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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 H. P. LeVan

The Bureau of Mines has developed a technically feasible continuous single-stage leaching and thickening system for extracting manganese from umber by a sulfuric acid-ferrous sulfate process; the cocurrent leaching and thickening system proved simpler to operate and control than the countercurrent leaching and thickening system developed earlier" Related tests investigated the use of a centrifuge to replace thickeners for separating the product liquor from are residues and compared several chemical agents for removing iron from the pregnant manganese leach solutions. Results of Some exploratory autoclaving tests are also given.

Jan 1, 1972

By Helen W. Lang

The Bureau of Mines has developed a very rapid gas chromatographic method for routine determination of oxygen, nitrogen, methane, and carbon dioxide in mine atmosphere samples. Analysis is accomplished in 3 min; readout appears on a single strip chart. The gas sample is split between two columns contained in separate chromatographs. A 5 A molecular sieve column separates oxygen, nitrogen, and methane; a porous polymer column separates carbon dioxide from an air peak. Direct selective analysis of methane from this unresolved air peak is accomplished using a hydrogen flame ionization detector (FID). Carbon dioxide is catalytically converted to methane and detected by FID.

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 Larry A. Haas

Carbonyl sulfide (COS) was decomposed to sulfur and CO in a silent electrical discharge. A threshold of about 4 kv at 60 Hz was required to dissociate the gas in a laboratory ozonizer at 790 torr with electrode gaps between 1 and 5.5 mm. Above the threshold value, the reaction rate increased with increasing voltage with helium or nitrogen diluent. With the latter diluent, higher voltages had to be applied to obtain the same yield in the 4-to 12-kv range. The COS decomposition rate increased with COS concentration, but a saturation value was reached at about 10 pct COS. The reaction rate decreased at low linear gas velocities as obtained at lower gas flows, larger electrode gaps, or larger reactor volumes. Increasing gas temperature also decreased the decomposition rate. The presence of solid adsorbents such as quartz wool, bauxite, or charcoal had no significant effect on the reaction rate. The addition of S02 did not affect the COS decomposition rate, but small amounts of water decreased the reaction rate. Over 50 pct of the COS was decomposed at room temperature and atmospheric pressure in a l7-kv ozonizer using a gas containing 0.9 pct COS in helium flowing at a rate of 0.3 liter/min. The average current was less than 5 ma. This method has possible application in eliminating the toxic air pollutant, COS, which is generated in petroleum refineries and in processes involving reactions between sulfurous and carbonaceous materials. Carbon monoxide that is formed can be further oxidized to CO2 after the collection of elemental sulfur.

Jan 1, 1972

By George J. Conroy

Electrical power generation was studied in a laboratory-scale, open-cycle vortex MHD generator, which offers several advantages over straight-channel generators that require separate combustors. Compactness, lower capital cost, and high-energy release are obtained by combining the combustor and generator into one unit in the vortex generator. In addition, the vortex generator uses a simple solenoid rather than the more complex and expensive saddle magnet required for straight channel generators. Although the vortex generator must utilize combustion gases with a low Hall coefficient in order to be efficient in direct comparison to the linear generator, the primary motivation for this experimental device in terms of ultimate objective was to investigate the vortex generator with applications to direct coal firing and with combustion taking place in specially designed expansion nozzles. The vortex device offers one decided advantage over the linear device in this regard because slag deposits do not degrade or short-circuit the coaxial electrodes as is the case for a linear machine. The experimental vortex generator consists of a modified cyclone burner 7 ½ in ID by 21 in long, with the inner wall used as one electrode together with a coaxial center electrode. Power was obtained by impressing an axial field of 3,000 G from an air core solenoid magnet. Tests were conducted by seeding natural gas seeded with potassium acetate and burning with preheated oxygen-enriched air. Power generation was lower than calculated because theoretical plasma velocities were not achieved.

Jan 1, 1972

By B. Dimitriades

Experimental work has been done to refine and to confirm an analytical procedure by which gas-liquid chromatographic (GLC) spectra are interpreted from retention time data alone. The rationale of this spectra interpretation technique involves whether or not a given peak invariably represents the same component or component mixture; if not, what factors influence changes in peak identifications. To answer these questions, peak-identification procedures, based mainly on the use of subtractive columns, were developed and applied to interpret GLC spectra of several exhaust (and fuel) samples.

Jan 1, 1972

By M. E. Tyrrell

Work in this investigation was undertaken by the Bureau of Mines to demonstrate how waste glass might be utilized to lower the required firing temperature and firing time of structural clay products. Mixtures of waste glass and common clays were formed by stiff-mud extrusion and fired to the temperature required to produce a body having 6 to 7 percent absorption. Substitution of glass for one-half of the clay in a red body reduced the firing temperature 500° F, which made possible a 30-percent increase in production; in a tan body, the firing temperature was reduced 400° F, which made possible a 23-percent increase in production.

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 J. D. Kalasky, Stephen Krickovic

A degasification experiment was conducted in a Pocahontas No. 3 coalbed mine in Virginia. It involved (1) drilling holes in the coalbed in the out- side headings of a set of five being developed in virgin area, and (2) conducting a methane emission rate study as mining progressed and additional holes were drilled. Degasification from all drill holes except the longest in each of the outside headings and the first three drilled (excluding the in-situ pressure hole), was erratic and inconsequential in methane emission rates. The two longest holes liberated 66 and 79 cfm of methane, which is significant for the coalbed, but such quantity lasted a relatively short time; the first three were uniform but low in methane emission.

Jan 1, 1972

By Stephen Krickovic

A degasification experiment was conducted in a Pocahontas No. 3 coalbed mine in Virginia. It involved (1) drilling holes in the coalbed in the out-side headings of a set of five being developed in virgin area, and (2) con-ducting a methane emission rate study as mining progressed and additional holes were drilled. Degasification from all drill holes except the longest in each of the outside headings and the first three drilled (excluding the in-situ pressure hole), was erratic and inconsequential in methane emission rates. The two longest holes liberated 66 and 79 cfm of methane, which is significant for the coalbed, but such quantity lasted a relatively short time; the first three were uniform but low in methane emission.

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 Robert B. Worthington

This investigation was undertaken to develop a more efficient copper smelting practice that would help meet the increasingly stringent antipollution standards. Continuous smelting to copper and a 0.8-to 5-percent copper slag using pure oxygen has been demonstrated for several hours at a time in a unique double furnace, which was devised to overcome the heat losses inherent in a laboratory furnace. The use of pure oxygen to effect the smelting and conversion of copper sulfide concentrate in a single unit to produce blister copper and a very high S02 concentration provides a much reduced gas volume for more economical and thorough sulfur recovery. Although the process was successfully demonstrated for several hours at a time, extended test work using longer runs will be required to balance the system and to obtain test data for adequately demonstrating its technical feasibility.

Jan 1, 1973

By Robert C. Steckley

A study of joints in Marathon County, Wis., was made to determine the orientation of regional paleotectonic stresses and to develop a method of using optical diffraction analysis (ODA) in studying joint orientations and spacings. Standard geologic and petrofabric techniques employing the use of a geologic compass and a Schmidt net were used in gathering, describing, and reducing joint orientation data. Analysis of selected outcrops with ODA indicates that ODA can be applied to study both joint orientations and spacings. ODA is shown to be a rapid method that can be used to complement standard petrofabric techniques, especially in the study of joint spacings.

Jan 1, 1972

By B. H. Eccleston

Experimental work is reported showing the effects of gasoline characteristics on auto emissions. Fuel volatility is shown to influence evaporative losses, with the higher losses associated with higher volatility. Fuel front-end olefin is shown to contribute significantly to reactivity of emissions. Large vehicle-to-vehicle differences were found. The study was conducted by the Bureau of Mines at its Bartlesville Energy Research Center in cooperation with the Coordinating Research Council Air Pollution Research Advisory Committee. The work was done using 15 1968-70 model autos and eight fuels were tested at ambients ranging from 20° to 95° F. Data on emissions from each vehicle-fuel-temperature combination are presented. Also included are calculated photochemical reactivity data and the distribution of hydrocarbon and nitrogen oxides during the test cycle.

Jan 1, 1972

By Alan H. Goode

Glass wool meeting requirements for commercial use was made from glassy fractions of urban solid wastes by the Bureau of Mines. This research was a part of the Bureau's program to develop building products and other usable materials from reclaimed urban waste materials. Mixes of molten glass were fiberized into glass wool during laboratory studies by impingement of a jet of compressed air on a stream of the molten glass. The principal test variable studied was composition of the melt; this was varied by adding dolomite and alumina to obtain molten glass with the handling characteristics required for producing final wool products of the desired composition and physical characteristics. When no charge is made for the waste glass and approximately $75 per ton can be obtained for the wool product, an interest rate of return on investment after taxes of about 12 percent can be obtained. If a charge of $5 per ton is required for the waste glass, a selling price of about $78 per ton would be necessary to obtain a l2-percent-interest rate of return on investment after taxes.

Jan 1, 1972

By George A. Savanick

The objective of this research is to develop a method for measuring the tensile strength at the interface between minerals in rock. These measurements reflect the strength of the attractive forces operating at crystalline interfaces in rock. Since these forces act in opposition to the forces set up in various rock fragmentation processes, measuring their strength may help in designing more efficient methods of rock fragmentation. The method developed for measuring the strength of intergranular adhesion in rock involves separating a bicrystal from the rock and determining the tensile strength at its solid-solid interface. This technique has been successfully applied to the study of quartz-feldspar interfaces separated from massive pegmatites, graphic granite, and the Rockville granite, yielding average tensile strengths of 5.86, 8.62, and 10.65 meganewtons per meter squared (MN/m2) (850, 1,250, and 1,524 psi, respectively). The data this technique provides indicate that the members of these bicrystals are strongly adherent. Examirtation of bicrystals broken at the crystalline interfaces indicates that the bonds responsible for this adhesion operate over only a portion of the interfacial area. This work conclusively demonstrates that tensile strength tests can be conducted on small selected areas; for example, grain boundaries in rock. The small-scale zones of strength or weakness determined in this way can be related to the overall strength of the rock.

Jan 1, 1972

By D. C. Fleck

Electrorefining yttrium from selected low-melting yttrium--base alloys is investigated, and various halide systems are studied as potential electrolytes for use in preparing low-oxygen yttrium by electrorefining unalloyed yttrium. Yttrium cathode products having significantly less metallic impurities than the anode materials were prepared from alloys containing nickel, iron, and manganese by electrorefining in LiCl-YC13 electrolytes at 900° to 1,000° C. Yttrium-copper and yttrium-magnesium alloys are not suitable as anode feed materials, An evaluation of chloride, fluoride, bromide, and mixed chloride-fluoride electrolytes showed that cathode products containing much less oxygen than the anode material can be obtained in the fluoride and mixed chloride-fluoride systems. Initial cathode current density has no apparent effect on the purity of the products obtained in both phases of the investigation.

Jan 1, 1973

By O. Q. Leone

A processing unit was developed for the complete cleaning of titanium alloy chips. The process uses solvent degreasing, magnetic separation, and anodic solution of nonmagnetic impurities in 10 weight-percent sulfuric acid. Vacuum arc-melted ingots weighing approximately 10 pounds each were prepared from cleaning chips according to ingot specifications.

Jan 1, 1973