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By Basil Dimitriades

The roles of hydrocarbons and nitrogen oxides in smog formation were investigated by the Bureau of Mines. Samples of automobile exhaust with varying HC and NOx levels were irradiated in a smog chamber under conditions that resulted in smog levels similar to those observed in the atmosphere. Results were used to define the patterns that describe the dependence of a number of smog manifestations on HC and on NOx. Using these dependence data and some simplifying assumptions, estimates were made of the ranges within which HC and NOx must lie in order to obtain specified levels of air quality.

Jan 1, 1970

By R. V. Lundquist

Past reports by the Bureau of Mines have described the extraction of alumina from numerous aluminum silicate materials by the lime-soda sinter process. The results from pilot-plant investigations of six materials, with alumina-to-silica mole ratios from 0.3 to 8.7, indicated a relationship between the alumina-silica ratios and the processing characteristics of the sinter. A series of laboratory tests was conducted to define this relationship. Sinter and leach tests determined that an alumina-to-silica mole ratio of 0.90 or greater resulted in the best alumina and soda recoveries while leaving the leach slurries practically free from any tendency toward gelation. The widely different chemical and mineralogic properties of the various aluminous materials used in compounding the mixes had no perceptible effect on the leaching characteristics of the sinter. The blending of low-cost, high-alumina materials with aluminum silicate materials to give an alumina-to-silica mole ratio of 0.90 or greater would improve alumina and soda extraction and minimize operating problems in the lime-soda sinter process.

Jan 1, 1970

By L. B. Pankratz

Enthalpies were determined for synthetic chalcopyrite (CuFeS2) between 298° and 1,050° K and for synthetic bornite (Cu5FeS4) between 298° and 1,100° K by copper-block drop calorimetry. Two transitions were found for each compound. The lower transitions were both crystal transformations from tetragonal (low-temperature form) to cubic (high-temperature form). The chalcopyrite transformation occurred at 830' K with a heat of transformation of 2,405 cal/mole; the bornite transformation was at 485° K with a heat of 1,430 cal/mole. The other transitions were of the second order and were presumed to be magnetic in character. The second-order transitions for chalcopyrite occurred at 930° K, and the one for bornite at 540° K. Enthalpy increments, entropy increments, and heat capacities are tabulated at even temperatures above 298.15° K. Equations of enthalpy are also given.

Jan 1, 1970

By Clarence O. Babcock

In this report, the Bureau of Mines presents a method for reducing the complexity of designing room-and-pillar mining systems by treating them as anisotropic soft inclusions in the surrounding ore or host rock. Theoretical models were derived for the calculation of the effective Young's moduli for these systems. The predicted behavior of the plate-type elements used in these models agreed well with test results from 21 plates each with 49 holes spaced on a 7 X 7 Cartesian grid. The plates behaved as anisotropic solids, the effective Young's moduli of which could be predicted from the scaled hole size and spacing. Actual hole shape was insignificant. The effective Young's moduli for simple mining systems are calculated in sample problems. This approach should provide information about field stress in the mining region and the stress distribution in the surrounding ore or host rock when the actual mining configuration is replaced by an anisotropic inclusion in a finite element analysis. The field stress within the inclusion can then be applied to the actual opening shape to determine the stress distribution within the mining region.

Jan 1, 1970

By Laurance L. Oden

The Bureau of Mines is developing melting data for binary combinations of the alkaline earth fluorides and yttria to facilitate the formulation of slag compositions. The present report deals with the CaF2-Y203 system for which solidus and liquidus temperatures and solid solubilities were determined. The information is presented as the phase diagram. All specimen compositions were blended from high-purity materials and encapsulated in Mo or Pt20Rh prior toheat treatment. Liquidus temperatures were determined by ceramographic examination of heat-treated and quenched specimens. Solidus temperatures were determined by differential thermal analysis and by electron microprobe analysis of quenched specimens. Terminal solid solubilities were derived by parametric methods. The peritectic system was found to be pseudobinary due to the formation of yttrium oxyfluoride at temperatures near the liquidus. The peritectic point occurs at 7 mole pct Y203 and 1,438° ± 5°C. The terminal solid solubility of Y203 in CaF2 decreases from 7 mole pct at 1,438° C to 1 mole pct at 1,100° C, and the solubility of CaF2 in Y203 decreases from 9.5 to 7 mole pct over the same temperature interval.

Jan 1, 1970

By Laurance L. Oden

The Bureau of Mines is developing melting data for binary combinations of the alkaline earth fluorides and yttria to facilitate the formulation of slag composition. Liquidus and solidus temperatures and solid solubilities were determined for the BaF2-Y203 system, and the information is presented as the phase diagram. The phase diagram was constructed from data obtained by ceramography, X-ray diffraction, and thermal analysis of specimens encapsulated in small molybdenum ampoules. The data indicate a simple eutectic system with maximum terminal solid solubilities of less than 1 mole pct. The eutectic temperature is 1,343° C, and the composition of the eutectic is less than 1 mole pct Y203.

Jan 1, 1970

By J. M. Singer

Approximate equations were used to compute the radiant heating of float coal dust by approaching flames for various combinations of particle size, dust path length (flame travel distance), flame temperature, dust concentration, flame speed, and flame length. The computed values of degree of radiant heating and flame travel distance for preheating the coal dust should be useful for estimating the increased fire hazard of different coal dust-flame parameters. Some findings relating to coal mine disaster control are-- 1. Coal dust clouds cannot be preheated to ignition temperatures by flame radiation alone when deflagration speeds are greater than about 10 m/sec. Thus it appears unlikely that radiation alone will cause flames propagating in dust clouds to accelerate to detonation velocities. 2. Small particles in the radiation flame zone caused by burnout and soot formation increase the degree of preheat significantly. 3. The concentration of float coal dust (radii = 3 to 40 microns) for maximum radiant heating usually peaks in the range 50 to 200 mg/liter of air.

Jan 1, 1970

By K. J. Miller

A laboratory electrophoresis column was designed to separate pyrite from fine coal by utilizing an observed difference in the electrophoretic mobilities of the two materials in water. The apparatus worked well when tested with synthetic mixtures of coal and pyrite, but some modifications in design and procedure were necessary to provide a sharper separation. After these changes were made, the column was tested with a high-pyritic-sulfur raw coal sample. The column successfully fractionated the sample, removing not only the pyritic refuse, but a siliceous refuse as well. The invest ion demonstrated on a laboratory scale that pyrite and other impurities can be separated from fine coal by electrophoresis.

Jan 1, 1970

By F. S. Karn

Measurements were made of the flow of helium, methane, ethane, butane, and toluene through thin disks of coal. All measurements were made on a dense layer in the Pittsburgh seam identified as attritus. Flow increased with pressure differential and temperature. At room temperature and a pressure differential of 1 atmosphere flow rates along the bedding plane of Pittsburgh seam coal were helium 881 X 10-10 cm2 sec-1, methane 1.2 X 10 -10 cm2 sec-1, ethane 0.54 X 10-10 cm 2 sec-1, n-butane 0.35 X 10-10 cm2sec-1, and toluene 3.8 X 10-10 cm2sec-1. Flow rates were 50 percent lower across the bedding plane of the coal than along the bedding plane. Activation energies were 3.9 kcal mole-1 for helium and 13.6 kcal mole-1 for methane, with diffusion measured either along or across the bedding plane.

Jan 1, 1970

By John R. Zelonka

Models made by encasing strain-gage networks in epoxy are described and evaluated. With this technique relatively complex models can be constructed in which any number of gages can be located and alined precisely. Although the gages are an integral part of the model matrix, they create no important mechanical or thermal stresses. Model construction techniques and experimental data proved reproducible and reliable. In addition, the sGlution obtained with these models to the problem of the state of stress around a circular hole in a plate subject to a plane stress condition was in agreement with theoretical, photoelastic, and finite-element solutions.

Jan 1, 1970

By A. W. Effinger

The Bureau of Mines used regression analysis and applied statistical methods in an effort to rationalize the results of an experiment examining the effects of certain variables on carbon deposition in a reservoir for thermal recovery of petroleum. Although none of the 15 trials of the original experiment resulted in the response of weight-percent of carbon regarded by the experimenter as adequate, values calculated using canonical analysis in two trials yielded responses 33 and 54 percent higher than the minimum acceptable figure. The actual responses differed by less than 3 and 6 percent, respectively, from the predicted responses. Methods are described for defining a path of increasing response based on the minimum point and the response surfaces and for defining a set of values for the parameters in question, which result in increased response, A detailed explanation of the mathematical process used in this analysis is presented in the appendix for ease in computer programing the technique.

Jan 1, 1970

By David E. Emerson

An improved method and apparatus for determining the impurities in helium by preconcentration and subsequent analysis by mass spectrometry are described. Preconcentration of the impurities is accomplished by passing a known volume of helium, at slightly above atmospheric pressure, through a metal coil and trap assembly immersed in liquid helium. The concentrated impurities are then analyzed by mass spectrometry. This method can detect impurities in the range of 0.01 to 600 ppm with an accuracy of better than ±0.05 ppm at the 1-ppm level. One operator can analyze 15 samples in an 8-hour day.

Jan 1, 1970

By Neil B. Young

Analytical results for nahcolite, dawsonite, total extractable alumina, and oil yield are presented for samples representing Green River Formation oil shales in the saline section of two cores from Colorado's Piceance Creek basin. Analyses are also reported for samples extending the analyzed section of Colorado corehole No. 3 beyond that reported previously. These data permit evaluation of the deposit for possible production of three coproducts--shale oil, alumina, and sodium carbonates--from the saline section of the formation at these sampled points.

Jan 1, 1970

By John Nagy

Large-scale tests in the U.S. Bureau of Mines Experimental Coal Mine show that the explosion hazard of coal dust on shuttle-car roadways can be con-trolled by proper application of water, dry rock dust, a saturated solution of ammonium phosphate, or mixtures of water or the water-phosphate solution with rock dust. The experiments were made with loadings of 1.0 and 5.0 pounds of mine size coal dust per linear foot of entry, and with a 3-or 4-inch-thick layer of coal rubble on the floor, The data from the tests with mine-size coal and rubble are comparable. The water contents of the dust loading were determined from samples collected just prior to initiation of a gas-air mixture in an ignition zone at the face Dust samples were collected 1 inch deep from the coal-rubble deposit. One experiment was made with the dust in the coal rubble bound with latex applied as a water solution by spray. The binding action was inadequate and explosion propagation was obtained.

Jan 1, 1970

By R. J. Heemstra

A method was developed for calibrating photographic emulsions and retrieving working curves for emission spectrography. The values obtained from a digital readout or a recorder chart of a comparator-microphotometer are converted to light intensity values using an emulsion characteristic curve derived from a quartic polynomial preliminary curve. The characteristic curve, consisting of Seidel transform versus the logarithm of intensity, is split into two cubic polynomials at the zero value of the transform, resulting in eight emulsion calibration coefficients. These methods allow use of the calibration curves even at very small and very high intensities, thus extending the range of analysis. Use of a small computer allows rapid calculations. A computer program was written to formulate, code, and file each working curve along with its statistical error. Proper coding of the input data permits the direct printout of the concentration of the elements under investigation.

Jan 1, 1970

By D. S. Burgess

An investigation of the hazard of spillage of liquefied natural gas (LNG) onto water is described. About 2,000 gallons of LNG were consumed in various tests. The initial vaporization rate of LNG following spillage was found to be 0.037 lb/ft2 sec; when the spill was confined, this vaporization rate was moderated after about 20 seconds by the growth of an ice layer on the water surface; when the spill was unconfined, a coherent ice floe was not observed and the vaporization rate was essentially time independent. The maximum diameter (in feet) of the spreading LNG pool was found to be given by 6.25 Wo 1/3, where Wo is the weight of LNG in pounds, Downwind of a natural gas source, time-averaged methane concentrations were given in good approximation by standard air pollution equations. However, peak concentrations were as much as twentyfold higher than average, adding an additional factor to the assessment of hazard. The effect of layering by the cold vaporized natural gas was similar to the effect of a temperature inversion on normal gases in the atmosphere. Small-scale explosions were observed on pouring LNG onto a water surface; no single explanation seems pertinent to all of the incidents observed.

Jan 1, 1970

By Frank G. Horino

This report presents a method of utilizing the Coulomb strength criteria for estimating the strength and stability of pillars and pit slopes containing planes of weakness. It is assumed that the Coulomb theory, as a special case of the Mohr envelope, is a satisfactory first approximation of failure in uniaxial compression or triaxial loading with low lateral loads. Accepting this assumption for brittle materials, an expression for the strength decrease of rock pillars containing a plane of weakness or fracture at any angle of orientation is derived. As few as six samples (three solid cores and three fractured cores at a failure-oriented angle) are required for testing uniaxially and triaxially to statistically determine the coefficients of friction and the shear strengths of both the solid rock and the fracture plane and the range of failure angles of the fracture plane. Interpretation of the data shows that the mean normal stress and maximum shear stress technique of analyzing the data is superior for solid core and that shear and normal stress values using angles of failure should be used for fractured specimens with failure-oriented angles. Plots of either the strength or strength ratios against fracture angles obtained from oriented drill core samples give a useful first approximation of strength decrease due to fracture. Using the same test conditions for both fractured and unfractured material increases the validity of the tests.

Jan 1, 1970

By Mary H. Brown

The heats of formation of oxalic acid and sodium, potassium oxalates, and lithium oxalates were related by solution calorimetry to the heat of formation of (COOH)2.2H20, a value believed to be reliable as reported in the literature. The following heats of formation were determined: (COOH)2(a), -198.1±0.1; (COOH)2(ß), -197.8±0.1; UAW,, -328.7±0.4; Na2C204 -316.2±0.1; K2C204, -321.9±0.2; and K2C204-H20, -393.5±0.2 kcal/mole. The heat of the crystalline transformation (COOH)2(a) ? (COOH)2(ß) was determined to be 0.30±0.02 kcal/mole at 298.15° K.

Jan 1, 1970

By Oleg Terichow

The Bureau of Mines studied the penetration of a slender cylindrical tube into a sand bed, simulating seafloor material under the application of a static load. The factorial experimental design was based on three factors: tube diameter, geometry of penetrating bit, and seawater saturation of sand, all of which were found to be significant in influencing the depth of penetration. The geometry of the penetrating bit, or shoe, is of major significance in the mechanics of penetration and should be considered the most important factor for additional study. Linear regression analyses of the load-penetration data show that the relationship is linear.

Jan 1, 1970

By Roy F. Abernethy

This report describes a method developed by the Bureau of Mines for the determination of beryllium in coal ash. Samples are put into solution by standard wet chemical procedures. Interfering elements are complexed with Na2EDTA, and the beryllium is separated by extraction of its acetyl acetone complex with chloroform or carbon tetrachloride. Final determination is made with Beryllon II.

Jan 1, 1970