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By J. A. Sanchidrián, P. Segarra, S. Gómez

Blasting is a common activity in mining that can cause significant damage in the remaining rock mass. The most commonly used method for predicting vibrations is the Swedish or Holmberg-Persson approach. It is a simple and fast method that uses empirical formulation to estimate the vibration levels based on the explosive charge weight, distance to the source, and other parameters. However, it has limited accuracy and does not consider the effect of free surfaces or other boundary conditions. On the other hand, recently developed methods as the full-field solution (FFS) can provide more accurate predictions of vibrations due to excitations provoked by cylindrical columns of explosive, but the inclusion of free surfaces in analytical methods is a challenging problem. This paper presents a new approach that includes free surfaces in the FFS to predict vibrations analytically in the near-field. The main obstacle to including free surfaces in the FFS was the belief that the solution was non-decoupleable in P- and SV-waves separately. The Heelan's approach was previously used to decouple them, but it only provides valid radiation patterns in the far-field and does not account for intrinsic attenuation. In this paper, we address this problem successfully, allowing for the inclusion of free surfaces in the FFS.

Jan 1, 2024

By J. W. Evans

ONE of the most important and frequent calculations that the extractive metallurgist is called upon to make is that of the standard free energy change of a reaction (?F°). For many reactions of metallurgical interest, the lengthy arithmetical calculations have been eliminated by the use of free energy-temperature diagrams which have been constructed by Ellingham,1 Richardson and Jeffes,2 Kellogg,3 and Osborn4 (e.g., for oxides, sulphides, halides) from critical surveys of existing data. The speed and simplicity of making calculations with these graphs make them of great practical value and, this should be stressed, in the majority of cases no greater accuracy is obtained by the individual calculations from specific heat data, entropies, and heats of reaction. With the increasing industrial application of vacuum methods to the winning of metals, notably at present magnesium and the alkaline earth metals, it is necessary to calculate low metal vapor pressures above reaction mixtures. The existing free energy diagrams usually give values where the solid and liquid metals are at unit activity. To obtain the free energy change associated with the reaction Metal (solid or liquid) = Metal (gas) it is customary to calculate this from either vapor pressure equations or from the appropriate free energy functions. This paper presents graphically the free energies of vaporization of a number of metals of economic importance which can be used in conjunction with other free energy diagrams. Certain metals have been excluded on the following grounds: titanium, tungsten, molybdenum, and platinum have very high heats of vaporization and boiling points and the uncertainty of these values arising from difficulties of high temperature measurements makes free energy values of doubtful accuracy; the data for cobalt, vanadium, and zirconium are uncertain; finally, arsenic, antimony, and bismuth could not be conveniently included. because of the presence of mixtures of polyatomic and mona-tomic vapors in the temperature range considered. Free Energy Diagram In Fig. 1, the standard free energies of vaporization per mol (?F°T) have been plotted for the temperature range 0" to 2000°C for the reaction M (solid or liquid) = M (gas) The data have been obtained from the free energy functions — (F-H298)/T for the solid, liquid, and gaseous elements and the heats of vaporization at 298°K, i.e., ?H298 (vapor). The values of these functions have been taken without change from the recent critical survey by Brewer;' the bulk of this data is from Kelley7 with adjustments in the light of more recent work. Values of the function — (F-H298) /T at T = 298°, 500°, 1000°, 1500°, and 2000°K were employed. Where possible, a further independent value was obtained by using the boiling point, i.e., where ?F°T = 0. All calculations are based on the assumption that the metal vapors are monatomic and that the boiling points refer to those temperatures at which the partial pressure of the monatomic vapor above the metal is 760 mm. For the alkali metals, e.g., sodium, potassium, and lithium, diatomic gas molecules are present as minor species; details of these are discussed by Brewer." On the basis of the above values and allowing for the change in slope at the melting point, straight line graphs were constructed and extrapolated to 2000°C. The deviation from a straight line did not exceed ±500 cal, which in all cases appears less than the probable error in the ?F°T values.

Jan 1, 1954

By N. S. Dalal, B. Jafari, F. H. Y. Green, V. Vallyathan

"INTRODUCTIONThe mechanistic details of the biological events leading to coal workers pneumoconiosis (CWP) are not yet fully understood, despite several decades of extensive epidemiologic1.2 and laboratory studies.2-6 Epidemiologic studies1.2 have shown, for example, that the incidence and severity of CWP differ markedly in the different regions and mines at comparable exposures, but laboratory investigations2-6 have demonstrated only partial correlation of the epidemiologic data with the differences in the mineral composition and the rank of coal mined. In particular, while epidemiologic data indicate1.2 direct correlation of the· prevalence and severity of CWP with the rank (i.e., % carbon content) of coal, this correlation has not been established by laboratory4'6 and animal exposure3 studies. In order to explain these results, in 1980 Artemov and Reznik' suggested that perhaps they arise from the fundamental differences in the surface properties of the coal. dusts inhaled by the coal miners and those used in the laboratory studies: while the miners inhale freshly fractured coal particles, henceforth called the 'fresh' coal dust, the laboratory studies generally utilize 'aged' coal dusts (i.e., dusts that have been stored for many days or even longer). Reznik and Artemov' used electron spin resonance (ESR) spectroscopy to show that the mechanical crushing of some Soviet Union coals generated organic free radicals and that the concentration and the decay times (hence the reactivity) of these radicals were higher for the coals of higher ranks. Since some of the radicals decayed within a few minutes in air, the authors surmised that while these radical species could lead to certain specific pathogenic reactions at the sites of mining operations, this might not be the case in the laboratory studies, due to the conventional use of 'stored' dusts which would be expected to contain significantly smaller free radical concentrations. This is consistent with the recent findings that, standardized, aged coal dusts exhibit minimal cytotoxicity. 8While the above mentioned work of Artemov and Reznik7 did suggest a possible new clue to the pathogenesis of CWP (i.e., the role of the coal based free radical species), no direct biological/cytotoxicity data were provided to show that 'fresh' coal dusts were, indeed, more pathogenic than the 'stale' ones. Because of the rather significant implications of the Artcmov-Reznik hypothesis to the understanding of 1hc biochemical mechanism and, hence, the strategies for the eventual containment of CWP, we have initiated a comparative study of the free radical formation and cytotoxicity properties of freshly crushed coal ·particles. As done by Artemov and Reznik, 7 we have used the ESR technique as the direct method of measuring the concentration and decay kinetics of the coal based free radicals. Our preliminary ESR studies on two Pennsylvania coals, a bituminous (carbon content 72 % ) and an anthracite (95 % carbon) coal, have confirmed the Artemov-Reznik finding that the crushing-induced free radical sites are higher on the coals with higher carbon content (i.e., higher rank).9-11 In the present work we describe our more recent results of a parallel study of the time dependence of the decrease in the free radical content of a freshly made anthracite dust (as measured via ESR) and that of the dust's cytotoxicity potential as measured by the extent of hemolysis of (sheep) erythrocytes. We have also investigated the effects of free radical scavengers on the cytotoxicity potential of the dust and deduce that indeed the free radicals could play a significant role in the initial events in the mechanism of the cytotoxic effects due to the inhalation of coal dust inhalation."

Jan 1, 1990

By Richard L. Fischer

Constant-volume charges of precipitated PETN (pentaeythrite tetranitrate) at three specific gravities (0.50, 1.00, and 1.50) were used in laboratory tests to examine the effects of changes in explosive properties on free-surface displacement pulses and on crater dimensions. The tests were performed in large blocks of cement-mortar. The values for the detonation velocity, detonation pressure, specific energy, energy density, and energy release rate were calculated from the explosive loading density. Calculated explosive properties were correlated with free-surface displacement pulse measurements, strain energy, and measured crater dimensions. Increases in explosive properties resulted in increased free-surface displacement pulse parameters and crater dimensions. The loading density, detonation velocity, energy density, detonation pressure, and energy release rate were found to be best indicators of explosive performance. Simple acoustic relationships involving impedance ratios were examined and could not be used to predict peak displacement amplitude or strain energy. Data are presented in the customary English units as well as the International System of Units (SI).

Jan 1, 1970

By R. Zhang, S. Azam, S. Liu, J. H. Golbeck, V. Kurashov, S. Bhattacharyya

Free radicals (FRs) present in coal dust directly influence the interaction behavior between lung cells and dust particles. FRs are atoms or groups containing unpaired electrons, with strong chemical reactivity and a short lifespan. FRs which are quite persistent in natural environments, termed environmentally persistent free radicals (EPFRs), have recently received much attention as new environmentally hazardous substances. EPFRs present on coal dust serves as an active intermediary to catalyze reactive oxygen species (ROS) production by oxygen molecules endangering mine workers’ health. Many EPFR species may be bonded to the particle surface or trapped within the particle during coalification and can be modified with progressive size reduction through cutting at the mining face or crushing/pulverization in the plant. This study measured EPFRs for lignite, sub-bituminous, and anthracite coal dust at various sizes. We especially focused on EPFRs for submicron coal dust prepared by cryogenic methods. The outcome of this study will directly improve the free radical-dependent toxicity quantification and ultimately contribute to the size-dependent coal dust toxicity quantification.

Mar 2, 2022

By J. C. Fisher

Martensite transformations in steels and other alloys are characterized in part by the absence of composition changes during the growth of a new phase. Transformation occurs rapidly, and there is insufficient time for long range diffusion or partition of alloying elements to take place; martensite reactions in alloys thus are similar to phase transformations in single component systems. A fundamental understanding of martensite transformations in steels is impossible without knowledge of the free energy change upon transforming austenite (face centered cubic iron containing alloying elements) to ferrite (body centered cubic iron containing alloying elements) of the same chemical composition. The present paper assembles the best information available concerning the influence of temperature and composition on this free energy change. Most of the material has been taken from the work of Johansson,' Mehl and Wells,2 Zener3,4 and Smith;5 and indirectly, through these authors, from the work of Austin.6 In agreement with the generally accepted viewpoint, martensite is assumed to be an ordered solution of carbon in ferrite of the same composition as the parent austenite; only at high temperatures and low carbon concentrations is the carbon in ferrite distributed at random. The properties of the disordered solution are estimated by extrapolating the known properties of iron-carbon solid solutions into the range of supersaturation, and the free energy change associated with ordering is estimated from the theory developed by Zener. By incorporating Smith's recent thermodynamic measurements and Zener's theory of ordering, the present analysis modifies previous estimates of the free energy change associ- ated with martensite transformations. Consider a two component system consisting of a solvent A and a solute B. Let Na and Nb represent mol fractions of A and B respectively, let aa = raNa and ab = YbNb represent activities, and let superscripts 1 and 2 refer to phases 1 and 2. The partial molal free energies of A and B in phases 1 and 2 can be summarized as follows: free energy standard state Fa' - Fao1 = RT In an1 pure A' Fa2 - Fa2 = RT In aa2 pure A2 Fb1 - Fbo = RT In ab1 pure B Fs2 - FB2 = RT In aB2 pure B. The free energy of a gram atom of phase 1 is* AF1 = Na'Fa1 + Nb'Fb1 and that of phase 2 is AF2 = NA2FA2 + NB2Fb2. A martensite transformation from phase 1 to phase 2 requires Na1 = Na2 = Na and NB1 = NB2 = Nb, and the free energy change per gram atom accompanying transformation is AFi-2 = NA(Fa2 - Fa1) + Nb(Fb2 - Fb1) = NA[RT In (aA2/aA1) + AFa1?2] + Nb RT In (aB2/aB1) = Na[RT In (ra2/ra1) + AFa1?2] + Nb RT In (TaVTB1). [1] where yn2, yn1, yB2, yB1 are activity coefficients, and where Ma'+* is the free energy change upon transforming a gram atom of pure A from phase 1 to phase 2 at the temperature in question. For martensite transformations in plain carbon steels, A = iron (Fe), B = carbon (C), 1 = austenite (7). 2 = ferrite (a), and Eq 1 is AFr ?a= NFe[RT In (rf.a/rfer) + AFF.r?a] + TVc RT In (eca/rc1)- L2] Nothing is known concerning the values of yFea and yca for carbon concen- , trations in excess of 0.025 pct. However, the approximation rf.7 = 7f." = 1 cannot be appreciably in error for small carbon concentrations, and Eq 2 reduces to Afr-a = NfeFfer?a1 + NC RT In (rca/rcr)- [3] Johanssonl and Zenera have calculated MFfr?a from the specific heat measurements compiled by Austin.6* Their calculated values agree closely, and are summarized in Table 1. The activity coefficients relative to graphite for carbon dissolved in iron vary with temperature according to the relationships d In rcr/d(1/T) = AHcr-R dlnyca/d(l/T) = AHCa/R where AHc? and AHca are the heats of solution of graphite in y and a iron. Assuming the values of AH to be independent of carbon concentration and temperature, In rCr = AHcr/RT + I1 In rca = AHCa/RT + 12

Jan 1, 1950

By J. R. Kyte, L. A. Rapoport, R. J. Stanclift, S. C. Stephan

Experimental studies covering a wide range of core materials and fluid properties have been conducted to determine the mechanism of oil displacement by water in a partially gas-saturated porous medium. In all instances, the presence of a gas phase was found to have a beneficial effect in reducing residual oil saturations. The practical significance of this benefit is discussed, and a simplified procedure is outlined for evaluating the effects of free gas on water flooding by means of short core tests. INTRODUCTION In addition to oil and water, reservoirs subjected to water flooding frequently contain, also, a gas phase. Common engineering procedures account for the presence of this "free gas" only from the viewpoint of volumetric balance, implying that the only role of the gas consists of providing "fill up" space. It is usually visualized that during the initial stages of the water invasion, the oil, moving ahead of the water, displaces part of the gas and that subsequently the remaining portion of the gas phase is totally compressed and dissolved in the advancing oil bank. Thus, consideration of a two-phase, water-oil flooding mechanism supplies an adequate basis for predictions of oil recovery if the pressure build-up caused by the flood is sufficiently great, so as to reduce the free gas saturation to a negligible value in any portion of the reservoir by the time that portion is reached by the advancing flood water. In many in- stances, however, waterflooding operations are carried out when the reservoir pressure is still relatively high SO that the pressure build-up associated with the water flood may not result in complete dissipation of the gas phase. Under such circumstances it is necessary to ascertain whether or not the presence of free gas has an effect on waterflood behavior and, if so, to account for any such effect in the evaluation of field operations. The difficulties encountered in attempting to arrive at a comprehensive picture of the displacement mechanism of oil by water in the presence of free gas stem from the fact that most of the published data on this subject were obtained under conditions that were either not clearly representative of those existing in a reservoir or not sufficiently controlled to permit evaluation of the effects specifically caused by the gas phase. Some of the most precise data found in the literature were obtained in tests using a "static" gas phase created prior to each water flood by circulating oil through partly gas-saturated cores until a "trapped," residual gas saturation was established throughout the system.' Other investigations were conducted under more representative conditions where the gas phase was free to move during the water flood: but in most cases the results of these tests were obscured by auxiliary phenomena which arise from the compressibility and solubility of the gas and preclude quantitative conclusions.2,3,4 Prior to water flooding, a reservoir usually contains oil and gas, distributed in a manner in which both are free to move. Thus, the principal objective of the present studies was to determine the type of displacement mechanism occurring when water invades a porous medium containing oil and a "mobile" gas phase. Further-

Jan 1, 1957

By W. H. Ode, W. A. Selvig

Briefly, this swelling test consists in heating 1 gram of pulverized coal in a silica crucible over a gas flame under prescribed conditions to form a coke button which is compared in size and shape with a series of standard profiles numbered 1 to 9. These profiles are intended to cover the size and shape of buttons obtained from coals covering a wide range in plastic properties. The number of the standard profile with which the maximum cross-sectional area of the button most nearly corresponds is recorded as the swelling index. Although the swelling test showed poor relationships with the various tests that were used for measuring expansion or contraction of coal during carbonization, it gave indications of having value in measuring free-swelling and coking properties of coals when burned on fuel tests. An opportunity to investigate this occurred when an engineering company reported pronounced differences in burning characteristics on grates of various shipments of Pocahontas coal. Some of these coals gave trouble by swelling excessively and clogging the grate. Samples were obtained, and it was found that the troublesome coals gave radically higher free-swelling numbers than did the coals that performed satisfactorily. Also, it was found that the free-swelling index test gave better differentiation between coals than could be obtained from the coke buttons from the standard volatile-matter test or iron agglutination-value results. The results of the free-swelling test were confirmed by the Subcommittee on Plasticity and Swelling, Coal, a special group of the Subcommittee, under the chairmanship of R.A. Shuman, worked along with the test method. Estberg, Limacher, and Shuman of the Battelle Memorial Institute investigated the various factors affecting the test and found that the swelling index was a good indication of the suitability of coal for performance on residential-type stokers from the swelling characteristics of the coal. Data were presented that also showed that the index was helpful in the selection of coal for industrial underfeed stokers.

Feb 1, 1948

By N. S. Dalal, B. Jafari, V. Vallyathan

Electron spin resonance measurements have now been completed on the decay kinetics of the organic free radicals formed on crushing or grinding of a well characterized anthracite coal. The free radicals exhibit a complex decay pattern for the first few hours after the grinding, and a smooth decay thereafter. Parallel hemolysis studies indicate. a half-life of the decrease in the cytotoxicity of the fresh· dust to be about half-a-day. The cytotoxicity of the freshly-made dust decreases on addition of superoxide dismutase, catalase and sodium benzoate. The hemolysis rate is lower for the dust stored in buffers as compared to air. A chemical model will be presented to accomodate the cytotoxicity and spectroscopic data, and ~heir implicati6ns to pneumoconiosis.

Jan 1, 1988

By Roy F. Abernethy

This publication by the Federal Bureau of Mines contains the free-swelling indexes for 2,812 samples of coal received from January 26, 1948, to July 15, 1957, and the Hardgrove grindability indexes for 2,339 samples of coal received from June 23, 1947, to July 15, 1957. These data consist of the origin of the sample, bed name, and analysis. Summaries show the high, low, and average values for each bed. The free-swelling index is a relative measure of the caking properties of a coal when burned on a grate, and the Hardgrove grindability index is used to estimate the relative ease of grinding coals. Development and standardization of these test procedures were at a much later date than those for the more familiar tests, such as proximate and ultimate analyses and calorific value determinations. The newer tests are valuable in supplying supplemental information, particularly for assisting in evaluating coals used in certain types of combustion processes.4/ Data from such tests are important to designers of burning equipment, operating engineers, and purchasing agents. Data from these newer tests are scarce and scattered through a number of publications. Special projects were started to determine the free-swelling and grindability indexes, in addition to the regular analyses on the tipple samples collected by Bureau engineers. Since the start of these special projects, all the coal fields of commercial importance have been adequately covered in the sampling program.

Jan 1, 1961

By Alla D. Mah

Combustion energies of barium and strontium were measured by means of the combustion bomb calorimeter. The heats of formation obtained for the oxides were ?H298.15 = -139,060 ± 700 cal/mole of barium oxide (BaO) and ?H298.15 = -144,440 ± 400 cal/mole of strontium oxide (SrO). Tables containing heats and free energies of formation from 298.15° to 2,000° K were prepared.

Jan 1, 1963

By K. K. Kelley

The heats of formation of two lead vanadates (Pb2V207 and Pb3V208) and manganese vanadate (MnV206) were determined by hydrochloric acid solution calorimetry, supplementing previous Bureau of Mines measurements of the vanadates of calcium, magnesium} and sodium. Heat and free energy data for 11 vanadates were assembled on a common basis. The stability of comparable vanadates (with respect to the oxides) increases in the following order: Magnesium, manganese, lead, calcium, sodium.

Jan 1, 1963

By E. Swartzman, G. C. Behnke

THE free-swelling index, a numerical value for the free-swelling properties of coal, is being used to an increasing extent in specifying coal for burning in various types of equipment. The empirical standard ASTM method for determining this index uses, as a source of heat, a gas burner which requires frequent calibration because gas pressures are not constant, relatively small changes in gas pressure resulting in rather wide variations in the temperature attained in a crucible and thus in the resultant size of the coke button. Furthermore, the quartz crucibles specified for the test are not standard equipment, and relatively small variations in dimension and wall thickness from those specified often result in rather wide variations in the resultant size of the button. A method of analysis to be satisfactory not only for a scientific laboratory but also for use in industrial control laboratories under varying conditions should employ equipment which is rugged, easily calibrated, and readily replaceable by standard materials. Gas is not universally available as is electricity, and it is generally easier to calibrate and control a simple electric furnace or heater than a gas burner, the voltage not usually fluctuating to the degree that gas pressure does. Quartz crucibles are fragile, and the size specified in the test is not normally used for any other purpose in the laboratory. Although more expensive, the 15-cc platinum crucible, available in all laboratories where volatile matter in coal is determined by the standard ASTM method, is sturdy and standard and easily replaced. Because of these considerations, a modification of the standard method has been developed which employs a standard laboratory 350-w cone heater and standard 15-cc platinum crucibles. The results of numerous tests conducted with such apparatus show conclusively that the free-swelling index values as judged by the buttons produced with this equipment are exactly the same as those obtained by the standard gas burner method. Thus it is suggested that this electric cone heater method employing standard 15-cc platinum crucibles be considered as an alternative to the ASTM method, Designation: D720-46. The free-swelling index of coal is determined by means of the ASTM method, D720-46. This method, which is an adaptation of the crucible swelling test for coal of the British Standards Institution, consists of heating 1 g of coal in a special covered quartz crucible in a regulated gas flame for a period of not less than 2.5 min in which time the temperature of the inner surface of the bottom of the crucible reaches a temperature of 82025°C. The residual coke button is then compared in size and shape with a series of standard profiles shown in Fig. 1 and designated by number from 1 to 9 in increasing order of size. As the method is empirical, it requires rigid standardization of the apparatus and repeated calibration of the gas burner. The dimensions of the low form quartz crucible recommended must be rigidly adhered to as small variations in diameter or wall thickness result in variations in the rate of heat transmission and thus in the resultant size and shape of the coke button. The gas burner must be calibrated almost every time a new set of determina-

Jan 1, 1952

By S Basu, S L. A Gowravaram

CaF2 has been a common constituent in a wide variety of welding fluxes, including those used for submerged arc welding (SAW). The widespread use of CaF2 stems from its role in lowering the liquidus temperature as well as the viscosity of the molten slag that covers the weld pool. However, the harmful effect of fluoride evaporation from molten flux, on the environment as well as the health of the users is becoming increasingly evident over the years. This has led to increasing attention towards reducing the CaF2 concentration in the fluxes. The fluoride-free formulations face the challenging requirement to maintain the thermo-physical properties (viscosity, liquidus temperature etc) like those observed in fluoride-containing fluxes. In the present work, three fluxes with compositions in the CaO-MnO-SiO2-Al2O3 system have been identified as promising alternatives to the CaF2-rich fluxes. However, the thermo-physical properties of any such flux need to be comparable to CaF2-based commercial SAW fluxes before it can be adopted for regular use. The single hot thermocouple technique (SHTT) has been used by several researchers in the past as a tool for observing the melting and solidification characteristics of fluxes. This device has been developed in the present work and is used to characterise the melting behaviour of the fluxes. The measured solidus and liquidus temperatures from SHTT were compared with the results from differential thermal analysis (DTA) and simulations using the FactSage™ software for a comprehensive understanding. In spite of having a slight deviation in the measured values from the multiple techniques, the results obtained from these multiple methods show that the selected compositions could be potential CaF2 free alternative welding fluxes.

Jun 19, 2024

By T. V. Jayaraman, Kranti Kumar, Paul Praveen J., Dibakar Das, A. R. James

"Lead free piezoelectric ceramics with high piezoelectric coefficients are in great demand for sensor and actuator applications. Synthesis and characterization study of one such lead free system, barium zirconate titanate - barium calcium titanate [xBZT-(1-x)BCT] (x = 0.5), via solgel method have been carried out. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the formation of single phase BZT-BCT nanoparticles (<50 nm). The as-synthesized powders were calcined at 1000°C and the powders were pressed into cylindrical pellets. Solid-state sintering of the green pellets at 1550°C for 2 hrs resulted in single phase perovskite structure. Hysteresis loops were obtained which indicates the ferroelectric nature ofBZT-BCT. The bulk ceramic samples with the highest sintered density (~93%) were subjected to electrical poling and the piezoelectric properties ( d33, kp, & i:,) were measured. The structure and piezoelectric properties were investigated and correlated for the given composition of the BZT-BCT system.IntroductionPiezoelectric ceramics are widely used in various sensors and actuators and most of the piezoelectric ceramics, which are presently used, are lead based, which contains at least 60% lead (Pb) by weight. The critical disadvantage of these lead based piezoelectric ceramics is their hazardous effect related to the toxicity of lead, which poses a serious environmental concern starting from their processing to the disposal stage[l]. It is well known that a material to be a good piezoelectric it requires a morphotropic phase boundary (MPB) i.e. the composition induced phase transition between any two ferroelectric phases."

Jan 1, 2013

By T. S. Plaskett

A striated structure perpendicular to the growth axis was observed by the copper-decoration tech-nique in dislocation-free, .float-zoned silicon crystals. The striations, which were spaced about 100 p apart, fitted the relationship d = f/u , where d is the spacing, f is the growth rate, and u is the crystal rotation rate. Each stria was resolved into an UNDOPED silicon crystals pulled from quartz crucibles by the Czochralski technique usually exhibit a striated structure perpendicular to the growth axis.&apos;-&apos; This structure has been attributed to oxygen segregation, with the oxygen being introduced from the quartz crucible. If the crucible is rotated, the level of oxygen contamination has been reported as high as 10° atoms per cu cm.10 These striations are similar to solute striations commonly observed in doped Czochralski-grown crystals. The periodic nature of the striations is caused by a periodic variation in the growth rate",12 which is attributed mainly to thermal gradients in the melt.13 A finer striated structure14 attributed to constitutional supercooling is sometimes observed between the coarse striae. The oxygen striations have been observed by infrared transmission techniques,&apos; by the copper-decoration technique,&apos; by X-ray diffraction microscopy,6-8 and by 9 p absorption measurements3 on crystals pulled from the melt both with and without dislocations. In this investigation float-zoned dislocation-free crystals were examined by the copper-decoration technique. The level of oxygen for float-zone material is less than 1016 atoms per cu cm the lower limit of detection by 9 p absorption measurement. EXPERIMENTAL TECHNIQUE The crystals were grown by the float-zone process with the rf heating coil outside of the quartz envelope containing the silicon. All float zoning was done under an atmosphere of purified helium. The Dash technique15 was used to grow the crystal dislocation-free. This involves growing the crystal initially with a diameter between 2 and 3 mm and at array of starlike precipitates of copper. The strucLure was not .found at the surface tor a depth of about 1.5 mm, or in a region of similar width ahead of a dislocation network. The structure is postulated to consist of vacancy clusterings or dislocation loops. very rapid rates, about 20 mm per min, for a distance of about 3 cm. The diameter of the crystal is then increased to the diameter of the source of silicon, which in this case was about 19 mm. Because of the arrangement of the apparatus, the zone was passed downward rather than upward, contrary to the standard float-zoning practice. Also, the source was rotated rather than the seed. ziegler17 has made dislocation-free crystals by a similar technique but has passed the zone upwards. The starting material was zone-refined and had a p-type resistivity of 150 ohm-cm. The major impurity was boron; the total impurity excluding the boron was reported by the supplier (Dow-Corning) to be typically less than 2 x 1013 atoms per cu cm. The crystals were examined by the Dash copper-decoration technique18&apos;19—a method in which about 10" atoms per cu cm of copper are diffused at a temperature between 900" and 1000°C into silicon which is then quenched to room temperature. On quenching, the copper precipitates on crystalline defects which are then visible when viewed by transmission infrared microscopy. The photomicrographs shown were taken either of the infrared image tube screen or directly on infrared film. All sections prior to decorating were chemically polished and, for some sections, given a sirtlZ0 dislocation etch-pit examination. After decorating, the samples were mechanically polished. RESULTS A photomicrograph, taken in transmission of a decorated cross section, is shown in Fig. 1. The portion of the section shown is near the surface of the crystal. The entire cross section showed no dislocation etch pits after being given a Sirtl etch treatment. It is seen that the copper precipitated randomly. Each precipitate, as has been reported by others, was found to have a starlike structure.

Jan 1, 1965

By Kenji Monden

"The creep properties of tin-based lead-free solders Sn3.0AgO.5Cu and SnO.7CuO.1Ni and lead solders 10Sn90Pb and 50Sn50Pb were investigated at temperatures between 298 K and 398 K. The creep-rupture time decreases with increasing initial stress and temperature. The analysis of the solder creep curves uses the Omega method. The creep rate E is expressed by following formula: 1n ? = 1n ?0 + O?, where ?0 and O are experimentally determined. The parameter Eo increases with increasing initial stress and temperature. The activation energy for ?0 is 108 kJ/mol for Sn3.0Ag0.5Cu and 85 kJ/mol for SnO.7CuO.INi. These energies suggest that the lattice diffusion of tin is dominant. The energy of 1OSn90Pb is 37 kJ/mol and that of 50Sn50Pb is 67 kJ/mol. The creep-rupture time is calculated using the parameters, ?0 and O. The calculated creep-rupture time is in good agreement with the measured creep-rupture time.IntroductionLead-free solders are replacing traditional tin-lead solders as part of a major trend toward protecting the earth's environment. However, tin-lead solders are currently needed for a high temperature range. Since creep is the main deformation mechanism in solder joints, understanding a constitutive model for creep and examining creep data for solders are important for reliability analysis of solder joints. A steady-state creep equation is generally used for solders [1,2], and it supposes that the secondary-, or minimum-, creep rate occupies the entire creep life. However, secondary creep accounts for only about 15 % to 40 % of the entire creep life for solders. Thus, the equation may not represent the entire creep life."

Jan 1, 2012

By Alla D. Mah

Energies of combustion of vanadium nitride (VN) and vanadium carbide (VC) were measured. Correcting to vanadium tetroxide (V204) as the final state, the heats of combustion were ?H298.15=-118,700±100 cal/mole of vanadium nitride and ?H298.15=-240,270±360 cal/mole of vanadium carbide. With vanadium pentoxide (V205) as the final state, the heats of combustion were ?H298.15= -133.440±100 cal/mole of vanadium nitride and ?H298.15=-255,020±360 cal/mole of vanadium carbide. Combining these results with vanadium oxide data, the heats of formation obtained were ?298.15=-51,880±200 cal/mole of vanadium nitride and ?H298.15=-24,350±400 cal/mole of vanadium carbide. Heats and free energies of formation of vanadium nitride and carbide were calculated to 2,000° K.

Jan 1, 1963

By J. S. Dunning

The Bureau of Mines investigated a series of Fe-Al-Mo alloys strengthened by ZrC (zirconium carbide) precipitates as chromium-free substitutes for stainless steels. Melting and fabrication methods were devised, and the effects of minor additions of columbium (niobium) and cerium on the mechanical properties and oxidation resistance were determined. Zirconium carbides could not be con-trolled reliably to produce fine precipitate dispersions. A more reliable carbide strengthening mechanism is required if the high-temperature strengths of types 304 and 316 stainless steels are to be duplicated. Workability and oxidation resistance of the alloy series were excellent.

Jan 1, 1982

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,&apos; is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors&apos; sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958