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By Wilbur I. Duvall

The borehole deformation gage and overcoring techniques developed by the Bureau of Mines form one of the primary methods of determining in situ rock stress. This report describes a least squares method of calculating the average rock stress components in the horizontal plane from more than three diametral deformation measurements in a vertical borehole. This least squares analysis provides a means of determining the multiple correlation coefficient, the variance, and the scatter for a set of deformation measurements. From this information, confidence limits can be calculated for the secondary horizontal principal stresses and their directions. The material presented in this report can be used as a guide to the development of least squares solutions for stress measurement techniques other than the borehole deformation method. Since the statistical information that results from the least squares method is extremely useful in the interpretation of results, it is recommended that a least squares analysis be used on stress measurement data whenever possible.

Jan 1, 1979

By G. E. Archie

The usefulness of the electrical resistivity log in determining reservoir characteristics is governed largely by: (I) the accuracy with which the true resistivity of the formation can be determined; (2) the scope of detailed data concerning the relation of resistivity measurements to formation characteristics; (3) the available information concerning the conductivity of connate or formation waters; (4) the extent of geologic knowledge regarding probable changes in facies within given horizons, both vertically and laterally, particularly in relation to the resultant effect on the electrical properties of the reservoir. Simple examples are given in the following pages to illustrate the use of resistivity logs in the solution of some problems dealing with oil and gas reservoirs. From the available information, it is apparent that much care must be exercised in applying to more complicated cases the methods suggested. It should be remembered that the equations given are not precise and represent only approximate relationships. It is believed, however, that under favorable conditions their application falls within useful limits of accuracy. Introduction The electrical log has been used extensively in a qualitative way to correlate formations penetrated by the drill in the exploitation of oil and gas reservoirs and to provide some indication of reservoir content. However, its use in a quantitative way has been limited because of various factors that tend to obscure the significance of the electrical readings obtained. Some of these factors are the borehole size, . the resistivity of the mud in the borehole, the effect of invasion of the mud filtrate into the formation, the relation of the recorded thickness of beds to electrode spacing, the heterogeneity of geologic formations, the salinity or conductivity of connate water, and, perhaps of greatest importance, the lack of data indicating the relationship of the resistivity of a formation in situ to its character and fluid content. On the Gulf Coast it is found that the effects of the size of the borehole and the mud resistivity are generally of little importance, except when dealing with high formational resistivities or extremely low mud resistivities. Fortunately, little practical significance need be attached to the exact values of the higher resistivities recorded. Low mud resistivities are not common, but when this condition is encountered it may be corrected by replacing the mud column. With the present advanced knowledge of mud control, invasion of mud filtrate into sands can be minimized, thereby increasing the dependability of the electrical log. The effect of electrode spacing on the recorded thickness of a bed is often subject to compensation or can be sufficiently accounted for to provide an acceptable approximation of the true resistivity of the formation. As development of a field or area progressively enhances the knowledge of the lithologic section, the resistivity values of the electrical log take on greater significance, ultimately affording acceptable interpretations. The salinity, and

Jan 1, 1942

By H. Biloni, G. F. Bolling

The microsegregation in tin specimens containing 0.2, 0.5. or 1 wt pct Pb has been studied m detail. The specimens were grown from the melt in a controlled fashion and exhibited a well-developed cellular substructure. In general, a severe microsegre-gation can be observed in all the photomicrographs presented. Some observations of special interest are: the distribution of a second phase, the presence of a eutectic in several forms, the evidence for dif- THE Smialowski or cellular substructure which forms during solidification has been extensively studied during the past decade.'* Many of the im- *Most references to the cellular substructure except for the last 2 years are reviewed by Winegard.' portant characteristics of this substructure, such as its occurrence and variability with growth conditions, its association with the phenomenon of constitutional supercooling, and its effect on dislocation production and mobility, have received quantitative fusion of solute in the solid, and the enhancement of segregation at a dislocation subboundary network ("striations"). On the basis of the metallographic observations, it can be deduced that the segregation observed is representative of the solute segregation produced during crystal growth. Some deductions are also made about the interplay of the two substructures, cells and striations, and about the mode of cellular growth. investigation both experimentally and theoretically. However, the concentration profile of the solute segregated during crystal growth has not been examined in detail. Tin crystals grown from melts containing various concentrations of lead have been most extensively studied. In a recent investigation of Sn-Pb alloys, Kramer et a1.2 were able to measure the effective solute distribution coefficient, k,, at the most advanced points of the solid-liquid interface, over a large range of growth conditions, finding it to approach the value of k,, the equilibrium distribution coefficient. As will be shown, this must lead to drastic segregation. Another recent study of several Sn-Pb alloys was made by Plaskett and winegard3 who investigated the variation of growth conditions

Jan 1, 1963

By C. G. Dunn, E. F. Koch, K. T. Aust

Strain-induced grain boundary migration was studied in a series of silicon-iron (3% pct Si) bicrystals of controlled orientations. Each bicrystal was given a 7 pct cold-rolling strain rind annealed at 1100°C. The direction of boundary migration was found to depend on orientation; results for several orientations related by a common [110] axis are given. Analysis of the micrographic and X-ray data is made in terms of the residual strain-energy densities within the crystals (energy per unit volurne) and a driving force on the boundary due to an energy density difference across the boundary. Relative strain energies were obtained for the various orientations investigated. A CHROME-acetic acid electroetching method for revealing dislocation sites in silicon iron was previously applied to clarify the structural features and the energetics involved in strain-induced grain boundary migration.',' The present paper is a continuation of this study, but is primarily concerned with the influence of crystal orientation. Sperry, as reported by Beck,3 attempted to determine the factors that influence the preferred growth of one grain over another in aluminum due to strain-induced boundary migration. He found that the particular grain of a pair which work hardened more was invaded, although exceptions to this correlation were noted. The index of work hardening was determined from microhardness measurements of each grain before and after cold-rolling. In the present study, orientation itself was taken as a useful variable for studying the behavior of individual grains in a bicrystal and the direction of boundary migration, since the extent of work hardening is orientation dePendent." The effect of strain on boundary migration is evident from a consideration of driving forces. Thus, in the absence of inclusions, the driving force (per unit area of boundary) for growth of grain A into grain B when a bicrystal is strained and annealed may be expressed as follows:2

Jan 1, 1960

By İbrahim Çınar, Hakan Özşen

Mine workers in heavy and dangerous work are under several physical risk factors, for example temperature, humidity, noise, vibration, lighting and air velocity. Thermal comfort includes parameters such as air temperature, air humidity, air flow rate, radiant heat, metabolic rate and garment insulation. In this study, thermal comfort conditions were evaluated using thermal comfort indices defined as predicted mean vote (PMV) and predicted percentage dissatisfied (PPD) which were determined by measurements taken from an underground coal mine for approximately 100 days. Although the metabolic rate (light work) was kept at 2 met, it was found that predicted mean vote ranged between − 2.58 and 1.68. The predicted percentage dissatisfied index was found to reach 95%. According to the results, it can be seen that thermal comfort may have negative effects on occupational health and safety. The change in thermal comfort index values in the Soma Underground Coal Mine was investigated in detail and the reasons for the changes were determined. Furthermore, determining the optimal working environment for the mine workers was also an aim of this study.

By Roland Trunk, Marcel Imbach, Yves Boissonnas, Jan Vesely

"INTRODUCTION The expansion of the Suez Canal, which runs between the Mediterranean and Red Sea, is at the top of Egypt’s economic agenda. The £8 billion development plan includes a new channel alongside the existing one which will double the number of ships able to pass each day and several tunnels to connect the Sinai peninsula to the main part of Egypt. The Egyptian government ordered three new tunnels under the Suez Canal in the area of Port Said as part of the Canal Region Development Plan. The three tunnels will contribute to the North Sinai expansion, helping to create a vast industrial zone and completing the coastal road extension from Rafah to Nuewiba. Two of these three tunnels will be allocated for roads and the third for railway traffic. A further part of the Suez Canal development mega project are an additional six tunnels in the area of Ismailia and Suez. The focus of this paper is on the two road tunnels in Port Said and will give an overview of the project and the challenges encountered regarding the technical complexity and tight time schedule both in its design and execution. PROJECT OVERVIEW The tunnels will be built in the area of Port Said (see Figure 1) which is the most northern part of the Suez Canal.The road alignment connects the Port Fuad Road in the east bank of the Suez Canal to the Port Said-Ismailia highway in the west bank with a dual carriageway section. Each of the carriageways has two lanes. The bored diameter of the 2.8 km long road tunnels is 13.050 m and will be driven with two Mix-Shield TBMs. The distance between the two tunnel axes is planned with 42.5 m (discussion about a reduction are ongoing). The width of the Suez Canal is around 340 m at upper level and around 170 m at the bottom. During the TBM drive, three main geological layers are expected. Below a depth of around 40 m in a very soft clay layer, a dense to silty sand layer is predicted. Within the sand layer another silty hard clay is expected in different depths with variable thickness. After finishing the excavation of the road tunnels, the same TBM will be used for the railway tunnel. The lowest points of the road tunnels will be located 59 m below the surface (tunnel invert to surface) and only 18 m of ground cover exists between the tunnel crown and the Suez Canal invert. Minimum ground cover over the tunnel crown is approximately nine meters at the tunnel portals."

Jan 1, 2016

By Randolph Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish or animal life in field tests or in controlled experiments.

Jan 7, 1950

By Mitsutaka Hino

The contents of gangue minerals, such as Al2O3. P2O5, crystalline water and so forth in the iron ore imported to Japan tend to increase year by year. Though the increments of such gangue contents arc approximately 0.1-0.2 mass%, some problems for the blast furnace operation in ironmaking process have already been reported, In order to clarify the mechanism of harmful effect caused by the small increment of gangue minerals, mainly Al2O3. on the blast furnace operation, the dripping behavior of Fe,O-CaO-SiO2-Al2O3-MgO slag from the iron funnel, which simulated the micro-porosity in sinter ore, has been observed with the wide range of basicity, Al2O3, Fe2O and MgO contents. The effect of MgO on the dripping behavior of slag has been summarized in this paper. It was found that the addition of 2mass% MgO resulted in large increase of hold-up on the most of the conditions. When Fe2O content was less than 20mass% and the basicity was lower than 0.8, MgO lowered the hold-up even if the slag contained 10mass% Ah03. Every slag hold-up showed the minimum at the basicity of less than unity on the conditions of constant Fe2O and Al2O3 contents, This trend became remarkable when the slag contained 2 mass% MgO.

Jan 1, 2003

By Michael E. Zellars

The distribution of phosphate in Pliocene-Miocene deposits of the Southeastern United States was controlled by the prevailing geologic setting. For each basin a unique set of conditions in terms of relationship of land mass to shelf, depositional environment and seawater composition, and movement controlled phosphate distribution. Concentration sufficient to recognize the deposits as a resource occurred in lagoons or shallow neritic zones, with clastics and carbonates diluting the section basinward. Each deposit within a basin displays similar metallurgy and lithology, notwithstanding post-depositional alteration.

Jan 1, 1978

By G. R. Fitterer

Trends in slag composition in acid open hearth practice, particularly the variation in iron and manganese oxides during refining, are reviewed. A procedure which is currently being used to control the refining reactions is described and partially explained through slag phase diagram considerations. In addition, the ionic nature of these slags is considered and it is proposed that silica combines with the oxide ion and forms a series of complex silicate ions. The effect of basic oxides such as FeO, MnO, and CaO is apparently additive in furnishing the oxide ion for this purpose. IT is now possible to control192 the refining of steel in an acid open hearth furnace to a surprising degree. This control has been brought about through the knowledge and use of several facts and tests. These are: 1—A planned charge analysis based on a knowledge of the type of fuel, the bath depth, etc. 2—Knowledge and control of rate of fuel input as well as its method of atomization, if any. 3—Determination of the slag fluidity. 4—Bath temperatures (use of the Pt-Pt-Rh thermocouple). 5—Periodic determination of carbon content (use of the Carb-analyzer or Carbometer). Through the use of these control methods, a heat may be made to "melt-in" with or without residual manganese and silicon. The rate of refining or carbon elimination may be controlled accurately, and the desired tapping (or "go-ahead") carbon may be approached at a rapid or slow rate according to preference and type of steel being made. Thus operating time may be predetermined and greatly reduced. Further, all of the refining can be done without any ore or other oxidizing additions, and the heat may be brought to the desired tapping temperature simultaneously with the attainment of the desired carbon analysis. This control procedure is being used in most acid plants in the United States today and has been de- scribed.', ' Although the slag metal relations are sufficiently well known to control the heat as stated, yet it is possible to account for only about two-thirds' of the 0, which must have been used for the elimination of the carbon and other metalloids. Phase diagram studies' of the slags, slag weights, the metal particle theory,' ore additions, limestone additions, etc., may all be taken into consideration; yet, the mechanism of oxidation and source of all the oxygen remain to be explained. This paper reviews some of the principles upon which the control methods were based and proposes other possibilities regarding the unexplained phenomena. Old and New Acid Open Hearth Practice Some of the recent statements in the literature regarding acid open hearth operation are based on old heat data which are not typical of modern American practice. These old heat logs have been responsible for many misconceptions regarding the acid hearth practice and represent heats which do not coincide with modern methods. In recent years, American practice has been altered materially and these changes will be briefly described. Modern American Practice: A typical log of a modern American acid open hearth heat' is shown in Fig. 1 which indicates that the refining time was only two hours, during which the carbon was eliminated rapidly and the bath temperature increased at a fast rate. The manganese and silicon contents of the metal were essentially eliminated and their oxides had become constituent parts of the slag at the "melt-down" period. During the course of the heat, the MnO content of the slag remained practi-

Jan 1, 1954

By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan' have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn' have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5', Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By K. E. Brown, J. P. Brill, T. C. Doerr

A wide range of intermittent gas-lift tests way conducted in a 1,500-ft experimental well through 11/4- and 11/2-in, nominal size tubing. The well was equipped with two gas-lift valves, four Maihak electronic pressure transmitters and surface facilities to measure casing and tubing pressures, temperature, liquid production and the rate and volume of gas injected. For each tubing size, tests were conducted varying the slug length, gas volume injected and liquid viscosity and surface tension. From these tests, an empirical "fallback" or liquid loss correlation has been developed. No general fallback correlation could be obtained, and the correlation is presented in the form of one curve for each slug length of a given liquid and lubing size. A conceptual model has been developed which combines the fallback correlation with equarions which govern liquid slug pow. A mathematical simulation of the model in the form of a digital computer program is used to calculate total recovery, gas volume used and clearance time for a given test. Tubing pressures at the gas-lift valve and at the gm-slug interface are calculated as a function of time. Tubing pressures at the surface during slug clearance ore also calculated. The results compare favorably with the test data and verify the conceptual model. The extent to which the model can be used for other tubing sizes, depths, liquids and gas-lift valves can only be determined with additional experimental data. Data are also necessary so that a fallback curve can be constructed for the particular test conditions studied. INTRODUCTION The flow of liquid slugs in vertical conduits has long been an established production method in the petroleum industry. Under the name "intermittent gas lift", many advances have been made in engineering design. However, the unsteady-state nature of liquid slug flow has discouraged attempts to describe the problem analytically. The result has been that intermittent gas lift is dominated by rules-of-thumb engineering practices developed over many years. The advent of slim-hole completions has increased the demand for a more rigorous solution to the intermittent problem. Small-diameter conduits offer more frictional per intermittent cycle. Small-diameter conduits are defined to be 1%-in. nominal size tubing or smaller. When oil is produced from the reservoir in which it is found, and transported to surface tanks by intermittent gas lift, three separate flow stages are encountered: flow of the fluids to the wellbore through a porous medium, vertical flow of a liquid slug from the point of gas injection to the surface, and horizontal flow of the liquid slug through the surface flowlines from the wellhead to the surface tanks. The three stages are depicted schematically in Fig. 1. The present study deals with liquid slug flow in both the vertical and horizontal conduits, ending when the bottom of the liquid slug reaches the surface. Due to the large number of variables involved, the analytical study of intermittent gas lift is extremely complex. The possibility of flow regimes other than slug type, the nature of the force fields acting on the system, the interfacial instabilities involved, the varying operational principles of existing gas-lift valves and the complete unsteady-state nature of the physical phenomena occurring in an intermittent gas-lift cycle relate some of the difficulties encountered.

By John G. Simmons

A tutorial account of the tunnel effect between metal electrodes separated by a thin insulating film is presented. Energy diagrams of metal-insulator -metal sandwiches are briefly discussed, and the isothermal and thermal J-V characteristics for symmetric and asymmetric tunnel junctions are derived from a generalized expression. Experimental data from tunnel junctions are presented, and it is shown how, correlation between theory and experiment permits a determination of some of the oxide properties. Finally, the barrier heights in AT-Al2O3-A1 junctions determined by various inr3estigators are discussed. The object of this paper is to give a tutorial account of the electric-tunnel effect between metal electrodes separated by a thin insulating film and to illustrate its utility in the study of metal-oxide interfaces. This paper will emphasize the theoretical aspects of the electric-tunnel effect: however, a brief account of the more recent experimental work will be presented. A more comprehensive experimental study of the tunnel effect will be presented in the following paper by Drs. Pollack and Morris, see p. 497. We will open with a discussion of the energy diagrams for metal-insulator-metal junctions and what we mean by the electric-tunnel effect. Following this is an account of the theoretical studies of Sommerfeld and Bethe, and Holm, and the recently reported calculations on symmetric and asymmetric junctions using the generalized formula. The theoretical presentation is concluded with calculations on the temperature dependence of the tunnel J-V characteristic. In the experimental section, it is shown how barrier heights and thicknesses are determined by comparing the experimental data with the theory. Finally, the results of various investigators on the determination of the barrier heights in Al-Al2O,-A1 systems are discussed. I) POTENTIAL BARRIERS BETWEEN CLOSELY SPACED ELECTRODES Since it is necessary to supply energy to a metal in order to observe electron emission from its surface, it is evident that the potential energy of an electron within a metal is lower than that of an electron at rest outside the metal. It follows, then, that the electron must undergo a change in potential as it crosses the metal-vacuum interface. In the Sommerfeld1 free-electron theory of metals it is assumed that the free electrons, the electrons responsible for the electrical characteristics of metals, move in a constant potential environment in the metal, and are contained within the metal by a potential barrier at the metal-vacuum interface. It will be evident that the idea of a constant potential environment is a very idealized model, since the potential energy of an electron is influenced by all of the atoms and the other electrons within the metal; however, its use is justified by the many excellent results it gives.2 Fig. l (a) is the energy diagram of the model envisaged by Sommerfeld; the metal is represented by a potential-energy well of depth V,; the vacuum level represents the energy of an electron at rest outside the metal. At 0°K the electrons, which exist in pairs in discrete energy levels, fill up the well to an energy ?, the Fermi level. The distance, Vo - ?, from the Fermi level to the vacuum level is known as the work function of the metal, and represents the minimum energy required to free electrons from the interior of the metal at 0°K.

Jan 1, 1965

By W. H. Emmons

Although gold is one of the rarer metals, it is widely distributed; it is found on all of the continents and in each of the grand metallogenic provinces of the earth. It is prominent particularly in the shield areas of the earth; these areas have produced a large part of the world's lode gold and in most of them gold lodes are more important than the lodes of other metals. The Scandinavian shield is the only one that has not produced much gold. Nearly all of the world's gold has been derived from lodes and from sands and gravels where gold placers formed by the destruction of lodes. The gold derived from magmatic segregations, from pegmatites and from contact metamorphic deposits is quite subordinate to that derived from auriferous lodes. The lodes include all veins and related deposits that are formed by hot waters that move along fissures or other openings and that deposit vein 'matter :in the fissures and by replacement of the country rocks along the fissures. All of the shield areas of the earth are characterized by large areas of granitic rocks including granitic gneisses, granodiorites and other acid intrusives which here are included in the general term "granite." The granites are intruded into schists, ancient lavas and other rocks which here are designated as the "invaded" rocks. The granites are parts of what once were great batholiths: that is, they are the remaining portions of great deep-seated bodies that slope outward, have very irregular roofs and so far as known have no floors but extend downward to great though unknown depths. Some of them are scores or hundreds of miles across and contain islands or "roof pendants" of the invaded rocks at places where the roofs of the batholiths were low—that is, where erosion has not yet completely unroofed the batholiths. It is in these islands of older rocks and in the narrow marginal belts and cupolas of the batholiths that practically all of the gold lode deposits of the shields are found. Valuable lodes are lacking generally in the granites themselves except in grahite within a mile or less from .the contacts with rocks of the islands (Fig. 1). It is probable that the great areas of granites and gneisses that surround the islands are not all of the same age, and that at places unmapped granite intrudes gneiss or older

Jan 1, 1932

By N. Rowlands, J. A. Finch, R. Espinosa-Gomez

The sulphation roast-leach process for complex sulphides results in phase changes due to roasting and leaching. The phases in the calcine, and in the neutral and hot acid leach residues were identified and their degree of liberation determined in order to design and Interpret separation tests on the residues. The hot acid leach residue was composed of hematite, silica, and lead sulphate with some associated silver. Magnetic separation was selected as the process for producing a lead concentrate, as the non-magnetic product. Separation was limited by -1 pm hematite reporting to the product, and hematite/lead sulphate agglomerates reporting to the magnetics.

Jan 1, 1984

By Ann M. Hagni

One of the most costly factors in the production of aluminum is the consumption of energy in the form of electricity. Energy consumption is increased as refractories in the Hall-Heroult reduction cells are corroded by penetration of the fluxes cryolite (Na3AlF6) and villiaumite (NaF). To decrease thermal conductivity and refractory waste, protective barrier linings are installed. Dry powder barrier linings form stable reaction products at cell operating temperatures. Four dry powders composed of vermiculite, corundum, wollastonite, and anorthite are characterized mineralogically by X-ray diffraction, reflected light microscopy, scanning electron microscopy, and cathodoluminescence microscopy in this research project.

Jan 1, 1998

By W. E. Wallace, P. S. Mike, C. A. Hill, V. Vallyathan, M. J. Keane

Respirable quartz duet and a kaolin clay dust have been found to be of comparable cytotoxic potential in vitro on a specific surface area basis (Wallace, et a1,1985), despite the distinctly different potentials of quartz and clay for causing pneumoconiosis or pulmonary fibrosis (Sheers, 1984). A respired particle depositing in a respiratory bronchiole or alveolus will contact a pulmonary surfactant hypophase, of which a primary component is diacyl glycerophosphorylcholine, or diacyl lecithin (DPL) (Clements, et al, 1970). Several studies have found that adsorption of such surfactant suppresses in vitro cytotoxic effects of quartz dust (Marks, 1957). Subsequent phagocytosis and digestion by a macrophage may remove the coating, restoring cytotoxic potential and initiating disease processes (Iles, 1979). Adsorption of dipalmitoyl lecithin (DPL) from emulsion in physiologic saline by respirable sized quartz dust and kaolin dusts, and consequent diminution of the dusts' hemolytic and macrophage cytotoxic potential have been reported (Wallace, et al, 1985). This report presents additional data on the cell-free in vitro phospholipase A2 enzymatic digestion of dipalmitoyl lecithin adsorbed on a quartz and a kaolin respirable sized dust (Wallace, et al, 1988) to investigate mineral specific differences in the rates of digestion and of consequent restoration of dust membranolytic potential. Respirable crystalline alpha quarts used was eighty percent smaller than 5 micorometer aerodynamic diameter with a nitrogen adsorption specific surface area of 3.97 m2/g. Respirable kaolin dust was ninety percent smaller than 5 micrometer diameter and had a specific surface area of 13.25 m2/g.

Jan 1, 1988

By Ralph Hultgren, Louis A. Carapella

When F. Heuslerl found in 1898 that certain alloys containing only copper, manganese, and tin were ferromagnetic, the discovery excited a great deal of interest and led to numerous investigations. It was early found that tin could be replaced by aluminum, arsenic, antimony, bismuth, or boron without destroying the ferromagnetic nature of the alloys.2 Copper may also be replaced by silver.% All these alloys have come to be known as "Heusler alloys." The aluminum alloys apparently were the most magnetic and have been most extensively investigated. However, no agreement has yet been reached as to the source of the ferromagnetism arising from these nonferromagnetic elements. Absence of reliable quantitative data makes speculation hazardous. The value of much of the earlier work was vitiated by lack of necessary precautions against contamination, and by lack of close control of heat-treatment. It was only recently established that in aluminum Heusler alloys4 the ferromagnetism arose from a single phase, an ordered body-centered-cubic structure. With modern methods of preparation, heat-treatment, and X-ray examination, it is possible to prepare these alloys without contamination, to heat-treat them intellgently, and to determine what phase or phases are present in the finished sample. In the present investigation, a series of pure alloys in the comparatively neglected copper-manganese-tin system have been prepared, which consist of a single, body-centered-cubic structure (the beta phase) and whose compositions vary within wide limits. The magnetic saturation values of these single-phase alloys have been quantitatively determined, so that considerable data on the effect of composition on the ferromagnetism have been made available. In the course of the investigation some information on the extent of the stability of the beta phase and the nature of phases in adjacent regions of the ternary diagram has been accumulated. Anomalies in earlier data. have been explained, and alloys have been prepared that are much more strongly magnetic than any previous Heusler alloys. Previous Work In the original work of F. Heuslerl and coworkers,2 a maximum magnetic saturation value of I = 107 was found at the composition Cu6Mn3Sn, while a value for CusMnAl of I = 443 was early measured. Ross and Gray5 found a second maximum at the composition Cu2MnSn, which was much more magnetic than Heusler's original alloy. F. Heusler6 hen reinvesti-gated the system, confirmed their results,

Jan 1, 1942

By Louis A. Carapella, Ralph Hultgren

When F. Heuslerl found in 1898 that certain alloys containing only copper, manganese, and tin were ferromagnetic, the discovery excited a great deal of interest and led to numerous investigations. It was early found that tin could be replaced by aluminum, arsenic, antimony, bismuth, or boron without destroying the ferromagnetic nature of the alloys.2 Copper may also be replaced by silver.% All these alloys have come to be known as "Heusler alloys." The aluminum alloys apparently were the most magnetic and have been most extensively investigated. However, no agreement has yet been reached as to the source of the ferromagnetism arising from these nonferromagnetic elements. Absence of reliable quantitative data makes speculation hazardous. The value of much of the earlier work was vitiated by lack of necessary precautions against contamination, and by lack of close control of heat-treatment. It was only recently established that in aluminum Heusler alloys4 the ferromagnetism arose from a single phase, an ordered body-centered-cubic structure. With modern methods of preparation, heat-treatment, and X-ray examination, it is possible to prepare these alloys without contamination, to heat-treat them intellgently, and to determine what phase or phases are present in the finished sample. In the present investigation, a series of pure alloys in the comparatively neglected copper-manganese-tin system have been prepared, which consist of a single, body-centered-cubic structure (the beta phase) and whose compositions vary within wide limits. The magnetic saturation values of these single-phase alloys have been quantitatively determined, so that considerable data on the effect of composition on the ferromagnetism have been made available. In the course of the investigation some information on the extent of the stability of the beta phase and the nature of phases in adjacent regions of the ternary diagram has been accumulated. Anomalies in earlier data. have been explained, and alloys have been prepared that are much more strongly magnetic than any previous Heusler alloys. Previous Work In the original work of F. Heuslerl and coworkers,2 a maximum magnetic saturation value of I = 107 was found at the composition Cu6Mn3Sn, while a value for CusMnAl of I = 443 was early measured. Ross and Gray5 found a second maximum at the composition Cu2MnSn, which was much more magnetic than Heusler's original alloy. F. Heusler6 hen reinvesti-gated the system, confirmed their results,

Jan 1, 1942

By N. S. Dalal, X. Shi

"Electron spin resonance (ESR) measurements on solutions and isolated powders provide direct evidence for the involvement of Cr(V) species in the reduction of Cr(VI) by NAD(P)H. ESR analysis of an isolated Cr(V)NAD( P)H solid yields 6 11 = 1.9831 and 6.i. = 1.9772, indicating that the unpaired electron occupies the d22 orbital of the Cr(V) ion, with square-pyramidal geometry. Addition of hydrogen peroxide (H2 0 2 ) to the N AD(P)HCr( VI) reaction mixtures suppresses the Cr(V) species and generates hydroxyl (""OH) radicals. The ""OH radicals were detected via ESR spin trapping, employing 5,5-dimethyl-1-pyrroline-N-oxide and a-(4-pyridyl-1- oxide)-N-tert-butylnitrone as spin traps. The dependence of Cr(V) and ""OH radical formation on the H20 2 and Cr(VI) concentrations indicates that the Cr(V) species react with H20 2 to generate the ""OH radicals. Similar results were obtained by using various diols (arabinose, cellobiose, FAD, fructose, glyceraldehyde, ribose, and tartaric acid), a-hydroxycarboxylic acids, and glutathione. Investigations with superoxide dismutase showed no significant participation of 02 in the generation of OH radicals. These results thus indicate that the Cr(V) complexes, produced in the reduction of Cr(VI) by cellular reductants, react with H20 2 to generate ""OH radicals, which might be the initiators of the primary events in the Cr(VI) cytotoxicity.In this paper we report an electron spin resonance (ESR)3 spectroscopic detection of Cr(V) species in the reduction of potassium dichromate, henceforth called Cr(VI), by NAD(P)H and other diols. Also reported here is the detection of the hydroxyl (""OH) radical in the reaction between hydrogen peroxide (H2O 2) and a variety of Cr(V) complexes. This work was undertaken because while the reduction of Cr(VI) to lower oxidation states has been suggested as a key step m the mechanism of Cr(VI) toxicity, mutagenicity, and DNA alteration, the details are not yet clear (1-5).Earlier studies on the mechanism of Cr(VI) reduction in cellular systems include those on the reduction of chromate by microsomes (6-8), rat liver DT-diaphorase (9), and aldehyde oxidase (10). All these studies imply that Cr(VI) can be reduced to Cr(Ill) by cellular constituents. Regarding the mechanism of Cr(Vl) carcinogenicity, Jennette postulated that Cr(V) is the ultimate carcinogenic form of chromium compounds (8). This conclusion has led to many further investigations of the formation of Cr(V) in the reduction of Cr(VI) under biologically relevant conditions (11-33). More recently, however, Kawanishi and co-workers (34) have investigated the mechanism of DNA cleavage induced by Cr(VI) in the presence of H20 2 and have argued that it is not Cr(V) itself that is carcinogenic, but it is the reactive oxygenated species (02, 10 2 , ""OH) (produced by the decomposition of the Crv(02) ¾ - ion) that cause the DNA alteration."

Jan 1, 1990