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By H. J. Rahilly

MINE FIRES, in the Butte District, have been a source of trouble and expense for the past thirty years, for while the actual fire area in most of the mines has been comparatively small, the handling of the gas has generally been a much larger problem than the actual putting out of the fire. The chief causes of these fires have been: Defective electrical equipment, incendiarism or carelessness, and spontaneous combustion. While fires from the first two causes have been numerous, they have generally been discovered and extinguished before they became very serious. Spontaneous combustion has been the cause of most of the large fires. Sufficient heat has been generated by ground movement, high rock temperatures, and decomposition to set fire to inflammable materials (tarred ropes, canvas, dry timber, manure, and hay) left in the gobs some years ago. Also, the heat resulting from the oxidation of the fine broken sulfide ore is sometimes sufficient to set fire to the timbers. In 1906, a fire was discovered on the 1100-ft. level of the Minnie Healy mine about 400 ft. (122 m.) west of the Minnie Healy shaft, which presumably originated, in one of the upper levels, from spontaneous combustion. The fire was walled off by concrete bulkheads and a pillar of ground 100 ft. (30 m.) thick was left below and mining resumed underneath. During subsequent operations, this pillar became cracked and broken and the fire passed into the new workings. It travelled downward and spread rapidly until, in 1917, it had become necessary to wall off portions of the Tramway, Leonard, and West Colusa mines on the 1300, 1400, 1500, 1600, 1800, 1900, and 2000-ft. levels, and the top of the 2200-ft. raises were sealed. The fire area now consists roughly of a block 1000 by 1200 ft. and from the 600-ft. to the 2200-ft. level. This block is composed largely of a series of parallel northwest-southeast nearly vertical veins and stringers that form a large orebody, with no well-defined walls but badly fractured and faulted, and known locally as "Horsetail Ore." These veins, or orebodies, are mined by the square-set or the rill method.

Jan 2, 1922

By F. C. Stanford

The work of an engineer is to direct natural forces so that the: bring about the results that he wishes to secure. Heretofore he ha concerned himself chiefly with physical forces and inanimate objects until he has secured a truly marvelous degree of control over them The great problem of the present age is to secure a like degree of know1 edge and control of the human factor. Progress has already been made along this line, but it is only a beginning. Wilhelm Ostwald says tha scientific knowledge enables a man to be a true prophet; but it must be remembered that a good many people do not seem to be able to main tain a high average in prophecy. In short, 'the average of knowledge is not equal to the average needs of the present time, but continually fails to keep pace with it. It has been aptly said that the really essentia need of the period is for more brains; if we only had sufficient knowledg and sagacity we could not only solve all difficulties, but prevent then from arising. This generalization holds good for an industrial organization. Th most vital need of the management is for more brains. The logica course for an engineer in charge of an industrial organization is, therefore to direct whatever forces may be at his command toward the development training, and guiding of all the brains in his organization. This is easie said than done, for it involves the carrying on toward two objective: the maximum of productive work, and the development of the individual who perform it. This is essentially like the rebuilding and enlarging of plant, keeping it in full operation the while. On the other hand, if th aim is merely for maximum production from an organization, withou offering opportunity for development, the final outcome will necessari be like that of a plant that is driven at full capacity without stoppin for repairs or improvements; it eventually becomes so run down th either a complete rebuilding is necessary or else it has to be abandone

Jan 1, 1918

By Owen F. Devereux

Two discrete types of microstructure me seen in cermets formed by the reaction: 4Al (liquid) + 3SiO2 (glass) — 2A12O3(a) + 3Si (solid) Relatively coarse-grained macroscopically isotropic specimens resulted from reaction with aluminum containing appreciable silicon, while macroscopically anisotropic fine-grained specimens were formed by reaction with aluminum low in silicon. Optical microscopy, electron microscopy, and X-ray diffraction suggest that the anisotropic material contains gross areas in which submicroscopic grains of a A12O3 are oriented along radial lines drawn from the specimen surface. These lines are presumed to originate at defects in an otherwise protecting surface layer. A unique cermet is formed by the reduction of high-silica glass by molten aluminum according to the reaction: 4A1 (liquid) + 3SiO2 (glass) — 2A12O3 (a) + 3Si (solid) The free-energy change accompanying this reaction is -150 kcal at 800°C; the volume change (volume of A12O3 and silicon minus volume of SiO2) is +6 pct. The reaction product, however, contains aluminum metal as well as Al2O3 and silicon because some of the product silicon is dissolved in the aluminum bath and is replaced by aluminum in the structure. The product is a hard gray solid that retains the external dimensions of the original silica article. The system has been studied in the past, the investigations culminating in patents to George1, 2 and Saw-chuk., The former emphasize that this reaction is but one of a relatively broad class of such systems, while the latter demonstrates that a marked improvement in the gross physical properties of the cermet can be obtained by dissolving appreciable quantities of silicon in the aluminum reactant. The system has also been studied by workers at Rolls Royce Ltd.,4-6 who have patented the addition of small quantities of arsenic, antimony, bismuth, or phosphorus to the reactant bath to SO impede the reaction that glass fibers may be metal-coated by immersion in molten aluminum.

Jan 1, 1969

By T. Egleston

The manufacture of charcoal in kilns was declared many years ago, after a series of experiments made in poorly constructed furnaces, to be unprofitable, and the subject is dismissed by most writers with the remark that in order to use the method economically the products of distillation, both liquid and gaseous, must be collected. It is asserted with truth that the number of kilns required for a large production of iron would be so great that it is doubtful whether any works would be justified in making the necessary outlay for their constructiou, but it can also be asserted with equal truth that for any such production in a given locality the use of charcoal as fuel would be eqnally unjustifiable. It appears to have been forgotten that there were other manufactures besides iron in which large amounts of charcoal were used, but these consumers seen] to have been guided entirely by the results of the experiments of the iron men, who necessarily made the largest qnantity of it. Some authors speak in a doubtful way of the quality of the charcoal produced, and a few concede that with great care good charcoal can he made in kilns, but that most of the workmen do not like kiln 'charcoal. This is the real secret of the opposition to this method of manufacture. Most of these objections were written when charcoal was the most important fuel used by the iron manufacturer, and when what was a largeproduction of iron for several furnaces was less than that produced by a single modern one, in localities where other fuels can be had. Almost all that has been written on the subject related to the use of the fuel for the manufacture of iron in the blast furnace, where very peculiar properties are required, and where the qnantity produced is limited by the height of the furnace, and this in turn by the crushing resistance of the charcoal. A large production was, therefore, only possible when the best and hardest woods were used. Of all these objections there is not a single one which is not eqnally applicable to any method of charcoal manufacture, whether it be meilers, pits, or furnaces. Until recently, therefore, the manufacturers of charcoal iron

Jan 1, 1880

By C. Altstetter, Y. Huang, E. de Lamotte

Nitrogen was introduced into pure niobium (colutn-bium) and dilute Nb- Zr alloy wires by equilibration with pure nitrogen gas at high temperatures. Room-temperature hardness was correlated with the alloy composition, heat treatment, and microstructure. Hardness was found to be most sensitive to the amount of nitrogen in solution; however, a significant hardening up to 500 Dph look place upon aging of quenched alloys. A coarse dispersion of nitride did not significantly increase the hardness of the material though the nitride was found to have a hardness of 1400 Khn. BY now the marked effect of nitrogen on the properties of bcc refractorv metals is we ll-documented. There are few studies, however, in which the state of the solute has been carefully controlled. Indeed, the composition-temperature-pressure relationships in nitrogen-refractory metal systems have been determined precisely for only niobium and tantalum.'-4 Most investigations on niobium have dealt with alloys High-nitrogen alloys cleaved on (100) planes and had negligible ductility. Precipitation was found to occur in either a discontinuous or a continuous fashion, depending on the composition and cooling rates. Upon cooling, the precipitation first proceeded discontinu-ously by the nucleation of nilride needles at subbound-aries and subsequent growth of a two-phase microcon-stituent. At lower temperatures continuous precipitation occurred in the subgrain interior ahead of the discontinuous precipitation interface. containing nitrogen, carbon, and oxygen in significant but uncontrolled and, in several instances, undetermined amounts. Thus, there has been some uncertainty regarding the presence and the distribution of precipitates. This paper presents results which relate the hardness and microstructure to the heat treatment and nitrogen content of niobium and Nb-Zr alloys. Niobium rod* produced by the Wah Chang Corp.

Jan 1, 1968

By O.W. Ellis

Recently there has been a considerable revival of interest in the effects of the various elements commonly added to brass for the purpose of increasing its strength. For many years the work of Guillet2 alone gave reliable information in this regard. Even today his determinations of the coefficients of equivalence of the various elements relative to zinc in brass are those universally employed in industry. This is so because these coefficients have stood the test of time—their substantial correctness has been proved in almost universal practice. It is not our intention to discuss here these coefficients or their use. Rather do we wish to emphasize the need for further systernatic studies of the mechanical properties of the ternary systems of copper, zinc, and other individual elements. Since Guillet published the results of his first investigations Millington, 16 Smalley33 and Thiband 45 have added somewhat to our information. In general they have confirmed the findings of Guillet, which may be stated in the following rather general terms: 1. The addition of aluminum to the 70:30 and 60:40 brasses progressively increases their hardness and strength and reduces their ductility and resistance to shock. 2. The addition of small amounts of iron to a 60:40 brass improves its strength without affecting its ductility. 3. The addition of small amounts of manganese to a 60:40 brass causes a progressive increase in its strength and reduction in its ductility. A considerable amount of information has been amassed in regard to the effect of nickel on brass (9, 22, 41) which it is unnecessary to refer to here, in view of the scope of this paper. The situation in regard to these alloys in 1926 was very clearly stated by an anonymous writer,47 in The Metallurgist of February of that year, whose remarks were so to the point that they are well worth quoting: It will he seen that there are still large fields remaining to be studied in each of these systems (those of the aluminum, iron, nickel and manganese brasses) before our knowledge is adequate. When we come to the more complicated systems the position is even less satisfactory, and on account of the very incomplete nature of the work which has been

Jan 1, 1929

By O. W. Ellis

Recently there has been a considerable revival of interest in the effects of the various elements commonly added to brass for the purpose of increasing its strength. For many years the work of Guillet2 alone gave reliable information in this regard. Even today his determinations of the coefficients of equivalence of the various elements relative to zinc in brass are those universally employed in industry. This is so because these coefficients have stood the test of time—their substantial correctness has been proved in almost universal practice. It is not our intention to discuss here these coefficients or their use. Rather do we wish to emphasize the need for further systernatic studies of the mechanical properties of the ternary systems of copper, zinc, and other individual elements. Since Guillet published the results of his first investigations Millington, 16 Smalley33 and Thiband 45 have added somewhat to our information. In general they have confirmed the findings of Guillet, which may be stated in the following rather general terms: 1. The addition of aluminum to the 70:30 and 60:40 brasses progressively increases their hardness and strength and reduces their ductility and resistance to shock. 2. The addition of small amounts of iron to a 60:40 brass improves its strength without affecting its ductility. 3. The addition of small amounts of manganese to a 60:40 brass causes a progressive increase in its strength and reduction in its ductility. A considerable amount of information has been amassed in regard to the effect of nickel on brass (9, 22, 41) which it is unnecessary to refer to here, in view of the scope of this paper. The situation in regard to these alloys in 1926 was very clearly stated by an anonymous writer,47 in The Metallurgist of February of that year, whose remarks were so to the point that they are well worth quoting: It will he seen that there are still large fields remaining to be studied in each of these systems (those of the aluminum, iron, nickel and manganese brasses) before our knowledge is adequate. When we come to the more complicated systems the position is even less satisfactory, and on account of the very incomplete nature of the work which has been

Jan 1, 1929

By L. W. McKeehan, W. C. Elmore

The magnetic powder method, long used for roughly mapping magnetic fields, has recently been refined1, "or investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter2 first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators:' have used Bitter's original technique, with slight modifications, to study the variation of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement ill the powder technique which led us to the discovery of a new effect throwing considerable light on the magnetic secondary structure of alpha iron4 and of nickel5 single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure. Specimens The following list describes the specimens used in the present investigation. Designation Description A1 Silicon ferrite furnished to us by Dr. W. E. Ruder, of the General Electric Co., for which lie gave the following typical analysis: C, 0.05; P, 0.038; S, 0.026; Mn, 0.15; Si, 3.24. Disk, 0.60 cm. diameter, about 0.05 cm. thick. By X-ray analysis angles between disk normal and [100] 75o, [0101 76" [00l] 21o. A2 Same as A1 except: diameter 0.75 cm. A, Same as A1 except: diameter 0.68 cm.

Jan 1, 1936

By L. W. McKeehan, W. C. Elmore

The magnetic powder method, long used for roughly mapping magnetic fields, has recently been refined1, "or investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter2 first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators:' have used Bitter's original technique, with slight modifications, to study the variation of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement ill the powder technique which led us to the discovery of a new effect throwing considerable light on the magnetic secondary structure of alpha iron4 and of nickel5 single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure. Specimens The following list describes the specimens used in the present investigation. Designation Description A1 Silicon ferrite furnished to us by Dr. W. E. Ruder, of the General Electric Co., for which lie gave the following typical analysis: C, 0.05; P, 0.038; S, 0.026; Mn, 0.15; Si, 3.24. Disk, 0.60 cm. diameter, about 0.05 cm. thick. By X-ray analysis angles between disk normal and [100] 75o, [0101 76" [00l] 21o. A2 Same as A1 except: diameter 0.75 cm. A, Same as A1 except: diameter 0.68 cm.

Jan 1, 1936

By W. T. Burns

Attempts were made in 1908, at the Great Falls Works, to produce ingots direct from the Butte precipitate by smelting the material in a reverberatory refining furnace. The ingots produced in this manner averaged 99.4 per cent. of copper and 0.40 per cent. of arsenic and antimony. The copper content being considered too low, it was decided to cast the copper into anodes and to treat the anodes in the electrolytic plant. No. 1 Furnace, in which the precipitate was treated, was a regular cathode refining furnace previously employed in making wire bar, cake, and ingot from electrolytic cathodes. The hearth of the furnace was 24 by 12 ft., having a capacity of 100,000 lb. of cathodes. The furnace was coal fired, and the copper was dipped by means of trolley ladles. The average composition of the furnace charges was as follows: Per Cent. Peer Cent. Copper. Precipitate,..........7.5.3 40 to 80 Purification cathodes,.....1.9 92 Refinery slag (oxide slag),.. 10.1 50 to 60 Electrolytic cathodes,... 2.1 99.9 Precipitate anode scrap,.... 3.1 99.0 Scrap copper,.........7.5 99.2 100.0 The slag from this furnace amounted to 46 per cent. of the total amount charged and was of the following average composition: Per Cent. Cu..............16.86 SiO2.............34.7 FeO.............18.8 A12O3.............13.0 CaO.............9.4 MgO.............2.7 S............... 0.47 As..............0.11 Sb...............0.006 Ag, oz per ton.....0.18

Jan 1, 1914

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

By Herbert H. Kellogg

IN 1930, Taggart, Taylor and Knoll1found that addition of various electrolytes to suspensions of ground minerals resulted in the stopping or starting of Brownian movement of the suspended particles. On the basis of the many new facts found, they rejected the "classical "[t] theory of Brownian movement and proposed an "ionization" theory. This new theory was further supported in later publications by Taggart.3,4 The acceptance of the ionization theory by men in the field of flotation may be judged by the mention given this theory in Gaudin's "Principles of Mineral Dressing,"5 Wark's "Principles of Flotation,"6 as well as in a recent paper by Fitt, Thomas and Taggart.7 The proponents of the ionization theory have gone further than the mere statement of the new theory. A parallelism between the Brownian movement of mineral particles and their behavior in flotation was reported.1,3,4 Likewise, the correlation between flocculation-dispersion of mineral particles and the Brownian movement of these particles has been investigated.7 Bankoff15 has suggested that "slime-coating" can also be directly correlated with the Brownian movement of the slime particles. In each of the instances mentioned it is the ionization theory of Brownian movement that has been used to "explain" the correlations that were found. The essential conflict between the kinetic theory and the ionization theory can be understood best by a brief description of each. The kinetic theory* proposes that Brownian movement is caused by the impacts of liquid molecules against the solid particles. At any instant of time, the molecular impacts on all sides of the solid particle will not balance, and the particle will receive a push in some direction. According to this theory, all particles suspended in a liquid are in Brownian movement. However, if the particle is very large, the impacts on all sides will very nearly balance and the motion will not be noticeable. Another factor, besides the size of the particle, that affects the magnitude of the Brownian movement is the viscosity of the liquid-the greater the viscosity, the less the displacement of particles by Brownian movement. This theory has been verified experimentally by measurement of the velocity of Brownian movement, and by measurement of the compacting of suspensoid particles under the influence of gravity.2 The originators of the ionization theory found that the addition of various electrolytes to slime pulps caused cessation or commencement of Brownian movement, depending upon the chemical nature of the particle and the electrolyte. The Brownian movement of quartz particles was observed to stop upon the addition of certain electrolytes, where the conditions of the experiment prevented flocculation

Jan 1, 1945

By Hsun Hu, B. B. Ruth

The rates of migration of high-angle boundaries in zone-refined aluminum crystals rolled 20 to 70 pct in the (110)[i12/ orientation were studied. Following a recovery anneal at an appropriate temperature to stabilize the polygonized structure, boundary migration rates of artificially nucleated grains were measwed isothermally at several temperatures. Results indicate that the rate of boundary migration depends strongly on the amount of deformation and on the cell size of the polygonized matrix, and is related to the driving free energy by a power function. The degree of anisotropy in growth 0.f the re crystallized grains nn&apos;th preferred mientation is independent of deformation; the migration rates of the fast-moving and the slow-moping boundary segments of a gowing grain differ by as much as one order of magnitude. The actir\ation energy fm a grain boundary migration, although nearly the same for both the fast-moving and the slow-moving boundaries for a given deformalion, decreases from 45 to 30 kcal per mole with an increase in deformation from 20 to 70 pct reduction. Re crstallization by the growth of the artificially nucleated grains results in preferred orientation. The Percentuge of&apos; grains favorably oriented for growth increases with increasing deformation. None of these grains corresponds to the ideal Kronberg-Wilson orientation relationship. The observed growth aniso-tropy is discussed in terms of boundary structure. The boundary velocity as a function of the cell inter -facial area, or the driving free energy, is discussed in the light of current theories of boundary migration. It is well established that recrystallization with re-orientation occurs by the migration of high-angle boundaries of strain-free grains. The driving force for this process is provided by the free energy stored in the metal during deformation. A quantitative study of the effect of varying driving force on grain boundary migration in deformed metals has not been possible heretofore, primarily because of: 1) concurrent recovery steadily decreasing the available driving free energy for boundary migration, &apos;-3 and 2) in-homogeneity of strain in the deformed metal.4 Aust and Rutter3 studied grain boundary migration in striated single crystals of zone-refined lead. Although the driving free energy in such crystals remains unaltered during annealing, this method does not provide a range of driving free energies over which measurements of grain boundary migration can be made. In the present investigation, the rates of migration of high-angle boundaries in deformed aluminum zone- refined single crystals were studied at various temperatures, after deformation ranging from 20 to 70 pct reduction by rolling at -78°C in the (ll0)[i12] orientation. The boundary migration rates along different crystallographic directions were determined under steady-state conditions, i.e., in the absence of competing recovery processes or impingement of recrystallized grains growing into the deformed single crystal matrix. Simultaneous recovery was eliminated by suitable anneals prior to the boundary migration measurements. The recrystallized grains, which grew a ni so tropically into the homogeneously polygonized matrix, developed flat boundary segments during early stages of growth. These boundary segments subsequently migrated along a direction approximately normal to the boundary plane into the matrix rystal. Increasing deformation over the range employed was estimated to increase the driving free energy for boundary migration by about five times. The kinetics of the boundary migration process, examined under these conditions, indicate that the boundary velocity is greatly affected by a small change of the driving free energy in the matrix crystals. These results were examined in the light of the current theories of grain boundary migration. EXPERIMENTAL PROCEDURES Single crystal strips (9 by 1 by 0.125 in.) of zone-refined aluminum, were seed-grown by the Bridgman method in a high-purity graphite mold (<lo ppm ash) at 1 in. per hr. Precautions were taken to minimize contamination of the metal during crystal preparation and subsequent handling. Spectrographic analysis of the metallic impurities in the grown crystals is Qven in Table I. The crystals were rolled in the (110)[112] orientation at -78°C to various reductions in thickness, ranging from 20 to 70 pct, in 10 pct increments. The desired reduction was achieved by many rolling passes, each being no more than 0.002 in. To minimize surface friction, the crystal was rolled between two thin layers of teflon. For those crystals rolled more than 40 pct, it was necessary to remove the disturbed surface layers by electropolishing at -5" to -10°C at an intermediate stage of rolling. The edges of deformed crystals were removed by a jeweler&apos;s saw while submerged in alcohol at -78° C to obtain samples of about ? by i in. The distorted metal at the cut edges and the surface layers were then removed by electropolishing, with removal of a minimum of 0.004 in. from each surface. The thickness of the crystals prior to rolling was chosen so that the final thickness was 0.025 in. for all samples. These deformed single crystals were each prean-nealed for 1 hr at an appropriate temperature in the range of 130" to 280°C, depending upon the amount of deformation. The purpose of this preannealing was to

Jan 1, 1970

By Rees D. Rawlings, C. W. A. Newey

The aging characteristics of an Fe-11 at. pct Mo alloy have been studied by means of light metallography together with density, Young&apos;s modulus, and hardness measurements. The results were consistent with the precipitation of a single intermetallic compound during aging; overaging was slow relative to that in other iron-based binary alloys. The solution treatment temperature had a small effect on the rate of hardening whereas deformation prior to aging had a marked effect on both the rate of hardening and the peak hardness. The density data indicate that the compound precipitated is Fe3MO2 and not the Laves phase Fe2Mo. Analysis of the modulus and density results gave values for the time exponent for precipitate growth of approximately 1.0 and 1.5 for the alloy aged with and without prior deformation, respectively. DETAILED studies of precipitation hardening in bcc matrices have been confined largely to the effects of carbides and nitrides. In view of this and the growing technological interest in intermetallic compound strengthening, e.g., in maraging steels, a study of precipitation in iron-based alloys with a low interstitial content has been undertaken. This paper is concerned with the aging behavior of an Fe-11 at. pct Mo alloy; the mechanical behavior of the alloy will be reported later. The early work of sykes on Fe-Mo alloys showed that precipitation of the intermetallic compound was accompanied by an increase in hardness and a decrease in volume of the material. More recent surveys of the strengthening associated with precipitation have been made3-5 and, in particular, Elsen and wassermann4 showed that deformation prior to aging increased the rate of hardening. These latter workers also followed the precipitation process by means of dilatometry, electrical resistivity, and lattice parameter measurements. Their results confirmed that there is a decrease in volume on aging. Except for the work of Hornbogen on an Fe-20 at. pct Mo alloy, neither clustering nor the precipitation of a nonequilibrium phase has been observed in Fe-Mo alloys. Studies of alloys of lower molybdenum content475 indicate that the equilibrium intermetallic compound is precipitated during aging. However, there is some doubt concerning the nature of the equilibrium precipitate phase. According to the phase diagram constructed by Hansen,8 the phase should be precipitated. This phase has a rhombohedra1 crystal structure which is characterized by the formula Fe706,&apos; although the composition of the molybdenum-rich boundary corresponds approximately to Fe3Mo2. The version of the diagram proposed by Sinha, Buckley, and Hume-Rother indicates that the A phase, a Laves phase Fe2Mo, should be precipitated. Their observation of a Laves phase supports the earlier findings of Bechtoldt and Vacher,13 although, in a recent study of the system by means of diffusion couples, Rawlings and Newey did not detect the phase. The work presented here describes the effect of solution-treatment temperature, aging temperature, and prior deformation on the aging characteristics of the alloy as revealed by light metallography together with hardness, density, and Young&apos;s modulus measurements. In addition the density data are used in an attempt to determine the compound precipitated during aging. EXPERIMENTAL PROCEDURE A 29-kg ingot of the alloy was cast at R.A.R.D.E., Fort Halstead, from deoxidized, Japanese electrolytic iron and sintered molybdenum. The ingot was homogenized for 6 hr at 1473°K and then worked, with intermediate anneals, into 6- and 16-mm-diam rods and 6-mm plate. Chemical analysis of the alloy gave, wt pct: Mo, 17.5 (11 at. pct); C, 0.003; Si, 0.002; S, 0.005; P, <0.002; and02, 0.0098. Solution treatments were carried out under a dynamic argon atmosphere in a vertical, "crusilite" element, furnace which had a facility for rapid quenching into iced water. Except for the study of the effect of solution treatment temperature, all specimens were solution-treated at 1573" * 2°K for 1 hr. Salt baths were used for the aging treatments. Specimens for hardness, density, and Young&apos;s modulus measurements were produced, after heat treatment, from the stock rod or bar using a precision silicon carbide slitting wheel. As described later, the quenching treatment produced local plastic strain in the stock material; consequently, care was taken to ensure that the specimens were not prepared from these regions. Those specimens used in the studies of the effects of prior deformation on the aging behavior were strained in compression in a Denison universal testing machine. Specimens for light metallographic observations were mechanically polished on successively finer grades of diamond paste down to and then etched in either alcoholic ferric chloride or in a 2 pct nital solution. Vickers diamond pyramid hardness data were obtained using a 30-kg load. At least five impressions were averaged for each determination. Density measurements were made using a displacement technique in which each specimen was weighed in air and in dibromoethane at 296°K. The specimens were cylindrical and weighed 3 to 4 g; all weighings were made on a balance reading to 1 x 10"5 g. For each specimen the mean value of five weighings was used to calculate the density. The density of the dibromoethane was determined using the displacement procedure and a standard nickel specimen. The error in an absolute density value was estimated to be HI.01 pct. To obtain the density as a function of aging time a single specimen was used and the density meas-

Jan 1, 1969

By David L. Holt, Walter A. Backofen, Anwar-uI Karim

Specimens of a hydrided Mg-0.5 Zr alloy were strained in tension at 500°C and constant rates of 2 x10-3 5 x 10-3, and 2 X 10" min-1. Hydride-denuded zones formed at grain boundaries normal to the tensile-stress direction as a result of magnesium transport during difusional flow. The width of the zones could be measured and the measurement used for calculating the diffusional component of the imposed tensile strain. The strain from diffusional flow was found to increase with imposed strain at a diminishing rate, tending to saturate at approximately 12 pct. Strain rate sensitivity of flow stress was low. The apparent non Newtonian character of the diffusional flow is attributed to a non Newtonian process acting in parallel with it which could be boundary shear. Fracture grows out of voids that form in the denuded zones. DEFORMATION of a grain by diffusion of atoms from boundaries stressed in compression to boundaries stressed in tension is Newtonian viscous,1-3 and evidence has accumulated in recent years that such a process may be responsible for the high strain-rate sensitivity of the flow stress of super-plastic alloys.4"7 One piece of evidence is that experimental stress: strain-rate relationships can be quantitatively explained.5-7 There is also metallo-graphic evidence of diffusional flow in superplas-ticity, but in a limited amount. The formation of striated bands on the surface of superplastically deformed specimens has been attributed to diffusional flow.5"7 The basis of that attribution came from experiments on a coarse-grained, nonsuperplastic and hydrided Mg-½ wt pct Zr alloy which formed hydride-denuded, light etching zones at tension-stressed boundaries when strained in tension at 270?C.6 The origin of these zones had already been traced to the diffusional flow of magnesium atoms to the boundaries.&apos; The particular observations in the more recent work were of striated-band formation on the surface and denuded-zone formation internally, with both the bands and zones having the same width and appearing at tension-stressed boundaries. It was argued that the bands were a surface manifestation of the zones and hence of diffusional flow. Of course in superplastic alloys which do not contain internal metallographic "markers", the surface bands can be the only metallographic indication. In the present work, denuded-zone formation was utilized, as it has been by others,9-11 to extend the observations of diffusional flow and to measure the strain, ed, resulting from it. Grain size had to be large to measure ed with accuracy. The grain size chosen for this study was -30 , and with that a strain of 10 pct from diffusional flow produces a denuded zone only 3 µ in width. The large grain size naturally precludes superplasticity. The observations of diffusional flow were complemented by determining the strain from the other operative deformation modes: slip, e,, and grain boundary shear, egb. An incremental specimen extension is the sum of increments from slip, and grain boundary shear as well as diffusional flow. Division by a common length is required to convert to strain. If this length is taken as the initial specimen length, then imposed engineering strain, e, is given in terms of the component engineering strains by e = ed + es + egb [1] Stress:strain-rate relationships are determined by the way in which this "strain balance" is made up. EXPERIMENTAL Material. Zirconium hydride markers were introduced into the Mg-0.5Zr alloy by annealing in hydrogen at 450°C for 30 min. The hydride concentration was particularly high at zirconium rich stringers, which was fortunate in that the transverse boundaries at which denuded zones form lie perpendicular to the stringers. Grain size after annealing was 30 µ. Photomicrographs of unstrained and strained material are shown in Fig. 1. Procedure. Specimens were strained in tension with an Instron machine at crosshead velocities of either 2 x 10"3, 5 x X or 1 x 10-2 in. min-&apos;. Specimen length and diameter were 1.0 and 0.2 in., respectively, so that initial strain rates in tests at constant crosshead speed were 2 x 10"3, 5 x X and 1 X l0-2 min-1. Tests were made at 500°C which is a compromise temperature at which diffusional flow is still measurable but grain growth is not active enough to interfere with metallographic measurements. The tests were made in a hydrogen atmosphere. Strain Balance. An equation additional to [I] is eg = ed + es [2] where eg is strain measured from grain elongation. Measurement was made of ed, eg, and, of course, e, which enabled all the strains in Eq. [I] to be determined. For this purpose, strained specimens were sectioned longitudinally, polished, and etched. The strain from diffusional flow, ed, was computed by measuring on photomicrographs the width in the tensile direction of denuded zones at either end of a grain XI, X2, adding them, and dividing by twice the initial longitudinal grain dimension L0, Fig. 2. Reported values are the results of measurements on seventy randomly selected grains; 95 pct confidence limits on ed were +1.5 pct strain. To measure eg, the maximum length, L, and the maximum width, W,

Jan 1, 1970

By H. H. Campbell

Many attempts have been made to write a formula by which to calculate the strength of steel from its chemical composition, but most of these endeavors have failed because there were too many disturbing conditions. It is idle to collect from the pages of trade-papers, books, or the proceedings of scientific societies, a multitude of observations. The combination of such results will simply show that steel of the same composition will vary in tensile strength through wide limits—a fact that has been known for generations. That cold-working, overheating, and many another form of heat-treatment alter fundamentally the strength of steel, is ancient history, although it is only recently that the microscope has pointed out the road to an explanation of the phenomena. It mag be urged that the microscopic structure must betaken into consideration in any formula giving the ultimate strength, but from the standpoint of the present investigation this is unnecessary. We are trying to determine primarily, not what changes in ultimate strength may be made by variations in the condition of carbon, but what effect is produced by changes in the amount of carbon, when its condition remains constant. For such an inquiry, in order that the condition of the carbon should remain as nearly uniform as possible, it is essential that all testrpieces be made under the same conditions; and it is believed that the tests described in this paper satisfy that requirement. The investigations were made at the works of the Pennsylvania Steel Company, Steelton, Pa.; the ingots from which the tests were made were 6 in. square in every case; they were heated in the same furnace and forged at the same ham-

Jan 1, 1905

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps : 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. .These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the molecules will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1964

By L. Seigle, R. Resnick

An inert-marker movement experiment indicates that the ratio of the intrinsic diffusion coefficients DC:DTa = 80:l in TaC at 2500°C. Measurements of the diffmion coefficient of carbon in nonstoichiometric TaC at temperatures from 1700° to 2700°C reveal that Dc increases with decreasing carbon content, but much less than expected from the probable change in vacancy concentration with carbon content. A diffusion process involving two simultaneously operating mechanisms is postulated, and shown to be theoretically feasible. The average value of the carbon diffusion coefficient is given by DC = 0.18 exp[(-85,000 ± 3000)/RT] sq cm per sec over the composition range 46 to 49.5 at. pct C. BECAUSE of their high melting points and hardness, the carbides of the IV, V, and VI group transition metals, along with those of uranium, have attracted considerable interest for applications at high temperatures. In these applications the reactivity of the materials is important, and, since rates of diffusion within the compounds influence reactivity, a knowledge of diffusion kinetics and mechanisms is desirable. While many investigations of the mechanical and electrical properties of these compounds have been made, only two fundamental investigations of diffusion in the carbides are known. Chubb, Getz, and Townleyl measured the diffusivity of carbon and uranium in UC, and Gel&apos;d and Liubimov2 measured the diffusivity of carbon and niobium in NbC. This paper describes an investigation of the diffusion of carbon in tantalum monocarbide and, in particular, the influence of carbon deficiency on this process. Tantalum carbide melts at approximately 3800°C, which makes it one of the highest melting materials known. The compound exists over a rather wide range of carbon Content.3-7 At the peritectic temperature, 3240°C, the phase extends from about 36 to 50 at. pct C. Although the compound can exist with a substantial carbon deficiency, the high carbon phase boundary remains near the stoichiometric composition over the entire temperature range; i.e., no carbon excess is observed. The structure of TaC is the NaCl type wherein carbon atoms normally occupy the octahedral sites in a somewhat expanded fcc lattice of tantalum. Decrease of the lattice parameter with decreasing carbon suggests that the removal of carbon introduces octahedral vacancies into the lattice. I) EXPERIMENTAL DETAILS AND RESULTS Inert-Marker Experiments. In a compound such as TaC the interstitial element would be expected to diffuse more rapidly than the metal. This was confirmed by an inert-marker experiment, following Srnigelskas and irkeendall.8 Ideally, the markers should be placed at the interface between a slab of low-carbon TaC and graphite, and their movement during subsequent inter-diffusion measured. Unfortunately, no solid could be found which is unreactive in contact with carbon at the high temperatures employed in these experiments. In order to circumvent this problem, a specimen was designed in which the markers consisted of several small canals running just below the surface of a tantalum slab. This specimen was prepared by machining grooves on the surface of the tantalum slab and then diffusion-bonding a thin plate of tantalum to the slab over the grooves. The surface of the plate was then ground down until the distance between the canals and surface was as small as possible (about 0.01 cm). Thus, the canals would lie entirely within the TaC phase after a short period of diffusion. The diffusion anneal consisted of immersing the metal sample in high-purity graphite powder and heating for approximately 10 hr at 2500°C under vacuum. At this temperature, the vapor pressure is sufficiently high and the transfer of carbon from graphite sufficiently rapid to allow the surface of the diffusion sample to attain the stoichiometric carbon concentration very quickly. Conclusions regarding the relative diffusion rates of carbon and tantalum in the compound layers (TaC and Ta2C) can be drawn from the location of the canals after the diffusion anneals. If the growth of the layers is governed mainly by the diffusion of carbon, as expected, the canals should remain close to the sample surface. If the diffusion of tantalum contributes appreciably to formation of the compound layers, the distance from the markers (canals) to the surface should increase. Fig. 1 shows, diagrammatically, the appearance of the specimens after diffusion, and Table I presents the depth below the surface at which the

Jan 1, 1967

Primarily, 1961 was a year for widespread application of tools and techniques which have become operational in the past several years • • • Raising --Raise climbers and climber raising techniques have been improved; narrow veins as low as 55° dip are now being mined from climber raises. Climber modifications include: larger motors, tighter radius curves negotiated, improved lubrication and new methods of stowing the climber during a blast. Climber raises are now ventilated in several ways: a 12-in. diam flexible vent tube behind the climber rail; a 6-in. diam pipe behind the climber rail (with fan); or a 6 to 8-in. diam drill hole along the axis of the raise. In hot raises, these ventilating techniques have resulted in more rounds per shift. When driving raises from crosscut and lateral development, mucking machine loading of raise rock is preferred over slusher ramp loading for the following reasons: a) faster set-up and teardown of climber facilities; b) easier access for climber maintenance, repair and loading of raising supplies; c) area at the bottom of the raise can be kept cleaner. Both wide and narrow veins are mined from 7 x 7-ft climber raises at Butte and at Republic, Wash. At Republic, climber rollers have been modified to support increased weight when driving 55°dip raises • Drilling-The new largebore, short-stroke push feed drills are much faster drilling than previous models and are most satisfactory in hard ground. Although reports on maintenance studies of the new drills are not yet available, increased steel and bit wear and breakage, and increased drill maintenance are seen as potential problems. Mines in Montana and Idaho continue to test rubber-collared drill steel. The fabricating methods used are successful but advantages in increased steel life have yet to be proved. Underground applications of down-the-hole drills continue. Drilling speed and accuracy are reported as the outstanding advantages. Manufacturers are now hopeful of making drills which will operate in any direction. Present applications are for ventilation holes (to 8 in. diam) for climber raises, holes for hydraulic fill distribution, drain holes and "predrilled" raises. Good drilling accuracy has been reported to a depth of 200 ft. Cutting holes in drifting is seen as a future application

Jan 2, 1962

Discussion of the paper of M. B. YUNG, presented at the Pittsburgh meeting; October, 1914, and printed in Bulletin No. 93, September, 1914, pp. 2451 to 2458. T. T. READ, New York, N. Y.-I might .point out that this paper of Mr. Yung&apos;s is on a field that is comparatively little known. It is not as well known as the Kochiu tin field, of Yunnan, which is probably the third . in tin output of the world. This field under discussion is considerably further west and the tin which is produced here is, according to Mr. Yung, of somewhat higher grade than the Yunnan tin, and is used by the refiners at Hong Kong to improve the grade of the Yunnan tin. Most of you know that the tin from the Yunnan is shipped to Hong Kong, where it is refined and shipped to Europe. Mr. Yung points out that the Fu Chuan deposits are entirely alluvial and not found in any veins. They .differ in that from the Kochiu deposits, which Leclere says are "nullement alluvionels; leur origéne filonienne est de plus evidentes." Granite is the country rock here; doubtless the tin occurred in veins in the granite, and the deposits have resulted from the disintegration of the granite. This is a country of strong erosive agencies. The country is semi-tropical, and the rainfall is heavy, so that one would naturally expect deep surface erosion of this kind.

Jan 4, 1915