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By S. Leber, R. F. Hehemann

Diffusion coefficients for the Cb-W system were measured using couples prepared from poly crystalline, commercially pure metals. The diffusion coefficients, measured in the temperature range between 1700° and 2300°C, decreased exponentially as the tungsten concentration was increased from 0 to 50 at. pct, then decreased abruptly at higher concentrations. A decrease of two orders of magnitude was observed over the entin? compositional range. The diffusion coefficients were in the range defined by the self-difiusion coefficients of the individual elements, indicating their general validity. An activation energy of 60,500 cal per mole was measured for the 20 pct W composition. Such low values, when compared with energies over 100,000 cal per mole for the pure constituent elements, indicated that transport mechanisnzs more rapid than volume diffusion were contributing substantially to inter dijfusion. Difference should, therefore, be expected between these data and the intrinsic diffusion coefficients. These differences should be significant in the kinetics of 'transport phenomena in practical systems. CONSIDERABLE attention has been devoted in recent years to the mechanical behavior and other properties of the refractory metals and their alloys. The Cb-W system has been of special interest as a base for the development of more complex compositions of commercial interest. In spite of the importance of mass transport to all aspects of elevated-temperature behavior, and especially to the production of alloys by powder-metallurgy techniques, little attention has been paid to diffusion in the Cb-W system. Results from a previous study of this system1 appeared to be anomalously high. The present investigation is, therefore, an attempt to obtain more accurate diffusion coefficients in this system. Intrinsic diffusion coefficients, of primary importance from the theoretical viewpoint, can only be obtained accurately from studies utilizing compositional gradients approaching zero. However, many practical problems involve diffusion under significant concentration gradients. The diffusion coefficients determined in this investigation were, therefore, obtained from couples prepared from elemental metals. The data obtained should be of value in the analysis of problems such as homogenization during powder-metallurgy alloying or reactions between base and clad in coated structures. In this vein, the investigation was conducted on poly crystalline materials of commercial purity. PROCEDURE Diffusion couples were prepared by sandwiching a columbium sheet between two sheets of tungsten. The composite was welded around all edges, the tungsten forming a protective can for the columbium. The composite was soaked for 4 min at 1600°C in a hydrogen-atmosphere furnace, quickly forged to 40 pct reduction in thickness, and then rapidly cooled to room tempera-

Jan 1, 1967

By G. T. Higgins

PREVIOUS workers1,2 have found evidence of exaggerated grain growth or secondary recrystallization on annealing sponge zirconium at temperatures high in the a, phase field, but no details of the orientation relationship between the secondary grains and "as-recrystallized" matrix were reported. In other hexagonal metals, namely dilute Mg-A13 and Cd-zn4 alloys, secondary recrystallization has been observed in which the secondary grains are related to the primary recrystallized structure by rotations about the c axis. These rotations are thus comparable with the rotations about the (111) axis observed in the secondary recrystallization of fcc metals. In the current work secondary recrystallization has been observed on annealing iodide zirconium at 800°C and the associated changes in crystallographic texture have been examined. The material employed was arc-melted iodide zirconium of the following composition: Impurity O H Fe Hf Pb I Ni C1 A1 ppm by wt 130 5 230 98 23 28 200 39 30 This was received as 0.25-in. plate, and, prior to the annealing studies, was cold-rolled to 0.040 in. Specimens 1 in. sq were chemically polished and annealed for various times at 800°C in a vacuum better than 5x 10-6 Torr. For metallographic examination specimens were first chemically polished and then anodized8 to enhance contrast between the grains when examined under polarized light. Changes in crystallographic orientation associated with the development of secondary grains were followed by (1011) and (0002) pole-figure determinations using a conventional Schulz goniometer in reflection. Filtered Cr Ka radiation was employed and great care was taken to avoid spurious re- sults due to the close proximity of the Bragg angles for the (1011) and (0002) reflections. Figs. 1 and 2 illustrate the change in grain structure on annealing at 800°C. After 24 hr the structure has ceased to be equiaxed due to the development of certain grains in preference to others. It is notable that the secondary grains do not grow to the extent observed in sponge zirconium.1,2 This appears to be due in part to the fact that normal grain growth is inhibited in the less pure sponge zirconium, with the result that the driving force for secondary recrystallization remains high, while at the same time the number of grains able to develop in the presence of the impurities is also smaller. As a consequence, in sponge zirconium those grains that do develop preferentially are able to grow into the fine -grained matrix without impingement, while in iodide zirconium the preferential growth of many grains leads to early impingement. The pole figures determined for specimens annealed for 5 min and 24 hr at 800°C are illustrated respectively in Figs. 3 and 4. These indicate that the dominant feature of the initial recrystallized texture consists of basal planes at an angle of 321/2 deg to the sheet surface, with a (1120) axis lying parallel to the

Jan 1, 1967

By J. D. Grace

Screening by centrifugal force is a unique subject, for all vibrating screens, with but one exception, depend on gravity alone to pass material through a sizing mesh or screen cloth. Centrifugal screening is one of the greatest advancements made in screening since the development of vibrating screens. It makes possible sizing in a range previously im-practical by mechanical methods. The centrifugal screen is specially designed for fine sizing from No. 4 separations to finer than No. 100 separations. Centrifugal force provides a positive control of factors that make fine particle separation practical and effective as opposed to gravity which is a fixed force acting only in a fixed direction, The centrifugal screen provides a control of the force of material against the screening surface, and also controls the distance of departure of the material from the surface and its rate of return. The centrifugal screen has a rotating drum that becomes a natural fan blowing air outward through the material being screened and carrying float dust and fines through the apertures with it. Screening by centrifugal force is an unique subject, for with the exception of only one vibrating screen presently on the market, all vibrating screens depend upon gravity to pass material through a sizing mesh or screen cloth. This one screen that sizes by centrifugal force and utilizes gravity only to convey material along the screen, is the Symons V-Screen. The requirements of the industrial minerals industry to meet ever-increasing stringent fine sizing specifications by a practical mechanical method accentuates the weakness of gravity, a fixed force acting in a fixed direction, as a prime force for fine sizing. It was apparent a force other than gravity was needed. This led to the development of a centrifugal screen to meet modern demands for practical fine sizing operations. Gyratory-type screens in use today were originally designed in a day when a 1/4-in. separation was normally considered fine sizing and 1/8-in. separations were extremely fine sizing. Although gyratory-type screens are sometimes used for separating below 1/8-in., they are not practical screens for this purpose. They were not designed to do this type of work. A growing demand for a practical means of making positive mechanical separations in a range of from 1/8 in. downward led to the development of the vibrating screen. These screens utilize higher speeds and lower amplitudes of vibration than

Jan 1, 1967

By R. F. Abernethy

The work discussed in this report was done by the Bureau of Mines to develop a method for determining trace amounts of fluorine in coal. Samples of coal mixed with calcium oxide as a fixative agent for fluorine were ashed at 600° C and the residue was fused with sodium carbonate. The melt was dissolved in phosphoric and sulfuric acids and distilled to separate the fluorine) which was determined in the distillate by a SPADNS-zirconium spectrophotometric method. Fluorine determinations of 83 commercial coals ranged from 0,001 to 0.019 percent.

Jan 1, 1967

By H. Kazemi

A pressure fall-off test on the injection well of a forward combustion project may permit us to calculate the distance to the burning front. In the mathematical description and analysis of test data, we have considered the effect of temperature on the thermodynamic properties of reservoir fluids. The temperature distribution predicted by Chu' for a combustion wave has been used in analyzing a field test. Numerical solutions were obtained by simultaneous solution of the flow equation, the continuity quation and the equation of state. Although this analysis conccntrated on isotropic systems, the results can be extended to systems having directional permeability. INTRODUCTION Conventional pressure fall-off tests have been used extensively to determine reservoir characteristics in gas- or water-injection projects.- such tests consist of injecting fluid into the formation at a constant rate until steady state is nearly achieved, then discontinuing injection and measuring the bottom-hole pressure as a function of time. A plot of pressure vs the logarithm of time (measured from the instant of shut-in) yields a smooth curve characterized by three distinct regions (Fig. 1): Region I reflects the permeability alterations in the vicinity of the wellbore; Region II reflects the reservoir characteristics further away from the wellbore; and Region 111, the characteristics in the displaced fluid bank. The curves in Regions II and III are straight lines! the slopes of which are proportional to the reciprocal of the flow capacity of the formation behind and ahead of the interface as shown by Eq. 1, respectively:

Jan 1, 1967

By P. M. Robinson, M. B. Bever

The heats oj formation at 273°K of the compounds CdTe, I)z2Te, InTe, In2Te3. In2Te5, SrzTe, and PbTe have been rleasrred in a liquid metal solutiotz caloritrete? 1.t1itlz bismuth as solvent. The?, are iterpretecl in yelation to tlze stability and bonding of the cott/pozltzds. Tile heats of fusion atzd the melting- points of tlze cotlzpounds InTe and Itzz,Te3 1lcti.e been measured in a cotrslant-temperature gradient calorimeter. The entropies of fusion are disc,ztssecl in YIIIS 01. the degree of order in the solid at the melting point. THE heats of formation of the tellurides of cadmium, indium, tin, and lead have been measured as a continuation of research on the thermodynamic properties of compounds of tellurim.' The tellurides of these metals were selected with a view to examining the relation between the heat of formation and the position of the metal in the periodic system. The elements cadmium, indium, and tin are in the same period and tin and lead are in the same group of the periodic system. The tellurides of indium are of special interest because four compounds, In2Te, InTe, In2Te3, and InzTe5, occur in this system. The available information on the heats of formation of the compounds investigated consists of values for CdTe, SnTe, and PbTe derived from electromotive-force measurements,J a value for CdTe obtained by tin solution alorimetr, and values for InTe and In2Te3 determined by combustion calorimetry.5 These values, however, refer to various temperatures ranging from 273' to 673°K and some of the reported error limits are large. Liquid metal solution calorime-try may be expected to yield more accurate values for the heats of formation than electromotive-force measurements or combustion calorimetry. The heats of fusion and the melting points of the compounds InTe and In,Te3 were determined in a constant-temperature gradient calorimeter. No published information appears to be available on the heat of fusion of these compounds. The results reported here give an indication of the degree of order in the solid compounds at the melting point. 1) MATERIALS AND EXPERIMENTAL PROCEDURE Materials. Samples of the compounds SnTe and PbTe were obtained from the Westinghouse Research Laboratories and samples of the compound InTe from Lincoln Laboratory, Massachusetts Institute of Tech- nology. Additional samples of the compounds InTe, SnTe, and PbTe and samples of CdTe, In2Te, In2Te3, and In,Tes were prepared from 99.995 pct Cd (Baker Chemical CO.), 99.999+ pct In (American Smelting and Refining Co.), 99.99 pct Sn (Baker Chemical Co.), 99.999+ pct Pb (Fisher Scientific Co.), and 99.999+ pct Te (American Smelting and Refining Co.). Stoichiometric amounts of the component elements were melted in sealed, evacuated Vycor tubes. The melts were held at approximately 100°C above the liquidus for about 16 hr and shaken repeatedly. The melts of the compounds In2Te and InzTe5, which form by peritectic reactions, were quenched into iced water. The melts of the other compounds, which have congruent melting points, were slowly cooled to room temperature. The samples were then annealed for 5 days at approximately 50°C below their respective solidus temperatures. Metallographic examination did not reveal any evidence of second phases or segregation. At least two batches of each compound were prepared. Samples from each batch were used in determining the heats of formation and, in the cases of InTe and In,Te3, the heats of fusion. The Heats of Formation. The heats of formation at 273°K of the compounds were measured by metal solution calorimetry with liquid bismuth at 623" as solvent. In this technique, the heat of formation is determined from the measured heat effects on dissolution of the compound and of a mechanical mixture of the component elements. The difference between these heat effects adjusted for changes in the composition of the bath gives the heat of formation at the temperature from which the samples are added to the bath (273°K). The experimental technique and method of calculation have been described in detail elsewhere.= It should be emphasized that the reported heats of formation depend on the thermodynamic data used in calculating the heat effects for the calibration additions. In the present investigation, the calorimeter was calibrated by adding pure bismuth at 273°K to the bismuth bath at 623°K. The reported heats of formation are based on a value of 4.96 kcal per g-atom for the difference in the heat contents of bismuth at 623" and 273". If a new value for this quantity becomes available, the reported results may be adjusted in direct proportion. The concentration of solute in the bath at the end of a calorimetric run did not exceed 1.7 at. pct and was usually less. In this range, the heat effect on dissolution of the solute was a linear function of the concentration of solute. In determining the heats of formation of the compounds in the system In-Te, a few runs were carried out in which two neighboring compounds such as InTe and In,Te3 and the corresponding mechanical mixtures of the components were added to the calorimeter. The

Jan 1, 1967

By R. J. Heemstra

A continuous flowing paper electrophoresis cell was used to separate petroleum and petroleum extracts into characteristic patterns. The electrophoresis of Bachaquero, Lagunillas, Boscan, and Gibson petroleums in nitro-benzene and acetic acid-based electrolytes was investigated. The extent of separation in the patterns was studied by measuring the metal and porphyrin contents of the effluents. Qualitative separations were achieved in some systems, whereas either system demonstrated only a high degree of electrophoretic migration.

Jan 1, 1967

By R. A. Deju, R. B. Bhappu

The basic structural unit of all silicate minerals is a tetrahedron with a silicon atom at the center and four oxygen atoms at the corners. The oxygen-silicon distance is about 1.6 & and the oxygen-oxygen distance about 2.6 &. The different types of oxygen-silicon frameworks in the various silicates are based entirely on the combinations of the tetra-hedral oxygen-silicon groups through sharing of oxygen atoms. In recent years, infrared spectroscopy has permitted estimation of the ratio of the ionic character of the oxygen-silicon bond to be a few times that of the oxygen-carbon bond and the ratio of electro-negativity of the two bonds has also substantiated this finding. On this basis, it is generally accepted that the oxygen-silicon bond is the strongest one occurring in silicate minerals. As the oxygen-silicon ratio increases from quartz to the olivines, a greater percentage of the oxygen bonding power is available for bonding to cations other than silicon. Hence, with an increasing oxygen-silicon ratio, there is increasing oxygen-to-metal bonding. Upon the fracturing of a silicate mineral crystal, the oxygen-metal bond, which is almost entirely ionic in character, should break more easily than the stronger oxygen-silicon bond, resulting in a greater number of unsatisfied negative forces on the surface. If, then the mineral is immersed in a liquid containing hydrogen ions, these negative forces should tend to be neutralized by hydrogen ions from solution, resulting in a change of the pH of the solution. An increase in the degree of adsorption of hydrogen ions is to be expected as the oxygen-silicon ratio in the crystal structure increases. This study attempted to correlate the oxygen-silicon ratio for various representative silicate minerals to the adsorption of hydrogen ions. Experiments to determine the effect of surface area on this adsorption and to investigate the effect of surface iron were also conducted. It is believed that such studies of the surface properties of silicate minerals will supply pertinent information about their behavior in froth flotation systems. EXPERIMENTAL PROCEDURE Ion Exchange: Carefully selected, hand-picked samples of the minerals investigated were dry-crushed in a ceramic ball mill and sieved to obtain a minus 100 plus 200-mesh sample. The sized samples were then run through the electro-magnetic separator to remove any iron-bearing particles. A 10-g sample of each mineral was placed in 100 ml of freshly deionized water previously adjusted to a pH of 3.50 with HCl. The beaker containing the sample and the water was placed under a bell jar from which the air was displaced at once by nitrogen gas from a tank. All experiments were carried out in a nitrogen atmosphere. The sample and solution were stirred gently but continuously during the entire experiment, the stirring speed being kept about the same for all runs. Changes in pH were followed with a Beckman Zeromatic pH meter and recorded on a

Jan 1, 1967

By August E. Vandale

I speak to you today on the subject assigned to me, "Subsidence - a Real or Imaginary Problem", as a representative of Consolidation Coal Company (a wholly owned subsidiary of Continental Oil Company). The information I relate to you is our experience in the Pittsburgh Coal Company Division of Consol and covers the Pennsylvania properties and mines with particular emphasis on the mines in the south- western portion of the State or in the immediate vicinity of Pittsburgh, Pa. Mining of Freeport and Pittsburgh seams of coal in the Pittsburgh vicinity dates back over one hundred years. Consol, or its predecessor, Pittsburgh Coal Company, has been actively engaged in mining in the area since Pittsburgh Coal Company was organized in 1900. Pittsburgh, Pennsylvania came into prominence as the Steel City largely because of the vast reserves of high grade metallurgical coal readily available in the immediate vicinity and also because of its favorable river transportation. Early in the 1900's we operated over 100 small coal mines, with operations located in the Counties of Allegheny, Fayette, Washington, Westmoreland. We have also operated mines in Somerset and Greene Counties. Titles in Pennsylvania can be in three estates: (1) title in fee, (2) title to the mineral, (3) mining rights permitting the removal and extraction of the mineral with or without waiver of surface damage. Consol has over the years acquired good legal title to the coal lands purchased from individual farm owners, with good broad mining rights, and in 98% or more of its title has a complete waiver of surface damage or the right to subside the surface land. In the early days of our Company, individual coal farms were purchased from land owners. Many of these titles severed the coal estate from the in fee title and good mining rights with waiver of surface were conveyed in the original severance deed. Thus, minable coal reserves were put together by the purchase of the coal under many individual farms in an area. In the early years, the mines practiced hand dug mining - later going to mechanical cutting with hand loading of the coal. Systems used were entry driving with room and rib panels. We have practiced full recovery mining as far as practical during the years of hand loading, as well as in the later years when the mines were mechanized. Mining system layouts, methods and procedures have changed from time to time to keep pace with improved mining machinery and new inovations, such as roof bolting and rubber tired haulage.

Jan 1, 1967

The point of the anode effect on carbon anodes of dcfincd surface area. during electrolytic decomposition of alumina dissolved in molten fluorides. has been determined from current-voltage curves. The reproducibility and accuracy was found to be better for cell voltage than anode current density. Results have been obtained for the effect of alumina concentration temperature and carbon type. The point of the anode effect was strongly dependent on both the alumina concentration and the carbon type. For high alumina concentrations it has been found that the anode effect approaches reversibility. From these results it is concluded that co-evolution of CO, and CF. occurs prior to the onset of the anode effect. The anode effect results when the CF, content becomes sufficiently high for the melt not to wet the electrode surface and is maintained because of the slow desorption of CF, and the high electrode potential that results.

Jan 1, 1967

By Renpei Yoda

An investigation was conducted to develop columbium alloys with e1evated-temperature strengths higher than those exhibited by more common commercial columbium alloys, and attention was given to improving the oxidation resistance and ease of fabrication. Additions of carbon, aluminum, and chromium were made to some columbium-base alloys, and their effects on workability, recrystallization, oxidation resistance, and mechanical properties at elevated temperatures were explored. The additions were made to take advantage of (1) solid solution strengthening, and (2) precipitation hardening. Three alloys displayed good high-temperature properties with relatively good oxidation resistance at 1,000° C, and tensile strengths from 26,000 to 32,200 psi at 1,400° C. When the properties of these alloys were compared with those of commercial alloys, B-66 and FS-85 (1),4 the outcome was favor-able for the alloys studied in this investigation.

Jan 1, 1967

By L. Messulam, A. S. Appleton

Iwo major studies of the Fe-Cr-C system are available in the literature. The earlier one of Kinzel and crafts' forms the basis for the data most commonly quoted in works of reference (e.g., Metnls HandDook) though the later work of Bungardt el a1.' is more extensive and amenable to analysis in terms of isothermal sections and so forth. However it is evident from examination of either of these studies that the delination of phase boundaries on the basis of the data obtained can only be very approximate. Indeed in several instances the data are so inconclusive that this delineation is a matter of opinion. This note is to report an analysis of experimentally determined carbon activity data in this system, which, originally intended as a means of checking the self-consistency of the data for a number of alloys, enables some conclusions to be drawn concerning the 10503C isothermal section of the iron-rich corner of the system as deducible from the data of Bungardt

Jan 1, 1967

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram' shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By F. L. Kadey

A discussion of fillers would not be complete without allotting adequate time to that unique and different mineral material, diatomaceous silica. Historical references to its use challenge the aesthetic aspect of man's curiosity; whereas modern scientific tools have provided a dimension of measurement that has motivated many of its more recent applications. A brief review of what is already known is in order. The diatom is a unicellular, plant-like, microscopic organism, related to the algae1. Its natural function appears to be that of a food for other marine or lacustrine organisms, The diatom's "claim to fame" from an industrial viewpoint is dependent on the fact that it secretes an opaline siliceous skeleton that must survive, chemically and structurally, the geologic processes that caused its formation in the first place; its subsequent demise, burial, consolidation, and alteration; and finally, its ultimate exploitation by man--in somewhat that order. In addition to its siliceous nature, the skeletal structure of the diatom possesses a variety of shapes, patterns, and sizes that have not only been the intrigue of microscopists for decades, but have served to set diatomite apart as an industrial mineral; and have reserved for it applications that cannot be satisfied by any other material. Its chemical inertness, its intricate structure, and its intrinsic hardness-coupled with fineness and friability-- are generally known and have accounted for its application in a wide range of filtration and filler uses. The increasing use of the electron microscope has considerably expanded our knowledge of heretofore unseen secondary and tertiary structure of submicron dimension in the diatom valve. The development of electro-sensing methods of particle size measurement which seem to supersede sedimentation and microscopic techniques has portrayed size distribution in a more realistic light. Interest in the surface chemistry of these silica structures has further strengthened our understanding for certain uses. Thus, new tools and ideas have made possible the introduction of diatomite into such sophisticated technologies as that of chromatographic supports, its improved utility in paint applications for the control of gloss and sheen, and its usefulness in the entirely new concept of "Dry Acid Concentrates." Each of these applications has been discussed elsewhere before people particularly interested in analytical chemistry, in paint, and in liquid handling, respectively, where the diatom has been a means to an end. The emphasis here, before the mining fraternity, however is on diatomite as a raw material with reference to the uses mentioned above. It is therefore toward an awareness and understanding of diatomite properties pertinent to these newer filler applications that this paper is directed.

Jan 1, 1967

By Thomas R. Bur

The strain and pressure gage methods for evaluating the relative performance of explosives in rock were compared. This comparison was based on a study of the responses of strain and pressure gages to explosion-generated seismic waves. Several explosives) representing a wide range of detonation pressures) were used. In general the relative performance of these explosives) as determined from amplitude) impulse parameter) and energy parameter measurements) is the same if the compressive portion of the strain pulse and the comparable portion of the pressure pulse are considered. Other similarities and differences of the two methods are also discussed.

Jan 1, 1967

By F. R. McDonald

This report presents a discussion of the spectra of 39 condensed thiophenes in which the structure includes at least 1 benzene ring. The vibrational bands present in three regions of the infrared spectra of these thiophenes were interpreted by comparing the similarities of the spectra of condensed thiophenes with the spectra of substituted benzenes. In the overtone-combination region 23 of the 39 condensed thiophenes had spectra which contained sufficient detail to be usable for correlating this region of the spectrum with the appropriate benzene spectrum. In the in-plane deformation region it was possible to make correlations for the vibrations of 18 of the 39 condensed thiophenes whose infrared spectra were studied. In the out-of-plane deformation region the C-H out-of-plane vibrations for hydrogen on benzene rings in the condensed thiophenes can be correlated using known data from substituted benzenes.

Jan 1, 1967

By E. J. Murphy

The Bureau of Mines developed a fast, reliable modification of the Griess-Ilosvay procedure suitable for field analysis for NO2 in the fumes from explosives. Known concentrations of NO2-air mixtures were analyzed for the nitrous acid or nitrite formed in the reaction with three Griess-Ilosvay-type reagents by diazotizing and coupling. Comparison was made of the Rider-Mellon, Saltzman, and Patty-Petty procedures; the three procedures are in agreement if sufficient time of contact between NO2 and the reagents is allowed. In experiments to obtain an accurate factor for converting NO2 to nitrite, overnight contact was allowed in order to be sure conversion was complete. The factor was found to be 75 percent with a standard deviation of ±3.2. Low and erratic results were found using either the Saltzman or Patty-Petty reagents as absorbing liquids unless several hours' contact was allowed. If dilute NaOH solution was used as the absorbing liquid instead of a Griess-Ilosvay-type reagent, 92 percent of the overnight conversion factor was found after a 3-minute shaking time and a la-minute standby time. The Saltzman reagent was preferable for fieldwork with the dilute NaOH solution as the absorbent because of its easy application, rapid reaction, and intense color even at low NOB concentrations.

Jan 1, 1967

By G. M. Gay, R. L. Perrine

This paper describes a method of numerical computation for three-dimensional, unstable, miscible displacement behavior useful for heterogeneous systems, as well as for more ideal conditions. In the method, flow equations are first linearized by a perturbation approach. The basic flow process is separated and a solution for its behavior readily obtained. The remaining problem of deviations from the basic flow caused by non-ideal conditions is then subjected to numerical analysis. Results obtained from use of the method are also presented. Although conditions assumed in the test cal-culations were severe, results show the type of dispersing flow expected and appear quite satisfactory. The method has eliminated or reduced in importance problems of oscillating values near steep fronts, excessive computer smoothing, etc. A unique advantage of the method is that the source of variations from ideal behavior can be observed. ,The one serious drawback results from the algebraic complexity of the perturbation approach, and the need for second-order terms to be retained in calculations of interest. Fewer array points are available and more computer time is required than would be desired. However, these difficulties are also experienced with other approaches to the solution of three-dimensional dispIacement problems. INTRODUCTION Prediction of behavior of the miscible displacement process within a porous medium for any system of engineering importance is plagued by a number of difficulties. With typical fluid properties the displacing fluid has the lower viscosity, and there is a natural tendency toward flow instability. The problem of predicting instability is compounded by the fact that every real system is heterogeneous. Permeability will vary from point to point — not entirely systematically, and yet not in a random fashion leading to a readily defined average. Furthermore, permeability is unlikely to be isotropic. These permeability properties, which are characteristic of any real porous medium, accentuate the effects of flow instability. Another factor to be considered is that flow dispersion accompanies the displacement process in a porous medium. Mechanistically, dispersion is due to the fact that flow between any two points in the medium follows multiple tortuous paths, each characterized by slightly different flow properties. The fact that the coefficient characterizing dispersive properties of the real medium JS a tensor with variable elements complicates matters. Further difficulties arise because the parabolic influence, while not negligible, is small. Thus, there is a tendency toward steep and uneven displacement fronts along which dispersion smoothing must be represented accurately. Yet frequently used numerical analysis schemes may tend toward either instability, oscillation or excessive smoothing, none of which gives the desired accurate picture of flow behavior. Thus, while many experimental and analytical studies of the process have been made, predictions of actual performance are still subject to considerable uncertainty and possible improvement. This paper reports on part of a study which attempts to develop improved methods for solution of the flow equations describing the miscible displacement process. Of necessity, the calculations were performed on a large digital computer. A three-dimensional system is represented, and the coefficients defining dispersion and permeability can be varied in a manner representative of a real system. Because the differential equations are nonlinear, a first step is to linearize them using a perturbation approach. Objective of this approach has been to separate the basic flow which would occur in an ideal system and for which predictions are readily made. Then the numerical analysis, which is necessarily complex, is directed toward solution of the perturbation equations. These equations state how the basic flow is modified

Jan 1, 1967

By Hillary W. St. Clair

The effective coefficient for rate of reduction of a sample of granular iron ore may be determined by passing the reducing gas through a bed of the are at constant flow rate and periodically analyzing the effluent gas, The method of analyzing the data is based on a mathematical model that takes into account the variation in composition of the gas and solids with time and position in the bed. A method is described for determining the value of the rate coefficient that gives best agreement between the observed and calculated analyses of the effluent gas.

Jan 1, 1967

By J. W. Spretnak

It is well-established that decohesions occurring at the interface of the matrix and rigid inclusions and second-phase particles are prime causes of ductile fracture initiation. It is not clear, however, how these decohesions occur. The idea that the interface bond is broken in tension is not particularly attractive when one considers the strength of such interfaces and the fact that plastic flow is not restricted under conditions of continuing flow required to initiate and propagate ductile fracture. A suggestion as to the mechanism of decohesion arises if one takes the position that, as the dislocation density increases with plastic flow and reaches some critical range of density, the phenomenon of flow can be regarded as fluidlike instead of the crystallographic motion of dislocations. As the spacing between dislocations decreases, the matrix becomes increasingly disordered in terms of loss of periodicity. At some critical degree of reduction of the periodicity, it is suggested that flow can be regarded as hydrodynamic, rather than crystallographic. Such a state has been referred to by rheologists as the "plasticized state", or the "fourth state of matter", between the liquid and solid state. A similar argument pertains qualitatively with the increase in equilibrium vacancy concentration as the temperature approaches the melting point. Taking the viewpoint that at larger strains the flow may become hydrodynamic in nature, a mechanism of decohesion is suggested. A well-known phenomenon in boundary-layer flow is that of "separation" locally of the boundary layer from the substrate.' Under certain conditions, the flow in the immediate neighborhood of the substrate becomes reversed, causing the boundary layer to separate from it. The exact condition for separation is that the velocity gradient normal to the substrate vanishes there, or It is of interest that blunt particles such as spheres and circular cylinders are most likely to give rise to separations because of unfavorable pressure distributions behind them. The source cited gives solutions for positions of separations for various geometries. In principle, such separations can also take place when metal is flowing over a "dead zone" of stagnant metal. This may explain the initiation of fracture at the elastic-plastic boundaries of plastic enclaves under a notch.

Jan 1, 1967