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By M. J. Ferrante

Low-temperature heat capacities and high-temperature enthalpies were determined calorimetrically for Na2Cr04, A reversible transition was found at 700° K with an isothermal heat of transition of 2,263 cal/mole. High-temperature X-ray diffraction analysis showed that the transition was a crystal change from the low-temperature orthorhombic form to the high-temperature hexagonal form. At 795° K the hexagonal form had the parameters a, = 5.691 and co = 7.478 A. Powder diffraction data for the high-temperature form are given and possible structures discussed. The melting point was determined to be 1,065° K with a heat of fusion of 5,810 cal/mole. Enthalpy and entropy increments from this investigation were combined with other data from the literature to calculate enthalpies of formation, free energies of formation, and equilibrium constants of formation from 298° to 1,400° K. Equations that represent enthalpies above 298° K are given.

Jan 1, 1972

By David J. MacDonald

Stability constants, that is, equilibrium constants for complex-formation reactions, have been determined by a titrimetric method for complexes formed by the transition metal ions Ni2+, Cu2+, Zn2+, and Cd2+ with the structurally analogous bidentate ligands N-ethylethylenediamine and 2-(ethylthio)-ethylamine. The sulfur containing ligand was found to be the weaker of the two chelating agents for each of the four metals. Absorption spectra of the individual complexes have been determined in order to calculate their crystal field stabilization energies. The combined results suggest a linear relation between free energy of chelation and ionic radius of the metal ion.

Jan 1, 1972

By F. N. Kissell, R. J. Bielicki, J. H. Perkins

A sorption apparatus for measuring the equilibrium sorption isotherm and the rate of diffusion of methane from fine-sized coal was designed and constructed. Preliminary work that used Pittsburgh and Pocahontas No. 3 coal shows that the diffusion coefficient varies with pressure and that the fracture spacing in these two coals is substantially different.

Jan 1, 1972

By R. J. Bielicki

A sorption apparatus for measuring the equilibrium sorption isotherm and the rate of diffusion of methane from fine-sized coal was designed and constructed. Preliminary work that used Pittsburgh and Pocahontas No. 3 coal shows that the diffusion coefficient varies with pressure and that the fracture spacing in these two coals is substantially different.

Jan 1, 1972

By G. W. Reimers

Metastable pyrophoric wüstite (FexO, with x between 0.89 and 0.95) was found to be much easier to grind to colloidal state than were its stable disproportion products magnetite or iron. The grinding of polycrystalline magnetite appears to be complicated by the magnetic flocculation arising from interparticle attraction. This is superimposed on the attraction of a fluctuating electric dipole for a neighboring induced dipole. More than 85 pct of the tumbling time was saved by grinding antiferromagnetic wüstite instead of the ferrimagnetic oxide of iron (Fe304). Disproportionation of colloidal wüstite to the stable ferromagnetic and ferrimagnetic colloidal particles of alpha-iron and magnetite, respectively, was accomplished rapidly at temperatures above 250° C but below 570° C, the eutectoidal stability point of the wüstite phase.

Jan 1, 1972

By Richard A. Dick

Eight blasts were fired in a 2-1/2-ft bench in the Stewartville member of the Galena Limestone formation in an aggregate quarry near Stewartville, Minn. The shots were dimensionally proportional to production-size bench blasts and were about 5 to 10 percent of full scale. The effects of site, timing of initiation, and burden-to-spacing ratio were studied in a 2 x 2 x 2 factorial experiment, using three boreholes, caw;, containing a 1/2-in charge diameter of high-density ammonia dynamite, in each blast. Detonation velocity measurements indicated that the dynamite detonated satisfactorily in the 1/2-in charge diameter. The effects of the three experimental variables were analyzed by weight for the percentage of oversized material produced and for size distributions determined by screening the entire muckpiles. The bench faces were painted before each shot in an effort to determine the origin of the oversized material. The square pattern (burden and spacing = 15 in) produced finer overall fragmentation and less oversized material than the rectangular pattern (burden = 15 in; spacing = 22-1/2 in). Sites 1 and 2 were about ft apart. Although site 2 produced slightly better overall fragmentation than site 1, the amounts of oversized material produced showed no significant difference. The timing of initiation (instantaneous or delayed) did not significantly influence the overall fragmentation or the amount of oversized material produced.

Jan 1, 1973

By J. B. Janus

This report, the 22d in a series, gives analytical data showing composition and quality of tipple and delivered samples of coal collected during fiscal year 1972. This coverage lists mines located in 20 States. Ultimate analyses are given for most of the coalbeds listed. Tipple samples were collected by Bureau of Mines engineers at tipples as coal was being loaded into railroad cars or trucks. The deliveries were sampled in accordance with instructions issued by the Bureau of Mines, and the samples were analyzed in the Bureau laboratory at Pittsburgh.

Jan 1, 1973

By E. G. Valdez

Three cryogenic systems that utilized liquid nitrogen, dry ice, and methanol with dry ice were investigated in conjunction with crushing and classifying techniques. The systems were used to aid in separating and reclaiming the metallic components contained in insulated wires, shredded automobile nonferrous metal concentrates, small motors, generators, and rubber tires. Wire strands, 2 to 6 inches long and insulated with polyvinyl chloride and neoprene, were chilled at -60° and -195° C, then roll-crushed and processed by water elutriation; this procedure resulted in two products--a sink fraction that was 99 percent metallic and a float fraction that was 99 percent nonmetallic. Excellent separation of zinc die-casting alloys from copper and aluminum contained in shredded automobile nonferrous metal concentrates was attained by chilling at -72° C for 1 minute, crushing in a grateless hammer mill, and screening. From the screened products, 97.2 and 100 percent of the copper and aluminum, respectively, were recovered in the plus Pinch fraction, and 100 percent of the zinc was recovered in the minus 1-inch fraction of over 97 percent zinc die-cast purity. Laboratory experimental results comparing direct and indirect chilling indicated that a sufficiently low temperature could be attained by indirect chilling to permit use of a liquid C02-dry ice system on insulated wires and mixed nonferrous metallic concentrates.

Jan 1, 1973

By G. L. Fitzpatrick

Future applications of seismic holography to "seismically transparent phase objects," such as rock inclusions, fracture zones, liquid-filled cavities, etc., will require techniques to improve the poor image contrast generally characteristic of these objects. Although conventional phase-contrast enhancement techniques could be used, these methods involve additional optical elements such as quarter-wave spatial filters. Owing to the anticipated practical difficulties of properly alining such optical devices and properly locating poorly defined image planes and filter planes, this approach is not considered to be well-suited to the case of seismic holograms and their laser reconstructions. Results similar to those achieved with spatial filters may be obtained without filters by specially processing the seismic hologram data. The new process, which is an extension of Gabor's subtraction holography, achieves an improvement in contrast by an interferometric technique. The process involves adding a ?before" hologram without an object present to a 90° phase-shifted "after" hologram with the object present. Then, the combination is reconstructed with a laser or by computer. Not only is the image contrast improved in such processed holograms, but the images are also phase-contoured. In general, the latter feature is not to be expected when conventional phase-contrast enhancement techniques are employed. The new technique is experimentally verified by examining computer-generated synthetic seismic holograms rather than by examining actual seismic field data. However, results of this study are directly applicable to real seismic data and should prove useful in future applications of seismic holography.

Jan 1, 1973

By Joan C. Biordi

A molecular beam-mass spectrometer-low pressure flat flame apparatus has been constructed for the purpose of examining the chemical microstructure of normal methane-oxygen-argon flames and those inhibited with Halon extinguishants. Details of construction and performance of this apparatus and of related flame temperature measurements are given. Particular attention is paid to the empirical characterization of the perturbation to the flame caused by the sampling probes. The composition profiles obtained for normal flames are compared to those of flames inhibited by CF3Br. In addition to the usual stable species (CH4, O2, CO, CO2, H2O, H2, and H2CO), the inhibitor, its products and intermediates associated with its reactions could be followed. In particular, hydrogen bromide, bromine atoms, hydrogen fluoride, and carbonyl fluoride were observed. The relatively rapid disappearance of inhibitor and early appearance of fluorinated reaction products suggest a short lifetime for the CF3 radical in this system. Observation of COF2 suggests that CF3Br is effective as an inhibitor, at least in part, by virtue of its interference with the oxygen containing species of the normal chain reaction. Profiles of the 17+ peak at low electron energy suggests that the hydroxyl radical may also be sampled, but the profiles obtained are not yet sufficiently accurate to determine the effect of inhibitor on this important flame radical.

Jan 1, 1973

By John Ward Smith

Aragonite, co-occurring with calcite and dolomite as matrix minerals, has been discovered in Mahogany zone oil shales of Colorado's Eocene Green River Formation, posing puzzles on the geochemical patterns of their separate origins, reasons for their simultaneous existence, and their interrelation. The presence of aragonite is demonstrated by X-ray diffraction. Amounts of aragonite and dolomite are significantly and inversely related, but the calcite quantity is essentially independent of either aragonite or dolomite quantity. A geochemical pattern outlining the deposition conditions that created the Green River Formation oil shale is postulated from characteristics of the oil shale. The development of the three separate carbonates--aragonite, calcite, and dolomite--the inverse relationship between aragonite and dolomite, and the independence of amounts of calcite and the other two carbonates are shown to be natural consequences of this oil-shale genesis pattern.

Jan 1, 1973

By J. S. Miller

The Bureau of Mines developed methods for fragmenting oil shale formations with chemical explosives to prepare oil shale for in situ retorting and to evaluate the extent of fragmentation by various methods. A combination of three methods of explosive fracturing was used: (1) The displacement and detonation of a liquid chemical explosive in a natural fracture system; (2) the use of 60-pct dynamite to relieve stress conditions of the rock around the wellbore; and (3) the use of pelletized TNT in a series of wellbore shots to fragment the oil shale. An attempt was made to seal or grout around the fragmented oil shale by drilling 67 holes and displacing approximately 200 bbl of neat cement in the fracture system to aid in evaluating the fragmented zone, Seven methods were used to evaluate the fragmented zone. The primary evaluation method was the recording of seismic waves to delineate the fragmented zone with results based on arrival time, amplitude, and record quality. The data from the seismic measurements indicated the extensively fragmented zone was approximately 95 ft in diameter and 70 ft thick. Results of the remaining methods of evaluating fractures--including air-flow tests, coring of the expected fragmented zone, elevation measurements to indicate overburden crowning, and surveys with high-speed camera, impression packer, and down-hole camera--agreed with and supported the data from seismic measurements. Further field application of explosive fracturing and evaluation methods is needed to determine when a zone of oil shale is effectively fragmented for efficient in situ retorting.

Jan 1, 1973

By G. A. Wancheck

Shear tests were performed on several prepared samples of granular and powdery bulk materials to investigate the following parameters: Particle size and distribution, particle movement, moisture content, consolidation of material, bulk density, void ratio, porosity, volume change, and strain rate. A series of shear tests was performed with weight-percent-ratios of minus 0.185-inch tertiary sand and 1-1/2-by l/2-inch tertiary gravel mixtures, and weight-percent-ratios of minus 200-mesh limestone (rock dust) and minus 200-mesh bituminous float coal dust. A comparison was made for shear test results obtained with rectangular and circular shear cells utilizing the large and small direct shear testers. Specifically, the shear results obtained include the angle of internal friction or shear strength of the tested material under known consolidating pressures, and the kinematic angle of friction or coefficient of friction between the interface of a bulk material and a sample wall material. The experimental procedure, tests, and results are given for each parameter investigated.

Jan 1, 1973

By W. T. Abel

The difficulties associated with wet-processing fine size coal led the Bureau of Mines to investigate a dry process for removing pyrite from coal pulverized to powerplant fineness. The dry process that was investigated consists of two cleaning steps: First, centrifugal separation is used to remove a fine, pyrite-depleted portion as a product; second, the remaining coarser, pyrite-enriched portion is taken to electrostatic separation in which pyrite is concentrated and rejected. Ball milling and Hardgrove milling were used to pulverize the coal. Three coals from the Pittsburgh seam were treated by the dry-removal process. Over 55 pct of the pyrite, which amounted to 70 pct of the available pyrite, was removed in a reject of 10 to 20 pct from one of the coals. Similar treatment of the other two coals removed about 35 to 50 pct of the pyritic sulfur, which amounted to about 70 pct of the available pyritie, sulfur from these coals. Both centrifugal and electrostatic separations were more efficient when pyrite particles were as large as possible. Separation efficiency was improved by confining the particle size of the feed to a relatively narrow range and by avoiding excessive amounts (more than 10 pct) of dust in the electrostatic range. The removal efficiency was increased with the use of stage grinding.

Jan 1, 1973

By R. S. Fowkes

A study was made by the Bureau of Mines of the penetration of selected granular materials in an unconfined state by wedge-shaped tools having dimensions comparable with the dimensions of the particles composing the materials. The output force for larger particles fluctuated radically. A custom-designed integrator was used to obtain work as a function of depth of penetration in the form of smooth curves. The influence of wedge angle, depth of penetration, penetration rate, entry angle, compaction state, and particle size on the force required and the work performed was ascertained. Empirical equations describing force and work as a function of penetration were obtained for each set of experiments.

Jan 1, 1973

By H. L. Gibbs

A portable radon monitoring instrument capable of making on-the-spot measurements of the radon gas content of uranium mine atmospheres was designed and constructed. The monitor was tested in the laboratory and in operating uranium mines. Good correlation was obtained between the monitor readings and radon measurements made on mine atmosphere samples taken in radon bottles.

Jan 1, 1973

By R. K. Koch

The normal spectral emissivities of liquid Ti, V, Zr, Mo, and Pt were determined at the fusion temperatures in an electron-beam furnace using a water-cooled copper hearth. The normal spectral emissivities were estimated above the melting points by using adjusted two-color temperatures as approximations of the true temperatures for substitution in Wien's equation. Simultaneous brightness temperatures were determined with a micro-optical pyrometer. The true temperature ranges covered were 1,668° to 1,885° C for Ti; 1,919° to 2,013° C for V; 1,855° to 2,367° C for Zr; 2,610° to 2,751° C for Mo, and 1,772° to 1,990° C for Pt. The spectral emissivities for titanium and zirconium decreased with increasing temperature. At an effective wavelength (?) of 658 mµ the emissivity of titanium ranged from 0.51 to 0.45 and zirconium, from 0.47 to 0.41. The emissivities of vanadium (? = 658 mµ) and molybdenum (? = 657 mµ) were constant at 0.41±0.02 and 0.33±0.01, respectively. The spectral emissivity of platinum (? = 658 mµ) was constant at 0.39±0.02 up to 1,900° C; above that temperature anomalous data were obtained. A mass spectrometric study indicated that platinum was reacting with back-streaming silicon vapors from the diffusion pump when the ambient pressure was greater than 2 X 10-5 torr.

Jan 1, 1973

By Ronald A. Munson

Samples of the naturally occurring zeolites phillipsite, clinoptilolite, erionite, and chabazite have been surveyed for their gas adsorption, ion exchange, and other characteristics. Chabazite and erionite, which are generally more stable, also have higher methane adsorption capacities than do the other natural zeolites. Both natural erionite and natural chabazite are classified as small-port zeolites on the basis of their inability to adsorb chlorotrifluoromethane. In the range of 8 to 100 mesh, the adsorptive capac-ity of natural zeolites is improved only slightly by a decrease in particle size. The capacity of natural clinoptilolite to adsorb methane is increased by cation replacement by the hydrogen ion and decreased by exchange with calcium ion. Natural phillipsite, which is easily decomposed by heat, adsorbed methane to a limited extent.

Jan 1, 1973

By Foster Fraas

This report describes the application of pulsed magnetic fields derived from alternating and intermittent magnetizing currents. Application of such pulsed magnetic fields to the matrix-type separator permits (1) the complete discharge of the magnetic fraction with wet feeds and (2) the dry separation at particle sizes down to 325 mesh. At smaller particle s indications are that frequencies above 60 hertz will be required. Applications of intermittent magnetizing current to the cross-belt separator give the cross-belt-separator an advantage over the conventional constant-field cross-belt and induced roll separators; the intermittent current enables the cross-belt separator to separate matted fibrous and magnetically coagulating feeds, a type of feed that occasionally occurs with mineral, industrial, and secondary materials.

Jan 1, 1973

By David E. Siskind

The Bureau of Mines has studied the fracturing and associated damage occurring in the vicinity of blastholes from five shots fired in the shale pillars in the White Pine copper mine, White Pine, Mich. Four types of explosives (AN-FO, commercial extra dynamite, ammonia gelatin dynamite, and a low-density, low-velocity permissible) were used. Cores were taken from the blast region and examined by ultrasonic and petrographic techniques. Pulse wave velocities were measured across the core diameters, and thin sections showing cracks and changes in lithology were examined in an attempt to establish zones of damage. Cores from the blast regions and areas near pillar free faces were found to have abnormally low pulse velocities. Petrographic study of the thin sections showed that the negative velocity anomalies were caused by cracks in the cores. Crushing and extensive fracturing prevented meaningful measurements on core fragments from the immediate blast vicinities. Compositional, changes and other rock nonuniformities, such as joints and preexisting fractures, tended to mask detailed damage differences among the four explosives; however, the two most energetic explosives (extra dynamite and ammonia gelatin dynamite) produced damage zones two to three times as large as the AN-FO and low-velocity permissible explosives.

Jan 1, 1973