamen, B. S. Lement, and P. A. Beck: Intermediate Phases in Ternary Alloy Systems of Transition Elements. Trans. AIME (1951) 191, p. 872; Journal of Metals (October 1951). "W. Hume-Rothery, H. M. Irving, and R. J. P. Williams: The Valencies of the Transition Elements in the Metallic State. Proc. Royal Soc. (September 1951) 208A. p. 431.

Jan 1, 1954

By F. Weinberg

The relative concentration of 1" at grain boundaries in controlled orientation bicrystals has been examined by autoradiographic techniques, and by activity measurements of grain boundary surfaces exposed by preferential ,melting. The autoradio-graphs indicate that thallium is concentrated at grain boundaries in as-grown bicrystals, but not in zcell-annealed bicrystals. They also indicate that the solute concentration and the distribution on as-grown bicrystal surfaces are markedly different than that of the bulk material. The boundary surface measurements are in agreement with the autovadiographic evidence. On the basis of these measurements, as-grown bicrystals containing approximately 100 ppm of Tl, solidified at rates between 5 and 30 cm per hr and with tilt boundaries greater than 10 deg, exhibited grain boundary segregation equivalent to roughly 10 atomic planes of pure solute. Higher solute concentrations (equivalent to 140 atomic planes of pure solute) were obtained in bicrystals solidified slowly (0.6 cm per hr); slightly higher values were obtained in specimens containing a large angle nantilt boundary. Annealing for various times over a range of temperatures eliminated grain boundary segregation within the experimental uncertainty of the results (equivalent to 1 atomic Plane of pure thallium at the boundary). The results for the as-grown bicrystals can be qualitatively accounted for by assuming the presence of a groove on the solid-1iq;id interface, at the grain boundary. SOLUTE segregation at grain boundaries may be considered in two parts, namely, nonequilibrium segregation associated with the solidification process, and equilibrium segregation in fully annealed materials.' There is much indirect evidence for nonequilibrium segregation, based on preferential etching at grain boundaries and the mechanical properties of as-cast alloys. In addition, some direct observations have been reported in which radioactive tracers were used as solute additions and segregation detected at the grain boundaries by autoradiographic techniques. However, there is little detailed quantitative data on solute concentrations related to grain boundaries, particularly for different freezing conditions and grain boundary configurations. Equilibrium segregation at grain boundaries has been considered both theoretically and experimentally. cean' has made an estimate of the maximum equilibrium solute concentration that might be expected at a grain boundary, based on the lattice distortions in the boundary region. He arrived at a concentration which was equivalent t a monatomic layer of pure solute. A similar value, based on thermodynamic arguments, was calculated by Cahn and Hilliard for the segregation of phosphorus in iron. Experimentally, much higher values of solute concentration at grain boundaries have been reported recently by both Inman and iler' for phosphorus in iron, and Ainslie et 1.' for sulfur in iron. They observed concentrations equivalent to as much as 20 to 100 atomic layers of pure solute at the grain boundaries. However, in both cases it was shown that the observed segregation was not due solely to equilibrium segregation at the grain boundary. In the former case, precipitation effectss due to trace impurities in the material were believed to account for the large amount of solute present at the grain boundary. In the latter case it was shown that a high density of dislocations in the boundary region could provide a large number of additional sites for solute atoms, other than at the grain boundary. Thomas and chalmera have reported on the equilibrium segregation of po210 in grain boundaries of Pb-5 pct Bi alloys. Using autoradiographic techniques, they observed a concentration of polonium along the boundary trace on the surface of annealed bicrystal specimens grown from the melt. The concentration only appeared after annealing, and varied with boundary angle, increasing as the boundary angle increased. Their conclusions have been questioned by Ward," who pointed out that the segregation they observed along the boundary trace was much too wide to be compatible with the usual concepts of the thickness of a grain boundary of several lattice spacings. Also, Maroun et al.,l1 with specimens similar to those of Thomas and Chalmers, found that segregation could only be detected on the specimen surface, suggesting that Thomas and Chalmers' results were associated with an oxidation effect of polonium, and not equilibrium segregation. Thomas and Chalmers replied12 that they did observed segregation at the grain boundary in the bulk material and suggested further experiments were necessary to resolve the difference. The purpose of the present investigation was to examine both nonequilibrium and equilibrium grain boundary segregation in melt grown bicrystal specimens as a function of boundary angle, growth rate, and solute concentration, and to de-

Jan 1, 1963

By M. E. Wadsworth, I. B. Cutler

Coprecipitation of anionic and cationic polyelectrolytes has been applied to floccula-tion of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves. DISPERSION of colloids has been of interest to surface chemists for many years. Flocculation studies have been employed to evaluate the limits of colloid stability. In water suspensions, colloids become unstable and flocculate when the ( potential, the potential of the kinetic solvation sheath, falls to a value at which van der Waals forces may act to draw the particles together. This may happen through an adjustment of the pH of the suspension or by addition of a salt. Optimum conditions for rapid formation of large flocs are found in the region of minimum ( potential. In addition to these well known considerations, colloids in water suspensions are known to be flocculated by certain large organic macromolecules. These polyelectrolytes in some cases minimize the i potential and in other instances increase the attractive forces by supplying sites for hydrogen bonding.' Use of organic polyelectrolytes in flocculation of mineral colloids has increased rapidly in recent years. These materials are now recognized as indispensable aids to fluid-solid separations in many extractive metallurgical operations. They have been found to increase both the settling rate in thickeners and the filtration rate of filters. In the elucidation of the characteristics of these organic reagents as floc-culants in this laboratory, it was discovered that interaction of certain polyelectrolytes had a surprisingly good effect on flocculation of mineral colloids. Experimental Procedure: The anionic flocculants used in this study were Lytron 886 and 887, produced by Monsanto Chemical Co. Both reagents are copolymers of vinyl acetate and maleic anhydride. Lime is added to Lytron 886, whereas Lytron 887 is all organic. These reagents possess two carboxyl groups for each acetate group and are therefore anionic in character. The cationic reagents used were the Peter Cooper Co. 1-X and 2-X glues. The structures are not definitely known, but the re- agents are amines and are cationic in character. The glues were prepared in the chrome-alum form. Both types of reagents may be classified as polyelectrolytes in that they are high molecular weight polymers and ionize in water. All data presented are in terms of sedimentation rate, measured in 250-ml glass-stoppered graduated cylinders. With suitable precautions such measurements are fairly reproducible and provide a sensitive means for selecting important parameters such as pH, reagent concentration, and floc size and density.2 Agitation was standardized with five complete end over end cycles of the suspensions in the stoppered graduated cylinders.

Jan 1, 1957

By I. R. Kramer

The apparent activation energy, U, JOY plastic deformation of aluminium, copper, and gold single crystals and polycrystalline aluminum was found to he dependent upon surface condition. At low strains, the value for U for aluminum single crystals was 4200 cal per mole ; however, this value decreased to 920 cal per mole when the specimens were polished during the test at a rate of 50 X 10-5 win-1 The activated volume also was found to increase with the rate of metal removal. That the surface plays an important role in plastic-deformation processes has been adequately demonstrated.1-4 Of particular interest at this time are the observations4 that the creep rate of single crystals of fee metals is increased markedly when specimens are polished during the deformation process. These observations were interpreted in terms of a dislocation debris layer at the surface regions of the crystal. This layer, which appears to be a region containing a high concentration of dislocations or segments of dislocations, not only will impede the egress of dislocations on the primary slip system, but will also provide a barrier against which dislocations may pile up. By this means, a stress which opposes the motion of dislocations will be generated. It is considered that this stress must be taken into account in any theory which describes the plastic-deformation process. Although a detailed dislocation model cannot be given at this time, it may be stated that the stresses opposing the motion of dislocations arise from the dislocations in the debris layer, Ts, and ti due to the resistance to motion imposed by internal obstacles such as Lomer-Cottrell barriers, subgrain and grain boundaries, forest dislocations, and so forth, as well as the resistance due to the presence of jogs on dislocations and the interaction of the stress fields of dislocations, and so forth. In essence, we have added an additional term, ts, to the usual form of the equation T = Ta- Tb, where Tb is the back stress due to the various types of obstacles which impede the motion of dislocation. Accordingly, the net stress, t, acting on a dislocation may be written as where Ta is the applied shear stress. For deformation which occurs by a thermally activated process5,8 ?=Ae-u/kT = A e(u,-VT)/kT [2] and U = Uo- Vt PI where U = activation energy for plastic flow, y = shear strain rate, Uo = activated energy for plastic deformation in the absence of stress and depends upon the particular deformation process, V = activated volume, k = Boltzmann constant, T = temperature, OK, and A = frequency factor. From Eqs. [I] and [3], U = Uo- V(Ta - Ti - TS) [4] and it is seen that if Ts decreases, the activation energy, U, must decrease if V remains constant. However, as will be shown, V is a function of the surface conditions. In their work on aluminum, Lytton and coworkers7 reported that at low strains the activation energy was 3400 cal per mole and at high strains it was 28,000 cal per mole. The lower value was interpreted in terms of the energy necessary to overcome the Peierls force, while the higher value was associated with the energy necessary for dislocations to move by a cross-slip process. It will be shown that the lower activation energy is associated with the surface debris layer rather than with the Peierls force. EXPERIMENTAL PROCEDURE Single crystals having a nominal cross section of 1/8 in. and a 3-in. gage length were prepared by a modified Bridgman technique using a multiple-cavity graphite mold. The initial purity of the metals was 99.997, 99.999, and 99.999 pet for aluminum, copper, and gold, respectively. The orientation of the specimens is given in Fig. 1. The measurement of the activation energy as a

Jan 1, 1964

By Jack Parker

The White Pine mine site lies five miles south of Lake Superior in Ontonagon County, Mich. Copper sulfide, mixed with some native copper, is mined by a room-and-pillar system from gently dipping Upper Kewee-nawan sediments. Depth of mining now varies from 700 to 1800 ft and the ore body continues to a depth of at least 3400 ft. An area roughly 21/2 miles square has already been mined. Mining height has varied from 61/2 to 22 ft. A rock mechanics program was set up in late 1963 to promote safety and mining efficiency. This note reports some of the findings. Rock Strength Compressive strength of small, dry specimens of sandstones, siltstones, and shales from the ore zone varies from 20,000 to 30,000 psi. This is intermediate between the softer coal mine sediments and the meta-morphic and igneous rocks of hard rock mines. Annual Cycle of Rock Failure Since 1963, every roof and pillar failure involving more than a few tons of rock has been examined and documented. Some 1500 stations have been installed for measuring convergence, -c1/1000 in., with Invar extensometers. At first it was thought that there was some kind of a cycle of roof failures; perhaps annual, perhaps even elated to the moon or to earth tides, but records (see

Jan 1, 1971

SMELTING is a thing essential to the end for which ores are sought, for without it every ore is a useless stone. This art is especially needed by those who, drawn on by hope, have mined ores in large quantities with great expense and effort. For this reason it is worth while to use one's wits and, if ordinary ways should not suffice, to consider how to find new ways of smelting the ores in order to extract the metals and to purge them of their earthiness. For this reason I shall now tell you of blast and other furnaces, and I shall also tell you, in order that you may be warned, that whoever wishes to do this well must first look at the nature and quality of the ore. You will already have had enlightenment on this from the experiments on assaying and with this as guiding star it is necessary to make ingenious structures and to provide for-the other needs as necessary, for one ore requires iron and another lead. Since I have already spoken of these in their own places on their ores, it is not necessary at present that I repeat, but here I wish to speak only of copper ore as a companion of silver and gold, and of where art is most required and where difficulties chiefly appear. For these things a machine must be built that is convenient to a good water supply in order to continue the work more easily. Its wheels should be large and easily moved, constructed in such a way that the force of the water lifts the bellows that are placed at the tuyère to direct the blast inside the furnaces that are to smelt the ores. For this, attention must first be given to the site of the machine, the quantity of water, and its fall; then to the wood for building the machine and for making charcoal; then to the stones that are used for the blast furnaces; then to the provision of good bellows that are wide, long, and full in their sides and made of cloth, for the better these are, the more they quicken the power of the charcoal

Jan 1, 1942

By Frank Firmstone

In the summer of 1842 my father, William Firmstone, was engaged by Charles Jackson, Jr., of Boston, to examine the conditions in the Lehigh valley as a site for blast-furnaces using anthracite for fuel. In consequence of his report, he was further engaged by Mr. Jackson to build a furnace for him and his partners on the Lehigh canal, 2 miles above the mouth of the river at Easton. Work was begun in the fall of 1842, and the first furnace blown-in in 1844. The history of the works, therefore, from 1844 to 1887, when my own connection with them ceased, covers only four years less than the whole period of the rise, culmination, and commencement of the decline in the smelting of iron with anthracite in America, the beginning of which, in a commercial sense, may be put in 1839.' Although this paper, as the title indicates, is concerned almost exclusively with the furnaces at Glendon, still what was done there was more or less influenced by current opinion in the district, and even reflects, to some extent, the changes in opinion and practice with mineral fuel the world over. No. 1 Furnace was built of red brick, on four piers, had three tuyeres and fore-hearth and tymp, as was universal with furnaces using mineral fuel until the introduction of Lurmann's cinder-tuyere. The dimensions and profile are shown in Figs. 1 and 2. The first hearth (Fig. 1) was of sandstone; all after were of fire-brick (Fig. 2). The profile was no doubt derived directly from Gibbons's furnace,2 for it appears from W. Firmstone's note-books that in October, 1840, he visited " Gibbons' new furnaces building at Corbyn Hall," and I have an old drawing,

Jan 1, 1910

By R. W. Regehr, R. A. Burmeister

Epitaxial growth of GaAs 1-xPx on germanium substrates was achieved using an open tube vapor transport system. The compositional range of 0.3 < x < 0.4 was examined. The best results were obtained with (311) orientation of the germanium substrate. The physical and chemical properties of the resulting layers were investigated using several techniques. Spectrographic analyses of the layers indicate substantial incorporation of germanium into the GaAs t-X Px layer. Evidence is presented which indicates that this incorporation occurs via a vapor phase transport process rather than by solid phase dijfu-sion. Electrical measurements suggest that the germanium thus incorporated behaves predominantly as a deep donor in the compositional range of 0.33 < x * 0.40 and has a deleterious effect upon the luminescent properties of GaAs1-x Px. The increasing technological importance of GaAs1-xPx for use in light-emitting devices has led to an evaluation of several aspects of existing growth processes. The method most commonly used to prepare GaAs1-xPx for electroluminescent device applications is vapor phase epitaxial growth on GaAs substrates.&apos;-4 In a typical electroluminescent diode structure the active region of the diode is entirely within the epitaxial layer and thus the electrical properties of the substrate are relatively unimportant since it is effectively a simple series resistance (assuming hetero-junction effects to be negligible). The use of germanium rather than GaAs as the substrate material is of interest for several reasons. First, GaAs of reasonable structural quality has been epitaxially grown on germanium4-2 and it is reasonable to expect that GaAs1-xPx could subsequently be deposited on the GaAs layer. Second, germanium substrates are readily available with both lower dislocation densities and larger areas than GaAs. Finally, single crystals of germanium are more economical than GaAs single crystals. The principal objective of the present investigation was to test the feasibility of growing GaAs1-xPx epi-taxially on germanium substrates, and to evaluate the properties of such layers with regard to electroluminescent device requirements. The approach used was to a) demonstrate epitaxial growth of GaAs1-xPx on germanium, and b) characterize the relevant structural, electrical, and optical properties of the GaAs1-xPx layers. The possibility of germanium incorporation into the grown layers was of special interest since there was some indication of this in previous studies of GaAs growth on germanium.5&apos;11,12 Although a study of the electrical properties of germanium in GaAs1-xPx was not an intent of this investigation, several features of the electrical properties of the layers grown in the present study which appear to be due to germanium are described. EXPERIMENTAL PROCEDURE The open-tube vapor transport system used for the epitaxial growth of GaAs1-xPx is illustrated in Fig. 1. This system utilizes the GaC1-GaC13 transport reaction and is similar in most respects to the larger system described elsewhere.&apos; The germanium substrates were n-type, with a resistivity of 40 ohm-cm (Eagle-Picher Co.). These were cut to the orientations of {100), {111), and (3111, and were mechanically polished and chemically etched in CP-4 (5 min at 0°C) prior to growth. In some cases, a GaAs substrate was employed in addition to the germanium. The orientation of the latter was {loo}, and they were also mechanically polished and chemically etched prior to growth. The initial composition of the deposited layer was pure GaAs. After approximately 10 microns of GaAs was deposited on the germanium substrate, the phosphorus content of the layer was gradually increased over a distance of approximately 15 microns to the desired concentration and maintained at this value throughout the remainder of the growth. Typical operating parameters used during growth are given in Table I. Selenium was used as a n-type dopant in several runs to facilitate comparison of the electrical properties of the layers grown on germanium with those of layers grown on GaAs substrates, which are usually doped with selenium. The concentration of H2Se in the gas phase was adjusted to a value which would normally yield a carrier density of 1 to 5 x 101 7 at room temperature in layers grown on GaAs substrates. The terminal surfaces of the epitaxial layers were examined by optical microscopy for structural characteristics. Laue back-reflection photographs (Cu radi-ation) were also made on the terminal surface to verify the epitaxial nature of the deposit. After these steps

Jan 1, 1970

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&apos; 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 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 blast-hole 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. Sucti 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, 1953

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 blast-hole 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. Sucti 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, 1953

By G. L. F. Powell

g samples of Cu-20 wt pct Ag alloy have been mdercooled to a maximum of 197°C by melting under a slag of commercial soda-lime glass in a vitreous silica crucible. No grain refinement of the primary copper was observed in samples undercooled to the maximum of 197°C. When the samples contained a small amount of oxygen, the copper dendrites were partially recrystallized at undercoolings greater than 97°C. In previous papers&apos;-3 reporting the grain structure of undercooled silver and copper, it was observed that grain refinement was dependent on both undercooling and oxygen content. Grain refinement occurred in undercooled silver when the degree of undercooling exceeded the range 153" to 175"C, while in Ag-0 alloys (0.12 wt pct) fine equiaxed grains were exhibited when undercooling was greater than 50°C. Similarly, copper samples undercooled as much as 208°C displayed fan-shaped growth from a single nucleation site, while the grain structure of Cu-O alloys (0.08 wt pct) was fine and equiaxed at undercoolings larger than 150°C. Thus the presence of oxygen greatly reduced the undercooling at which grain refinement occurred. It was also observed that the change in grain size resulted from recrystallization and was not due to an enhanced nucleation rate in the liquid-solid transformation. It is possible that the influence of oxygen on recrystallization is due primarily to its presence as a solute element. walker4,&apos; reported that, although a grain size change did not occur in pure nickel until the undercooling exceeded 150°C, small grains were observed in samples of Ni-Cu alloy solidified at small and large degrees of undercooling. Jackson et al.6 suggested that the fine grained structure of the Ni-Cu alloy resulted from the melting off of dendrite arms during recalescence. This remelting process may occur in alloys as a result of segregation during freezing which causes a variation in liquidus temperature from point to point within a dendrite. It was therefore decided to undercool copper with a metallic alloying element to ascertain whether the presence of a metallic solute would have a similar effect to oxygen in inducing grain refinement. A Cu-Ag alloy was chosen, since both metals had been shown to behave similarly on undercooling. The alloy Cu-20 wt pct Ag was selected since the eutectic constituent outlines the initial growth form of the primary copper, so that the as-frozen grain structure is not obscured if subsequent recrystallization occurs. This paper describes the results of undercooling experiments carried out with Cu-20 pct Ag samples undercooled to a maximum of 197°C and the effect of oxygen content on the grain structure of the undercooled samples. EXPERIMENTAL Melting was carried out in a small cylindrical resistance furnace using "fine" silver granulate and oxygen-free high conductivity copper. The procedure adopted was to melt the required quantity of silver in air in a clean vitreous silica crucible for approximately 15 min, freeze, and add granulated commercial soda-lime glass to form a complete surface slag cover, after which the sample was melted and frozen several times to reduce the oxygen content. The glass slag cover was approximately 3 in. thick. Pieces of copper (=50 g) were added to the crucible until the required quantity to make 350-g samples of alloy had been charged. Each piece was added quickly to the crucible which was held at a temperature slightly above the melting point of silver. The piece was quickly pushed beneath the glass to minimize oxidation and any oxide coating usually decomposed before the piece had settled down into the silver. After the full quantity of copper had been added, the melt was stirred with a silica rod to hasten homogenization and a Pt/Pt 13 pct Rh thermocouple enclosed in a vitreous silica sheath inserted for temperature measurement. Heating and cooling curves were recorded on a potentiometric chart recorder fitted with a zero suppression unit. The milli-voltage range of the recorder was adjusted so that temperatures could be read to 1°C. Heating and cooling curves were taken every hour until three consecutive readings gave the same solidus-liquidus range, consistent with the solidus-liquidus range for this alloy composition by reference to Hansen and Anderko.7 Metallographic examination of samples frozen at this stage, failed to show any variation in composition from bottom to top of the ingot. Consequently, it was considered that the melt was homogeneous at this stage and undercooling experiments were then car-

Jan 1, 1970

By Chikaosa Tanimoto

INTRODUCTION The committee on Rock Mechanics, Japanese Society for Civil Engineers, has been discussing &apos;soft rock engineering in Japan&apos; and presented several papers concerning dam, tunnel, bridge and slope constructions to International Symposium on Weak Rock, Tokyo 1981. This is the summarized paper based on References of Okamoto et a1 (1981), Iida et a1 (1981), Working Group on Tunneling-JSCE (1981), Working Group on Bridge Foundations-JSCE (1951) and Kikuchi et a1 (1981), which can convey general view on engineering experiences with weak rocks in Japan. From the point of view to the origin and/or distinctive physical properties, weak rocks in Japan may be classified into (1) sedimentary, (2) weathered, (3) low welded-pyroclastic and (4) fractured ones. Their typical characteristics are summarized in the following section. Concerning dam foundations on soft rock, several hundreds have already been constructed and, at present, nearly one hundred are under construction or at planning stage. These dams, almost without exception, have some problems such as site selection, material selection for fill-type and concrete dams, design of dam and its foundation, and construction procedures, requiring special ingeneous and cautious measures to cope with the local geotechnical difficult situations. In tunneling, for the decade of 1970s, the number of tunnels in soft rock either completed or under construction was at least 160, including Seikan Tunnel of 53.9 km long, Nakayama Tunnel of 14.8 km long and so on. Most of these tunnels are distributed in the northern half of Mainland, consisting of a basement of Paleozoic strata and Plutonic rocks, overlayed by Neogene Tertiary formations which include large

Jan 1, 1982

By R. D. Schoone, J. T. Michalak

Recovery, recrystallization, and texture development of a cold-rolled aluminum-killed steel have been studied during simulated box annealing. Two different initial conditions existed prior to cold rolling: 1) essentially all of the nitrogen in solid solution and 2) most of the nitrogen precipitated as AlN. The combined effect of nitrogen and aluminum in solid solution before annealing was to inhibit recovery and sub-grain growth at temperatures above about 1000°F and to raise the recrystallization temperature range on continuous heating at 40°F per hr from 1000"-1050°F to 1065"-1085°F. For the material with nitrogen and aluminum initially in solution there was an inhibition in the nucleation of the (001) [110] texture component and an enhancement of the (111) [110] texture component. The differences in annealing behavior mzd texture development are attributed to preprecipitation clustering of aluminum and nitrogen at subboundary sites developed by prior cold working. THE annealing of cold-worked aluminum-killed steels has been the subject of numerous investigations.&apos;-&apos;2 These studies have been concerned with kinetics of recrystallization, with microstructure and texture development, and with the individual and combined effects of composition, thermal history prior to cold rolling, and heating rates during subsequent annealing. It has been shown that the inhibition of recrystallization, and the development of the pancake-shaped grain and recrystallization texture characteristic of aluminum-killed steels, can be associated with the precipitation of A1N particles during a recrystallization anneal involving heating rates in the range 20" to 80°F per hr. If the AIN is precipitated before cold rolling or if more rapid heating rates are employed, the cold-rolled steels recrystallize more rapidly to an equiaxed grain structure and texture comparable to that of rimmed low-carbon steel. The retardation of recrystallization, the development of the elongated grain structure, and the pronounced (111) texture have been attributed to: 1) precipitation of A1N at prior cold-worked grain boundaries to form a mechanical barrier to grain boundary migration;&apos; 2) precipitation on the boundaries of the growing recrystal-lizing grains as well as on cold-worked grain boundaries;&apos;" and 3) preprecipitation clustering or precipitation on subboundaries to retard recovery, nucleation, and growth. The present study was undertaken to study in more detail recrystallization and texture development during commercial box annealing of cold-rolled aluminum-killed steels. Comparison of the annealing be- havior after cold rolling, for two different conditions prior to cold rolling, was made in an attempt to define more clearly the role of aluminum and nitrogen in forming the recrystallization texture. A) MATERIAL AND PROCEDURE The material used in this investigation was a commercial low-carbon aluminum-killed steel which was hot-rolled with a finishing temperature of about 1565"F, then coiled at about 1020°F. The composition, in wt pct, was: 0.050 C, 0.30 Mn, 0.007 P, 0.019 Si, 0.03 Cu, 0.02 Ni, 0.02 Cr, 0.045 Al, and 0.004 N. Two 4.5 by 13 by 0.078 in. sections were cut from the center section of a hot-rolled panel and one of these was reheated to provide two different conditions prior to cold rolling: low AlN: as commercially hot-rolled, with aluminum and nitrogen in solid solution; and high AlN: as commercially hot-rolled, then reheated at 1300°F for 3.5 hr to precipitate most of the nitrogen as AlN. ~etallc&a~hic examination indicated that the reheating did not change grain size nor carbide distribution (some spheroidization of pearlite was noted). Texture analysis at half-thickness level showed that both sections had the same substantially random as-hot-rolled texture. The results of check chemical analysis of each sample are given in Table I. Both sections were cold-reduced 65 pct on a laboratory rolling mill to a final thickness of 0.027 in. Cold rolling, in one direction only, was in the direction of the prior hot rolling. Specimens 1.0 by 1.25 in. were cut from the cold-rolled sheets and given a simulated box anneal in an atmosphere of 2 pct HZ-98 pct He. Specimens were heated at a constant rate of 40°F per hr from room temperature to various temperatures in the range 750" to 1300°F and cooled immediately by withdrawal to the water-cooled end of a tube furnace. The temperature in the 6-in. uniform hot zone of the furnace was controlled within 3"F. Selection of the individual specimens was made to give a random distribution of annealing temperatures with respect to location in the cold-rolled sheet. At least two specimens of each condition were annealed to the same temperature and smaller specimens for light microscopy, transmission electron microscopy, and X-ray studies were prepared from each of these. Rolling-plane sections for each of these studies were taken at half thickness. Light microscopy and transmission electron micro-

Jan 1, 1969

By M. J. Hordon, M. A. Wright

The well-defined increase in fatigue life observed o many metals cyclicly strained at vacuum levels below 10-1 to 10-3 torr has been attributed to the critical retardation of oxygen or water vapor chemisorption at the crack tip during crack propagation.1-3 In the absence of strongly adsorbed surface films, crack re-welding during cyclic compression or dislocation escape from the plastic zone around the crack tip has been proposed to account for the observed decrease in the rate of crack growth. The increase in the critical pressure required for the transition in crack growth rate with temperature experimentally determined for aluminum was found to be generally in accord with the adsorption rate model.4 However, although the adsorption mechanism would also predict an increase in transition pressure and fatigue life with increase in cyclic loading rate, and such effects were noted by Snowden5 for lead and Hordon3 for aluminum, the opposite results were reported by Kramer et al.B in studies on aluminum. The present note describes some recent measurements of the fatigue properties of 1100-H14 aluminum at low pressures to determine the specific effect of cyclic strain frequency in the transition pressure range. Flat cantilever-type specimens of 1100-H14 aluminum shaped to produce a uniform strain gradient along the gage length were tested in reverse plane bending at constant deflection amplitudes in two independent multi-specimen vacuum fatigue systems. One series of tests using 2-in. gage length specimens was conducted in an ion pumped apparatus with 107 torr and 50 cps capacity, denoted as Unit I, utilizing fixed mechanical cams to impose the strain amplitude. An independent test series using shorter 1-in. gage length specimens was conducted in a cryopumped apparatus designed for extremely low pressures below 10-10 torr, denoted as Unit II, using an electromechanical vibrator at non-resonant frequencies up to 150 cps to provide the deflection. Both vacuum fatigue units and associated test procedures have been described previously.3&apos;7

Jan 1, 1969

By T. O. Massalski, J. D. Ayers

A massive transformation, 0 —am, takes place in a number of copper-based systems where the ß phase field at high temperatures extends to compositions that are slightly less solute-rich than the limits of the a phase field that exists at lower temperatures. Consequently a solid-state transformation becomes possible that does not involve a change of composition. Within this narrow range of composition the massive am phase can be usually produced in two ways: by a fast quench from the ß phase through the a phase field, or by pulse heating into the a phase field of an undecomposed ß phase retained at room temperature by a prior quench. In the Cu-Ga system the occurrence of a massive am phase has been also observed in alloys whose composition falls outside the equilibrium a phase field1 but not in the Cu-Zn system.2 We have recently observed the occurrence of the ß — am transformation also in two silver-based systems, Ag-Zn and Ag-Cd. The a and 0 phase fields in these systems again slightly "overlap" in a narrow composition range. In the Ag-Zn system this range falls between 36.7 and 40.2 at. pct Zn, and in the Ag-Cd system between approximately 41 and 42.5 at. pct Cd. Alloys were prepared from high-purity materials and cast in quartz tubes under inert atmosphere. No significant change of composition occurred during casting. After homogenizing in the 0 phase field, small pieces of each alloy were reheated at the homogenizing temperatures for a few minutes and quenched into various media. There were examined metallographic-ally after removal of surface layers that may have suffered from contamination or from the loss of the solute element. In the Ag-Zn system extensive areas of the am phase (identified by selective etching, observation of the slip trace variants, and occurrence of twinning) were observed in a comparatively low-zinc alloy (37.8 at. pct Zn) for all quenching media employed: iced

Jan 1, 1969

By Daniel R. Hull

IN 1026 Genders&apos; reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan,3 and by Phillips and Brick,2 so that no resume is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. VAPOR SEGREGATION There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table I, which represents a [ ] cylindrical billet 7 in. in diameter by 5; in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. The lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps up a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By Frank Firmstone

WE found it necessary, in December, 1874, to repair the upper part of the lining in No. 5 furnace at Glendon, and, as we succeeded in doing it with comparatively little trouble, a description of the plan followed may be of service to those having a similar operation to perform. On two opposite sides, as shown by the sketch, the lining was completely gone for a height of about four feet, below which it increased gradually in thickness, being nine inches thick about three feet lower down. On a plane at right angles to the section drawn, the brick were nowhere entirely gone, but were in some places not more than two or three inches thick, being still sufficient to sustain the upper part, where the brick, being above the level of the stock, were not at all worn. The furnace was blown down, so that when we cast and closed the tuyeres, about 7 A.M., on December 8th, the top of the stock was about twenty-four feet below the filling-plates. The walls were quite hot, and a good deal of gas was given off for several hours after the tuyeres were closed. The hopper and bell were thrown into the furnace, and were covered by filling several charges of cold stock over them, which at once greatly cooled off the top of the furnace. A wrought-iron pipe, thirty inches in diameter, in five sections, each six feet long, was then put down, and made to stand upright, as nearly as possible in the centre of the furnace. Around this we filled a double charge of coal, taking care to heap it up next the pipe, and let it get thinner as it got to the walls. This was covered with about two feet of fine ore, leaving the lowest joint in the pipe entirely uncovered. We were now ready to put in our scaffold to get at the

Jan 1, 1876

Alabama.1 Arizona 1 Arkansas 2 California 2 Colorado 7 Connecticut 8 Delaware 9 District of Columbia 9 Florida 10 Georgia 11 Idaho 11 Illinois 11 Indiana 13 Iowa 14 Kansas 14 Kentucky 14 Louisiana 15 Maine 16 Maryland 16

Jan 1, 1952

By Vanderlei Beisiegel, Arthur L. Bernardelli, Arthur W. Ruff, John H. Tremaine

Estimated reserves of high-grade iron ore at Serra dos Carajás total 16 billion metric tons and have an average grade of 66.7 per cent iron, 2.2 per cent combined silica and alumina, and 0.05 per cent phosphorous on a dry basis. Hematite is predominant and no significant sulfur on other deleterious elements are present. Serra dos Carajás is located in northern Brazil, about 550 kilometers southwest of Belém, Pará. It is six degrees south of the equator between the Xingu and Tocantins Rivers. Both rivers flow northward toward the Amazon River. The greater part of the area is covered by thick jungle, and the most practical means of access is by air.

Jan 1, 1974