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By F. D. Sutterfield

This study was conducted to provide experimental evidence on the effect of modifications of gasoline front-end composition on the photochemical specific reactivities of automotive emissions. Evaporative and evaporative-plus-exhaust emissions from an automobile operated with four fuels of different volatility and varying levels of C.-C5 olefins were irradiated in a 10040 environmental chamber at three sets of initial hydrocarbon-nitrogen oxides concentrations. Reactivity was measured and expressed in terms of rate-of-NO2 formation and dosages of oxidant, peroxyacetyl nitrate, and formaldehyde. The compositional changes that were necessary in reducing fuel volatility were found to have no significant effect on the reactivity of the emissions. However, replacing C4-C5 olefins with saturated components resulted in sharp decreases in all reactivity manifestations observed for the evaporative emission samples. A lesser influence (of C4-C5 olefin replacement) was found with the composite exhaust-plus-evaporative samples; the effect that was observed could be attributed to the evaporative emission portion of the sample. The data therefore suggest that saturation of front-end fuel olefins had no large effect on exhaust emission reactivity.

Jan 1, 1971

By J. R. Ruark

This report presents results of the research and development work and operations performed during stage II of the gas combustion retorting research program conducted by the Colorado School of Mines Research Foundation and six major oil companies at the Bureau of Mines Anvil Points Research Facilities. The experimental program, including retort modification and air-gas distributor development, effects of shale quality and particle-size distribution, and other variables on the process, is discussed. Although operating problems are not fully resolved, it appears that the gas combustion retorting process can be successfully applied to achieve oil yields in excess of 85 percent of Fischer assay at mass shale feed rates of 500 pounds per hour per square foot of cross-sectional bed area, approximately twice the rate previously demonstrated to be reasonably practicable.

Jan 1, 1971

By Robert E. Wood

[The temperature dependency of the low-density thermal conductivity coefficients, ?°T, of nitrogen, 100° to 1,200° K, is correlated with the Keyes' equation, ?T ½ -1 -12/T) WT = aT+ bT 10 The equation ?T,P = ?°T +a[ ]ß represented 509 experimental higher V pressure thermal conductivities in the temperature range 131.2° to 973.15° K for pressures to 500 atmospheres, with a mean absolute deviation of 2.35 percent. This equation was used to compute thermal conductivities of gaseous nitrogen for 47 pressures, 1 to 240 atmospheres, and 110 temperatures, 133° to 740° K, which are common to conditions encountered in Bureau of Mines helium purification processes. Isobaric heat capacities, CP, and viscosities, ?T,P, from previous work were combined with the present thermal conductivities, ?T,P, to compute Prandl1 numbers, C?T P / ?T ,P, of nitrogen. Tabular values of Prandtl num¬bers are presented for 49 pressures, 1 to 240 atmospheres, and 75 temperatures, 133° to 740° K. Estimated uncertainties are ±5 percent in the tabulated thermal conductivities and ±15 percent for the computed Prandtl numbers. However, the uncertainty may rise to ±10 percent for thermal conductivities and to ±30 percent for Prandtl numbers as the critical conditions of nitrogen are approached.]

Jan 1, 1971

By Lester J. Crow

A preliminary survey was performed to investigate the impregnation of relatively weak, porous volcanic tuff and a relatively strong, dense sandstone with five different monomers. Increases in compressive strengths by factors of 2 to 5, and elastic moduli by factors of 2 to 3.5, are reported for natural rocks (tuff., sandstone, dacite), which were impregnated with five monomers (methyl methacrylate; chlorostyrene; 40 percent TMPTMA-60 percent styrene; 40 percent TMPTMA-60 percent chlorostyrene; 60 percent polyester-40 percent styrene); polymerization took place after monomers were forced into the rock. Impregnation was performed (1) by pressurizing rock specimens from one end, or (2) by a vacuum-soak operation. Polymerization was accomplished by either radiation or chemical initiation techniques. Strength improvement is dependent on (1) the type of monomer used, (2) the amount of polymer incorporated into the rock, and (3) the degree of water saturation of the rock. Water saturation strongly reduced the effectiveness of the method for the polymer systems tested. The more viscous monomers (for example, 60 percent polyester-40 percent styrene) were more effective in displacing the water from the rock, and compressive strengths of wet rock were doubled with these systems. Water saturations ranging from 25 to 100 percent of maximum saturation gave essentially identical results. Further tests on other types of mine rock; including shale and coal, are planned. Water-compatible polymer systems should be developed, or present systems should be suitably modified. For application to tunnel stabilization, design studies evaluating the improvement in rock strength and its influence on the support system are also recommended.

Jan 1, 1971

By David E. Nicholson

This report investigates the mechanical behavior of fine soils in a lunar environment in engineering gravity-flow bins. The ultrahigh vacuum, absence of moisture, and a lunar gravity one-sixth that of earth gravity represents a unique environment, both advantageous and detrimental to these systems. On earth, moisture and gases contained in powder masses can be responsible for complex descriptions of gravity flow. Their absence appear to simplify the lunar soil behavior. However, simulation of the lunar gravity and vacuum complicates the development of experimental data for designing bins. The properties of a dry soil powder, its behavior under one-dimensional compression, and its torsional and direct shearing strength under earth atmosphere are described in part 1 of this paper. These properties provide the parameters for a finite-element analysis to optimize the design of bins, to be described by Dr. William Pariseau in part 2. Shear tests assess the failure criteria for the material. Compression tests provide modulus and (Ko) stress-ratio values from the loading portion of the compression cycle, duplicating the condition of a bin at rest with the discharge closed. During the unloading portion of the compression cycle (soil overconsolidated), the residual Ko values rise. It is postulated that this phenomenon creates a high-lateral stress in bins when they approach incipient flow. Assessment of the Ko value, overconsolidation ratio, and the void ratio state is proposed as a criterion to determine the flowability of powder.

Jan 1, 1971

By A. W. Maynard

Simple chemical spot tests for the identification of major alloying elements in aluminum-base alloys are described. The tests are suitable for use by nontechnical personnel working outside a laboratory. Tests for zinc, copper, manganese, and magnesium employ electrographic sampling methods and sample papers. Use of electrographic sampling in a test for magnesium in aluminum is made possible by using glass fiber filter paper. Differentiations between magnesium and magnesium-silicon alloys of aluminum and between aluminum-base and magnesium-base alloys are made by direct chemical solution tests. Description of a device for obtaining reliable electrographic samples is included. A sequence of testing for identification by alloy groups is given.

Jan 1, 1971

By J. A. Lamonica

The Bureau of Mines studied a pulsation damping device designed to smooth pulsating flow in personal respirable dust samplers. The effect on the pulsation dampener efficiency of six parameters was investigated, as follows: Volume, diaphragm elasticity, diaphragm area, center orifice area, inlet-outlet orifice area, and geometry (LID ratio). The results indicate that volume pre-dominates in determining snubber efficiency, while the other parameters become important at small volumes. Geometry has no effect on snubber efficiency. Criteria for an efficient pulsation dampener construction were obtained.

Jan 1, 1971

By D. R. Corson

The Bureau of Mines instrumented two similarly backfilled stopes--one filled in the normal manner and the other with the fill densified using vibratory compactors--to evaluate the effect of fill compaction on subsequent vein-wall closure proposed as a adjunct process for strengthening cemented fill. Hydraulic pressure cells to monitor pressures within the fill and mechanical closure devices to measure vein-wall movement and the procedure for their installation are described. The field compaction work was generally performed manually by utilizing small commercial concrete vibrators. A prototype immersible vibrator using slusher cables to propel the vibrator in the stope was used on several lifts of fill. Although compaction efforts were less effective than anticipated in increasing the final density of fill, analysis of the field data does indicate somewhat improved strain characteristics and an increased pressure buildup for the densified fill. The effects of a prolonged period of inactivity and of rock burst occurrences in the immediate area are also reflected in plots of strain and pressure within the two instrumented stopes.

Jan 1, 1971

By R. V. Higgins

The results of two separate but related studies are given. In the first study, four equations were tested; the object was to determine which would produce a curve that would best fit data points that represent a trend of declining oil production in 90 California fields. Two conventional equations (the Arps and semilog) and two novel equations (extreme-c and double semilog) were tested. The curves were first fitted to the initial 9 years of the 15-year production data and then extrapolated for 6 years to determine how well the extrapolated curve would fit the data points. The generated curves were also extrapolated beyond the last data point to predict rates of future production. The results of the first study showed that no equation was clearly superior to the others in all respects. The semilog equation resulted in the best fit to production data for the first 9 years, but the Arps and extreme-c equations produced a better fit for the extrapolated data for the period of 9 to 15 years. The Arps and extreme-c also gave more realistic production rates when extended to the point where cumulative production equaled reserves. A second study was made to determine if the least-squares technique applied to the Arps equation would result in more accurate extrapolations. The merits of the logarithmic and the nonlogarithmic forms of the Arps hyperbolic equation were also tested. For the logarithmic expression, it was found that one of the constants of the Arps equation reached a value so small or so large that the equation was not applicable to the data of 40 of the 90 California fields. The nonlogarithmic form of the Arps equation was applicable to neither the same 40 fields nor to a few additional ones. When the data and the Arps equation were compatible, the use of the least-squares technique as compared with other methods improved the extrapolation accuracy somewhat.

Jan 1, 1971

By R. D. Groves

Techniques were developed for preparing metallurgical-grade copper powder from industrially produced cement copper. Flotation was used for rejecting discrete gangue particles, acid leaching to remove residual iron and aluminum, hydrogen reduction to eliminate oxygen, sintering to consolidate the fine-sized copper, and grinding to obtain copper powder. Powders prepared from six different cement copper samples contained, in percent, 98.5 to 99.0 Cu, 0.10 to 0.05 Fe, 0.10 to 0.08 insoluble material and the remaining individual impurities less than 0.15 percent. The apparent density, flow characteristics, and other physical properties were suitable for powder metallurgy applications. An economic evaluation showed that this process was economically feasible. Processing costs appeared modest when considering that copper powder commands a price normally about 17.5 cents per pound over that of electrolytic copper.

Jan 1, 1971

By S. C. Schaefer

Thermodynamic properties of indium oxide (In203) have been studied with a high-temperature galvanic cell employing stabilized zirconia electrolytes. In the temperature range 790° to 1,230° K the free-energy change for the cell reaction 21n(1) + 3Cu20(c) = In203(c) + 6Cu(c) together with the standard free energy of formation of cuprous oxide gives the standard free energy of formation of indium oxide from the elements as ?Gf° = -218.78 + 75.34 X 10-3T ±0.7 kcal/mole. A third-law analysis yields the standard enthalpy of formation: ?Hf°298.15 = -221.5 kcal/mole.

Jan 1, 1971

By J. A. Lamonica

The Bureau of Mines conducted an environmental noise survey to determine the noise levels to which underground coal mine employees are exposed, to evaluate noise survey techniques and equipment, and to compare noise exposures using two criteria, Walsh-Healey and CHABA, for determining allowable exposures that were under consideration for the Federal Coal Mine Health and Safety Act of 1969- Time study techniques and Bureau-approved standard sound level meters were employed. The shift exposures of 20 percent of the miners studied were in excess of the safe standards established by both criteria. The shift exposures calculated using the Walsh-Healey criteria were greater than those calculated using the CHABA criteria owing to the intermittent nature of the exposure. Ultimately the CHABA criteria were rejected, and the Walsh-Healey criteria were adopted.

Jan 1, 1971

By L. B. Pankratz

Enthalpies above 298° K were investigated for four crystalline sodium borates by copper-block drop calorimetry. Determinations were made to 1,200° K for NaB02, 1,003° K for Na2B407, 1,005° K for NaB305, and 1,046° K for Na2Be013. No phase transitions or other thermal anomalies were found. The enthalpy determinations, when combined with known heats of formation at 298° K and other supplementary data, enabled the calculation of the heats and free energies of formation of the compounds to their melting points. Values of relative enthalpies, entropies, heat capacities, free energy functions, enthalpies of formation, free energies of formation, and equilibrium constants of formation were tabulated at even temperatures.

Jan 1, 1971

By J. Grumer

Nine dust and gaseous inhibitors of propagating coal dust-air flames (lean, stoichiometric, and rich) were evaluated in a newly developed 15-cm-id, 3.6-meter-long instrumented flame duct, under conditions such that wall quenching was virtually absent and the dust concentration was temporally and spacially uniform to within about t5 percent. Listed roughly in order of increasing efficiency, the inhibitors evaluated were rock dust (calcium carbonate), powdered oyster shells (calcium carbonate), Halon 1301 (trifluorobromomethane), Halon 1211 (difluorochlorobromomethane), sodium chloride, Super-K (potassium chloride), regular-grade fire extinguishant powder (sodium bicarbonate), Purple-K (potassium bicarbonate), and Monnex (potassium bicarbonate combined with urea). Experiments were extended to clouds containing 1 and 2 volume-percent of methane. The inhibition of lean, stoichiometric, and rich methane-air flames without coal dust was also examined in a few instances; results agreed with those obtained for coal dust-air flames.

Jan 1, 1971

By Thys B. Johnson

A three-dimensional dynamic programing method is presented for determining the optimal ultimate open pit limit. The method given is based on the block concept and is an extention of the two-dimensional Lerchs-Grossmann approach. The three-dimensional technique presented herein is fast and simple and may be used for an initial open pit evaluation when only limited data are available or as a more refined model when the entire deposit is well delineated. The method is illustrated by simple numerical examples and is also presented in algorithmic form. A computer program was written in Fortran IV which implements the three-dimensional algorithm and some computational aspects are discussed.

Jan 1, 1971

By W. L. Staker

Alternatives were developed to the conventional ammoniacal carbonate leaching-steam stripping procedure for recovering copper as an oxide from contaminated scrap metal. By entraining air bubbles in the leach solution, the copper dissolution rate was increased to 1.5 g/in2 of copper surface per hour, compared to 0.5 g/in2/hr produced by conventional agitation in stirred tanks. Using entrained nitrogen gas bubbles for agitation in conjunction with powdered sulfur not only resulted in rapid dissolution but also simultaneous precipitation of the copper from solution as a high-grade cuprous sulfide.

Jan 1, 1971

By John J. Mulligan

The Bureau of Mines sampled a gold-bearing schist series 50 miles east of Nome near Bluff, a dormant mining camp on the southern shore of the Seward Peninsula, Alaska. Gold is unevenly distributed through a section of a schist series that extends from the coast northward 4,500 feet. In this section the schists dip westward 20 to 38 degrees and have an outcrop width of about 1,000 feet and a normal width of about 500 feet. An intensely fractured zone within the schists averages 0.015 to 0.017 ounce of gold and 0.03 to 0.05 ounce of silver per ton for outcrop widths of 200 to almost 500 feet. The grade of the remainder of the schist series ranges downward to scant traces. Gold eroded from these schists collected in solution channels in metalimestones to form the Daniels Creek placers, which also extend from the beach southward under the sea for an unknown distance. The lode sources of the gold placers elsewhere in the southern Seward Peninsula may be similar schists that occupy a similar position in the metasedimentary series.

Jan 1, 1971

By E. Morrice

The effect of the temperature of SmF3-LiF electrolyte on the electrolytic preparation of samarium-cobalt alloy by the consumable cathode technique was investigated. The temperatures of the cathode zone, alloy collection zone, and samarium oxide (Sm203) feed zone had to be controlled carefully to obtain a satisfactory samarium-cobalt alloy product. Any appreciable deviation from certain temperature values adversely affected yield and product quality.

Jan 1, 1971

By C. M. Frost

The hydrodesulfurization characteristics of a Venezuelan topped crude oil and a Venezuelan reduced crude oil were determined at temperatures from 740° to 850° F, pressures from 800 to 1,600 psig, and space velocities from 1.0 to 2.0 Vo/Vc/hr. Kinetic calculations showed that under these conditions the desulfurization reaction was first order with respect to sulfur and had an average activation energy of 32.5 kcal/mo1. Catalyst life tests made at 750° F, with pressures of 800, 1,200, and 1,600 psig and space velocities of 1.0 and 1.25 Vo/Ve/hr, showed that the decrease in the relative activity of the catalyst was a logarithmic function of time or volume of oil processed and the amount of vanadium deposited on the catalyst. Comparative tests made with residual fuels prepared from a Wilmington, Calif., crude oil and a Wyoming asphaltic crude oil showed that catalyst life may be extended by processing fuel oil with a low metal content, but it may be shortened by the presence of large amounts of asphalt in the feed.

Jan 1, 1971

By George R. Schottler

The Bureau of Mines investigated the distribution of uranium and various methods of ore sampling in a uranium deposit typical of those in the Morrison Formation sandstone of the Ambrosia Lake area, Grants mining district, north-western New Mexico. Chemical and radiometric assays of diamond-drill core samples are compared in detail by statistical techniques, and the assay data are correlated with the stratigraphy of the deposit. Conclusions applicable to ore-reserve estimation in geologically similar uranium deposits are drawn.

Jan 1, 1971