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By J. B. Hess, C. S. Barrett

TO reach equilibrium between different phases in cobalt-rich alloys requires prohibitively long annealing cobalt-richalloystimes when temperatures are below about 700°C. The fact that a transformation from face-centered cubic to close-packed hexagonal readily tered takes place at temperatures below this in the cobalt-rich solid solutions is not an indication that thermally activated processes occur at an appreciable rate, for the transformation is well established as martensitic in nature. Wide divergence between heating and cooling experiments and high sensitivity to prior heat treatment make it difficult to judge temperatures of equilibrium between the phases.&apos; One object of the present work was to see if the information object of on the relative stability of phases could be gained by substituting plastic deformation for thermal agitation. Procedures were worked out that led to the determination of a diffusionless type of phase diagram, which represents the temperature of of phase equal stability for phases of the same composition, and the technique was applied to the Co-Ni system. Another object of the work was to see whether or not deformation would generate frequent stacking faults when these were thin lamellae of quentstackingfaultsa phase having higher free energy than the parent phase. The alloys were prepared in 80 to 100 g melts from cobalt (with metallic impurities estimated spectrochemically as follows: Ni, 0.05 pct; Fe, 0.001 pct.; Mg, Si, Cu, Cr, Al, < 0.001 pct) and Mond Car-bony1 nickel (with Fe, 0.05 pct; Si, 0.003 pct; C, 0.61 pct.; Cu, 0.001 pct; Co, Cr not detected, < 0.01 pct). The metals were melted in pure Al2O3 crucibles. An atmosphere of argon, that had been purified by passing over hot magnesium chips, was used for the alloys that, by analysis of the portions of the ingots actually used, were found to contain 15.3, 25.7, and 35.0 pct Ni, and vacuum melting (after degassing) was used for those containing 29.4 and 31.5 pct Ni. After induction melting the alloys were allowed to solidify in the crucible, and slices % in. thick x ½ in. in diam were annealed 12 hr at 1350°C for homogenization. These same specimens were used throughout the series of experiments, with annealing treatments of 4 hr at 900°C in purified hydrogen followed by furnace cooling, alternating with the deformation and X-ray tests discussed below. Results Spontaneous transformation was observed on cooling to room temperature in all alloys containing 29.4 pct Ni or less and by cooling the 31.5 pct alloy to — 195°C but was not observed in the 35 pct alloys after cooling to —195°C. These results are in satisfactory agreement with the cooling experiments of Masimoto.4 From these data it is clear that the temperature of beginning transformation M,,, drops to 20°C with the addition of about 30 pct Ni. The test for spontaneous transformation was metallographic. Specimens were thermally polished by annealing 10 hr in hydrogen at 1350°C, then furnace cooled; if trans- formation had occurred there were relief effects visible on the thermally polished surfaces. These markings were narrow straight lines, usually resolvable at high magnification as clusters of fine lines that resembled slip lines. It was concluded that they resulted from displacements on (111) planes, for the number of directions in individual grains often reached but never exceeded four, and lines could always be found parallel to the thermally etched (111) boundaries of annealing twins. The markings were thus consistent with the idea that the transformation occurs by (111) plane displacements (Shockley partial dislocations moving on (111) planes). This was further confirmed by X-ray tests for stacking disorders. Using an oscillating crystal technique previously employed to detect strain-induced faulting in Cu-Si alloys," streaks indicative of the stacking faults were looked for and found on X-ray films of the spontaneously transformed 25.7 pct Ni alloys, as expected by analogy with Edwards and Lipson&apos;s results on pure cobalt." The streaks were much intensified after rolling at room temperature. Transformation induced by plastic strain was investigated as a function of alloy composition and temperature of deformation. A series of tests was made to determine suitable straining and X-raying techniques. Filing was found inferior to abrasion in converting cubic samples to hexagonal, and abrasion was less effective than peening in producing smooth unspotty Debye rings in the X-ray patterns. Because the diffraction lines were broad, Geiger-counter spectrometer records of filings were less sensitive in revealing small amounts of transformed material than X-ray patterns recorded on films in a small diameter camera. After these exploratory tests the following methods were adopted. Specimens that had been annealed at least 4 hr at 900°C and furnace cooled were mounted in a block of aluminum, brought to temperature, and peened thoroughly with a mullite pestle preheated to the same temperature. The specimens were then quenched to room temperature. In peening, a circular area of % in. diam was given 500 blows. A few control tests showed that an additional 1000 blows did not detectably change the proportions of the phases present. The amount of transformation was judged by X-ray reflection patterns from the peened surface, using the innermost four lines of the cubic and the hexagonal patterns with filtered CoKa radiation,

Jan 1, 1953

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.&apos;&apos; The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-&apos; "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

Jan 1, 1959

By L. H. DeWald

During the examination of various commercial brands of copper wire bars, which had exhibited different degrees of adaptability for being drawn into fine gages of wire by the present-day high speed machine, it was found that each brand had a more or less characteristic crystal macrostructure. The extremes of these macrostructures are similar FIG. 1.-EFFECT OF METAL TEMPERATURE IN CASTING ON CRYSTAL MACROSTRUCTURE OF BAR. Reading from left to right, metal temperatures were 1166" C., 1149" C., 1132" C.. 1121" C., 1093" C. to the maximum variation shown in the photomacrographs reproduced in Fig. 1. As the various brands did not differ materially in chemical composition, it was concluded that the differences in structure were the result of variations in casting technique.

Jan 1, 1931

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.&apos; Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.&apos; Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971

By Bai Shiwie, Li. Guangyu

This paper presents the study in situ on stress field of rock mass in a large dam site. By means of two different measure instruments and the method of stress relief, a lot of measure in situ has been done, including stress measurement of three dimensions at ten points and two deep-hole stress measurements in the perpendicular boreholes which are 59.4m and 53m deep seperately, and the basic accordant results corresponding two methods have been got. In the process of the deep-borehole stress measurement we got the stress value in critical state in which cylindrical core would become core-disking in the high stress area, which was first got in the world. The maximum principal stress was up to 650 kg/cm2. The stress value obtained by test and the thickness of rock disks all basically accord to the analysis by mechanical mechanism of core-disking The plane linear elastic finite element analysis has been completed. Results of inverse calculation all ac- cord to the measurement results in four different positions. The whole outline of the stress field of dam site was delineated clearly.

Jan 1, 1982

By S. A., Taylor

IT is very difficult to arrive at exact figures for the cost of maintaining excess capacity of coal mines, but we can approximate the various items. To do this, I will take the Pittsburgh district of Pennsylvania and the other districts can be compared to this one. I believe we can take the depreciation item of plant ac- count as a whole and discount it over a period of 20 years; while this is high for some items it is low for others and I believe it is not far from a safe basis. This equals 5 per cent per year, and this depreciation will take place about as rapidly when not in use as when in operation. A fair value in the Pittsburgh district to- day for plant and houses is close to $4 per ton per annum. At 5 per cent this will equal 20 cents per ton per year. The item of keeping the mine in condition, free from water, etc., will be close to an average of 2y2 cents per ton per annum.

Jan 1, 1928

Jan 1, 1886

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.&apos; Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2&apos;4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy&apos;s equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.&apos; were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By R. G. Bentsen, D. A. T. Donohue

The cyclic steam injection process has become the most widely applied and most successful thermal recovery technique in use today.1-4 Normally, steam stimulation is repeated several times during the life of a project. The problem is to select the optimum number and size of steam treatments so that the profits realized over the entire life of the project are maximum. Obviously, operating costs rise directly with the frequency and amount of steam injection. Operating efficiency, on the other hand, can be adversely affected if the amount and frequency of stimulation are insufficient. Thus arises a multistage decision problem; that is, a decision must be made at each sub-period (day, for example), as to whether steam should be injected, and, if so, how much. It is desirable that these decisions be made in such a way as to secure maximum net profit before taxes. This can be achieved by dynamic programming. To use dynamic programming, we must be able to predict not only the production rate-time curve resulting from a given stimulation, but also how changes in stimulation policy will affect this curve. In this study, the effect of steam injection on well performance is estimated on the basis of a simple model that takes into account both steady-state and transient flow. Oil production rate is calculated for both types of flow, and the larger of the two values is used. This allows the calculation to change to radial steady-state flow at such time as this mechanism becomes more effective than the transient mechanism. We propose to show how dynamic programming can be used to optimize the steam soak process with respect to net profit. For this, a mathematical representation of the steam soak technique is necessary. A further objective, therefore, is the formulation of a mathematical model capable of realistically simulating the physical process. Oil Production Response Model The advantage of using a mathematical model is its generality and ease of manipulation. However, the model must be an accurate representation of the physical process, for a solution derived from a model can be no better than the model itself. The question now arises as to how well the model should be expected to simulate reality. In general, the simplest model should be tried first, for additional accuracy is apt to require additional cost and time. Also, the search for a high degree of accuracy may yield only greater complexity and difficulty without yielding significantly better results. With this in mind, we kept our model as simple as possible, yet generally representative of the actual physical process. The number of state variables is limited to three, and stochastic variations in the parameters are ignored. As a consequence, use of this model should be restricted to cases in which the underlying assumptions are not severely violated. In

Jan 1, 1970

By Sidney Fischler

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

Jan 1, 1964

By Carrol A. Quam

DURING the first years of operation of the titanium and iron mine of the National Lead Co. at Tahawus, New York, efforts to increase production were hampered by the increased load put on the facilities for sharpening churn-drill bits. The ore and rock are extremely hard and abrasive and it was necessary to sharpen and harden a large number of bits per day to keep the churn drills supplied. Efforts to increase the capacity of the bit shop by a two-shift operation were not wholly successful in that it was hard to train men to do a satisfactory job of sharpening and tempering the bits. The number of bits that were improperly tempered increased, thus boosting the daily requirements for bits at the drills and increasing the load on the bit-sharpening facilities.

Jan 1, 1949

By J. C. Swartz

Measurements of the effect of precipitation stresses on the solubility of cementite (Fe3C) precipitates in a iron are reported. Solubilities were determined from measurements of the Snoek relaxation due to interstitial carbon after quenching from various equilibrium treatments. Stress-free precipitates were obtained by a spheroidizing treatment of vacuum-melted Fe 0.06 wt pet C. Subsequent equilibration treatments were designed to suppress nucleation of other precipitates. The results for stress-free cementite give a heat of solution of 14.8 i 0.2 keal per mole and an entropy change of 1.1 i 0.2 eu in the temperature range 400" to 715°C. Comparison with previous data indicates that the heat of solution increases about 6 keal per mole as temperature increases from 700" to 1000°C. Data on self-stressed cementite in quench-aged specimens of Fe 0.013 wt pet C indicate 1) an apparent heat of solution of 12.1 i 0.4 keal per mole in the range 280" to 690°C, 2) a strain energy of- 1.1 keal per mole Fe3C accompanying precipitation at 280°C, and 3&apos;) a gradual decrease in the strain energy of precipitation with increasing equilibration temperature. In com-parison with 2 and 3 the strain energy calculated for an isotropic model is 1.7 keal per mole Fe3C. The lower values obtained from the experiment indicated substantial stress velaxation by dislocation motion. WHEN a supersaturated solution of carbon in a iron is aged at temperatures in the range 200o to 700oC, the carbon clusters by interstitial diffusion and forms cementite (Fe3C) precipitate particles. Unstressed cementite has a volume per iron atom 9 pet higher than that of a iron;&apos; hence, cementite precipitate particles are usually under pressure from the iron matrix. The pressure would tend to increase the solubility of cementite in iron.&apos; This report describes anelastic measurements of the solubilities of self-stressed and stress-free cementite in a iron. Previous determinations of the cementite solubility are summarized in Table I. The method of cementite formation for each reference was studied to ascertain the state of stress of the cementite. The results judged to be for stress-free and stressed cementite are distinguished in the table. In the next section an estimate of the stress effect is obtained which is clearly too small to account for the large difference between the previous results in parts A and B of the table. THEORETICAL Let AGO be the standard free-energy change of the reaction Fe3C (eem.) = 3Fe (a) + C (in a) [1] in the absence of stresses. Since cementite precipitates appear to be rather pure10 and the carbon is so dilute in the iron,8 the cementite and iron of Eq. [ I] for the stress-free case have essentially unit activities and the activity of carbon equals its atom fraction xoC Then the stress-free equilibrium is expressed by RT In XoC = -?GO 121 To first approximation the change in the chemical potential of carbon due to the precipitation stresses equals the elastic strain energy W accompanying precipitation of a mole of cementite.2 Hence, in the presence of the precipitation stresses the equilibrium is described by RT In x sq = -?G° + W [3] where xsC is the mole fraction of dissolved carbon in the stressed case. An approximate value of W can be obtained from analysis of the inclusion problem in elasticity theory. The inclusion is a small portion of the matrix phase which has suffered a transformation while still imbedded in the matrix. In the absence of the constraint of the matrix the transformation would be equivalent to a uniform dilational strain eT. Both the matrix (a) phase and inclusion (0) phase are assumed to be homogeneous, isotropic materials. When the a and 0 phases have the same elastic moduli, which is approximately true for iron and cementite,11 the total strain energy per mole ß is12 2µVß(eT)2(3 +4 µx)-I [4]

Jan 1, 1968

By E. H. Denny

IN the past few years many men, including technically trained engineers, have been asphyxiated in metal mines, coal mines, tunnels and surface wells where a few relatively simple precautions with regard to ventilation and air testing would have saved them. Death from mine gases is analogous in some respects to death from poison and from drowning. The respiratory passages of a victim who has breathed oxides of nitrogen from burning explosives are badly irritated and a few hours or even a day after exposure he may develop a quick and fatal pneumonia; if, however, he enters without respiratory protective apparatus an atmosphere deficient in oxygen (a condition that may occur in unventilated or poorly ventilated parts of all underground mines) he collapses and if not rescued dies more quickly and surely than a lone nonswimmer who falls suddenly into deep water. An example of an atmosphere virtually without oxygen was demonstrated by an air sample taken by a Bureau of Mines engineer wearing oxygen breathing apparatus in a Cripple Creek shaft some years ago, during the recovery of the bodies of two victims of asphyxiation; analysis of the sample by the Pittsburgh laboratory of the Bureau showed the presence of 18.40 per cent of carbon dioxide, 0.27 per cent of oxygen, and 81.33 per cent of nitrogen, although the atmosphere apparently was clear and normal. In a mine one can pass from good, breathable air to an atmosphere that will kill as quickly as one can dive from a board to deep water below. SOME INSTANCES OF ASHYXIATION BY GASES IN METAL MINES The following typical examples of comparatively recent instances of asphyxiation in metal mines were taken chiefly from reports of various kinds of the U. S. Bureau of Mines.

Jan 1, 1938

By Martin A. Mayers

Five-sixths of all the coal that is mined in the United States is burned, without previous treatment other than screening, for the production of heat and power, so that its value is fixed by its suitability for this purpose. Nevertheless, the characteristics of individual coals that determine their fitness for use in particular pieces of combustion equipment are not yet well known. This condition is due not only to the small extent of our knowledge concerning coal itself, but also to our comparative ignorance of the nature of the combustion process. The following paper is an analysis of the combustion process as it occurs in industrial furnaces, based largely on the results of laboratory research on combustion rates. From this analysis it is possible to determine the characteristics of the fuel that limit the capacity of a given piece of combustion equipment. Limitations imposed by other factors than the attainable speed of combustion will not be considered, since they are subject to a different type of analysis involving the balancing of maintenance costs against fixed charges. In order to observe the relations among the various factors that affect the speed of combustion, representative particles of fuel will be followed through two types of furnaces. A pulverized-coal furnace will be considered first, because the independence of the individual particles facilitates the analysis of the effect of furnace conditions. The second example will be a grate-fired furnace in which ignition of the fuel takes place on the underfeed principle. This includes both underfeed and chain grate stokers, (8)† but does not include hand-fired furnaces and some overfeed stokers. The furnace will be considered to be large enough, the temperature high enough, and enough air provided, to burn the fuel completely, without, for the moment, specifying these quantities more completely. Furnaces Burning Pulverized Coal In a pulverized-coal furnace, the fuel particle is carried, in a stream of air, into the furnace, where it is subjected to radiation from the flame and from the hot walls of the furnace. The increase of particle tempera-

Jan 1, 1936

By Martin A. Mayers

Five-sixths of all the coal that is mined in the United States is burned, without previous treatment other than screening, for the production of heat and power, so that its value is fixed by its suitability for this purpose. Nevertheless, the characteristics of individual coals that determine their fitness for use in particular pieces of combustion equipment are not yet well known. This condition is due not only to the small extent of our knowledge concerning coal itself, but also to our comparative ignorance of the nature of the combustion process. The following paper is an analysis of the combustion process as it occurs in industrial furnaces, based largely on the results of laboratory research on combustion rates. From this analysis it is possible to determine the characteristics of the fuel that limit the capacity of a given piece of combustion equipment. Limitations imposed by other factors than the attainable speed of combustion will not be considered, since they are subject to a different type of analysis involving the balancing of maintenance costs against fixed charges. In order to observe the relations among the various factors that affect the speed of combustion, representative particles of fuel will be followed through two types of furnaces. A pulverized-coal furnace will be considered first, because the independence of the individual particles facilitates the analysis of the effect of furnace conditions. The second example will be a grate-fired furnace in which ignition of the fuel takes place on the underfeed principle. This includes both underfeed and chain grate stokers, (8)† but does not include hand-fired furnaces and some overfeed stokers. The furnace will be considered to be large enough, the temperature high enough, and enough air provided, to burn the fuel completely, without, for the moment, specifying these quantities more completely. Furnaces Burning Pulverized Coal In a pulverized-coal furnace, the fuel particle is carried, in a stream of air, into the furnace, where it is subjected to radiation from the flame and from the hot walls of the furnace. The increase of particle tempera-

Jan 1, 1936

By E. H. Denny

In the past few years many men, including technically trained engineers, have been asphyxiated in metal mines, coal mines, tunnels and surface wells where a few relatively simple precautions with regard to ventilation and air testing would have saved them. Death from mine gases is analogous in some respects to death from poison and from drowning. The respiratory passages of a victim who has breathed oxides of nitrogen from burning explosives are badly irritated and a few hours or even a day after exposure he may develop a quick and fatal pneumonia; if, however, he enters without respiratory protective apparatus an atmosphere deficient in oxygen (a condition that may occur in unventilated or poorly ventilated parts of all underground mines) he collapses and if not rescued dies more quickly and surely than a lone nonswimmer who falls suddenly into deep water. An example of an atmosphere virtually without oxygen was demonstrated by an air sample taken by a Bureau of Mines engineer wearing oxygen breathing apparatus in a Cripple Creek shaft some years ago, during the recovery of the bodies of two victims of asphyxiation; analysis of the sample by the Pittsburgh laboratory of the Bureau showed the presence of 18.40 per cent of carbon dioxide, 0.27 per cent of oxygen, and 81.33 per cent of nitrogen, although the atmosphere apparently was clear and normal. In a mine one can pass from good, breathable air to an atmosphere that will kill as quickly as one can dive from a board to deep water below. Some Instances of Asphyxiation by Gases in Metal Mines The following typical examples of comparatively recent instances of asphyxiation in metal mines were taken chiefly from reports of various kinds of the U. S. Bureau of Mines.

Jan 1, 1940

By E. H. Denny

In the past few years many men, including technically trained engineers, have been asphyxiated in metal mines, coal mines, tunnels and surface wells where a few relatively simple precautions with regard to ventilation and air testing would have saved them. Death from mine gases is analogous in some respects to death from poison and from drowning. The respiratory passages of a victim who has breathed oxides of nitrogen from burning explosives are badly irritated and a few hours or even a day after exposure he may develop a quick and fatal pneumonia; if, however, he enters without respiratory protective apparatus an atmosphere deficient in oxygen (a condition that may occur in unventilated or poorly ventilated parts of all underground mines) he collapses and if not rescued dies more quickly and surely than a lone nonswimmer who falls suddenly into deep water. An example of an atmosphere virtually without oxygen was demonstrated by an air sample taken by a Bureau of Mines engineer wearing oxygen breathing apparatus in a Cripple Creek shaft some years ago, during the recovery of the bodies of two victims of asphyxiation; analysis of the sample by the Pittsburgh laboratory of the Bureau showed the presence of 18.40 per cent of carbon dioxide, 0.27 per cent of oxygen, and 81.33 per cent of nitrogen, although the atmosphere apparently was clear and normal. In a mine one can pass from good, breathable air to an atmosphere that will kill as quickly as one can dive from a board to deep water below. Some Instances of Asphyxiation by Gases in Metal Mines The following typical examples of comparatively recent instances of asphyxiation in metal mines were taken chiefly from reports of various kinds of the U. S. Bureau of Mines.

Jan 1, 1940

By J. A. Fellows, Earnshaw Cook, H. S. Avery

THE increased use of heat-resistant alloys (26 per cent Cr, 12 per cent Ni, 16 per cent Cr, 35 per cent Ni, 12 per cent Cr, 60 per cent Ni, etc ) in recent years has been accompanied by continued demands by the consumer for improvement in properties The manufacturers of these materials, of necessity, have resorted to more critical studies of the basic causes of variations in fundamental properties To keep pace with the need for augmented information, previous techniques of investigation have been refined and new test methods and instruments created It is the purpose of this paper to describe the apparatus, experimental technique and precision of measurement that were employed in the exploration of properties of heat-resistant alloy presented in a companion paper† The detailed precautions in experimental procedure essential for attainment of accurate and comparable data at elevated temperatures cannot be too highly emphasized THE CREEP TEST Since the fundamental concepts of creep testing have been recognized for the past 20 years, present interest is restricted to refinements in equipment and experimental procedure The creep-test laboratory constructed for the American Brake Shoe and Foundry Co is designed to permit 1000-hr tests in the temperature range of 1200° to 2200°F with a choice of applied stress extending from 50 to 50,000 lb per sq in in increments of 50 lb per sq in To simplify the calculation of weight combinations, the loading beams (Fig I) are provided with counterweights to eliminate the tare The precision of the knife-edges (10 1 ratio) is such that a 10-gram weight placed on the upper specimen grip will be exactly balanced by a 1-gram weight attached to the loading shackle Check of the loading weights proved the maximum error to be 0 06 per cent Axial alignment is provided by crossed knife-edges in the grip seats The furnaces are similar in design to those of Crane and Company, Battelle Memorial Institute, and the U S Steel Corporation An 80 per cent Pt, 20 per cent Rh No 19 B and S gauge wire is used as the heating element The details of construction are shown in the radiograph reproduced in Fig 2 The windings are held in place on an alundum tube with alundum cement, the distribution of turns is adjusted to give a maximum temperature gradient of ± 1°F over a 4-in gauge length (Fig 3) To avoid sharp temperature differentials at the ends of the test section, the length of the furnace is four times the gauge length Sixteen-inch coupons are used to reduce the temperature of the threaded

Jan 1, 1942

By Alfred H. Bell

IN 1945, Illinois produced 75,210,000 bid. of oil, or 4.4 percent of the total for the United States, and ranked sixth in the nation in oil production for the third consecutive year. Production decreased about 3 per cent from that of 1944, when the total Illinois production was 77,413,000 bbl. This is the smallest percentage of decrease in production in the state for any year since a peak was reached in 1940. Daily average production for 1945 was approximately 206,000 bbl. Daily averages by months were as follows:

Jan 1, 1946