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By R. F. Abernethy

A modified Unterzaucher method was applied to the direct determination of oxygen in coal. Coal samples were pyrolyzed in a nitrogen atmosphere, and the gaseous oxygen compounds liberated were converted to carbon monoxide by a platinized-carbon catalyst at 9000 C. After passing over heated copper and through a tube containing soda-asbestos and magnesium perchlorate, the purified carbon monoxide was oxidized to carbon dioxide by iodine pentoxide--liberating an equivalent amount of iodine. The iodine was titrated with 0.02 ~ sodium thiosulfate; in a few tests the weight of carbon dioxide produced was determined. Direct oxygen determinations of coal included organic oxygen from the coal substance, plus a small quantity of inorganic oxygen derived principally from carbonate minerals and from combined water of silicates in the mineral matter. The influence of mineral matter on the direct oxygen determination was investigated by testing (1) untreated coal, (2) demineralized coal from which most of the mineral matter except pyrite was removed by treatment with hydrofluoric and hydrochloric acids, and (3) coal samples treated with dilute hydrochloric acid.

Jan 1, 1966

By R. L. Benner

The Bureau of Mines investigated the ZnO-Fe2O3-Fe3O4 system at 1,000°, 1,300°, and 1,400° C, with oxygen pressures between 1.0 and lx10-4 atmospheres. The results, divided into the thermodynamic properties as related to the spinel structure, and the thermodynamic properties as related to zinc concentrate roasting, were used to calculate the activities of ZnO, Fe2O4, and Fe3O4 within the spinel solid solution region of the ternary system, and the pseudo-binary activities of ZnFe2O4 and Fe304. The activities of both systems show large positive deviations from Raoult's Law, especially at high Fe3O4 concentrations. The free energies, the enthalpies, and the entropies of mixing for the binary system were calculated from the binary activities, and the entropies of mixing were compared with two statistical models, one representing an ideal solution, and one representing the mixing of a normal with an inverse spinel. The binary entropy of mixing seemed to be better represented by the latter statistical model, indicating that the tetrahedral and octahedral cations of the reactants tend to remain in the product, even at the high temperatures of the study. This comparison also indicated that the cations of the components are the major contributing factors to the thermodynamic properties.

Jan 1, 1966

By Willard L. Hunter

The Bureau of Mines studied the effect of temperature upon the reduction of chromite by carbon and the relative reducibility of chromites as a function of their composition. Ferric oxide was also studied to provide comparative data. Pellets weighing approximately 1 gram and containing 70 percent ferric oxide, chromic oxide, or chromite and 30 percent graphite were subjected to closely controlled temperatures under a flow of argon for 15 minutes. The amount of CO and CO2 evolved was measured, and the reduced sample was analyzed by X-ray diffraction techniques. The reduction of Fe2O3 was studied over a temperature range of 600° to 1,400° C, while the reduction of Cr2O5 and chromite was conducted from 9000 to 1,621° C. The temperature above which appreciable reduction of Cr203 by graphite took place was 1,125° C. The temperature at which significant reduction started for three of the four chromite samples was approximately the same, indicating that there was concurrent reduction of iron and chromium oxides in the chromite mineral rather than selective reduction of iron oxides followed by reduction of chromic oxide. Rhodesian chromite appeared to dissociate at a lower temperature with concurrent reduction of iron. Based on the temperature at Which chromite was 50 percent reduced in 15 minutes, Transvaal chromite reduced most easily, followed by Mouat, then by Kampersian, and finally by Rhodesian DFC material. Statistical analysis of test results indicated that the ferric iron content of chromites affects their reduction behavior more than any other constituent.

Jan 1, 1966

By Harry R. Johnson

Laboratory experiments were conducted to study the carbon deposition characteristics of a high-gravity, paraffin-base crude oil. The results of these experiments indicate that a fuel supply adequate to initiate a combustion wave can be deposited in high-gravity-oil reservoirs. These results are significant because there has been considerable doubt whether oils over 35° API gravity are able to deposit sufficient fuel. Considered in these studies were the effects of air flux, temperature, initial oil saturation, and time on carbon deposition. Conditions that maximized carbon deposition in the laboratory and an understanding of the nature of carbon formation are shown by graphical interpretation of the data. Statistical techniques were used to design and analyze the results of the retort tests. For the same amount of laboratory work, this approach yields more information about the systems that were studied than the classical method of research presently used in many laboratories. In addition, the accuracy of calculating the effect of each variable on carbon deposition is twice that of the classical approach. This paper develops the statistical approach to research without complex mathematics, thus enabling the reader to grasp the concept of how statistics can be applied to study many complicated problems.

Jan 1, 1966

By Jack G. Croeni

A study was made by the Bureau of Mines to determine the influence of high energy-rate deformation on the structures and properties of low-carbon steel, stainless steel, titanium, titanium-6 percent aluminum-4 percent vanadium, beryllium, molybdenum, and tungsten. The purpose of this study was to determine relative formability, the effect of energy and temperature on metalworking parameters and resulting structures, and the properties of materials formed by this technique. Forming techniques were limited to upset forging and direct extrusion on pneumatic-mechanical forming machines. Results show that considerable grain refinement can be achieved by careful control of deformation and forming temperature by high energy-rate techniques. Significant improvements in strength were observed as a result of this refined structure. Approximate deformation resistance as a function of temperature was determined for a variety of materials.

Jan 1, 1966

By James W. Myers

The Bureau of Mines studied factors affecting ignition of coal mine refuse and on methods for control of burning. Laboratory experiments showed that air permeates more readily through segregated than through nonsegregated refuse and that air permeability is greater through coarse than through fine particle refuse. Minus 3-1/4-inch refuse ignites spontaneously more readily than minus 1/4-inch refuse. The burning of a 1,000-pound conical coal pile was con-trolled by capping with an 18-inch-thick layer of minus 1/4-inch refuse containing 37 percent combustible. In field trials, the burning of refuse at operating mines was controlled by capping with a layer of fine refuse. Water, applied as a spray or by injection, quenched surface flames and cooled the burning waste. Inspection of refuse piles at operating mines showed that the spontaneous ignition tendency is affected by the exposed surface relative to the total volume and the segregation of particles during dumping.

Jan 1, 1966

By W. H. Tavenner

The Bureau of Mines gathered test data on the use of a continuous borer in mining an anthracite bed, which was 30 feet thick on a pitch of 15° to 45°. Gangways were driven with the continuous borer, ventilation openings between gangways were driven with a large-diameter auger, and the blocks of coal between completed gangways were mined by the long-hole method, Conveyors were used to transport the mined coal. The continuous borer operated on a coal floor that was frequently soft because of heaving. The continuous borer could not bore openings on a grade exceeding 27 percent (15° pitch). Because 150 was also the lower limit of the pitch, of the bed, the continuous borer was used only to drive gangways. The continuous borer virtually filled the workplace, leaving insufficient space to place heavy-duty timber and cushioning material between the timber and coal back to allow for normal expansion of the uncut coal. The light? weight yieldable steel arch against the coal back gave inadequate support to control convergence, which in a disturbed area sometimes occurred with explosive violence. This exposed the machine operator to a hazardous condition, since a satisfactory solution could not be found, the company discontinued the use of the continuous borer.

Jan 1, 1966

By J. M. Singer

Quenching distances for flames of methane-coal dust mixtures were determined with air and oxygen-enriched air. Coals used were Pittsburgh, Sewell, and Pocahontas No.3. Quenching distances were greater for flames of hybrid mixtures of coal dust and methane than for methane flames of corresponding stoichiometry. From the data of quenching distances and methane-coal dust concentrations was calculated the quenching equivalence, which is the increase in coal dust concentration required to maintain a given quenching distance value as the methane concentration decreases. These equivalences could be useful in identifying hazardous methane-coal dust mixtures in mines.

Jan 1, 1966

By H. C. Fuller

Submerged combustion and inverse solubility methods were investigated as promising alternative means for crystallizing manganese sulfate from solutions produced by leaching manganese ores with either sulfuric acid or sulfur dioxide. Evaporation of water from typical manganese sulfate solutions by sub-merged combustion techniques enabled production of a slurry containing 32 to 39 pct MnSO4.H2O crystals suspended in a saturated solution of manganese sulfate. Such a slurry required further processing by thickening or filtration and drying to produce crystals of MnSO4.H2O. In a second approach, semicontinuous processing of manganese sulfate solu¬tions by thermal crystallization under pressure effected a recovery of 94.5 pct of the MnSO4.H2O as dry free-flowing crystals. Treatment of a solution containing about 100 grams manganese per liter at 189° C, produced a "barren" solution containing only 1.9 grams manganese per liter. Calculations made on comparable manganese sulfate solutions show that the heat requirement of the thermal crystallization method was about one-third to one-fourth that of the submerged combustion method.

Jan 1, 1966

By Alton B. Cook

A material balance equation was derived for calculating (1) the initial oil volume and (2) the relationship of average reservoir pressure to net gas in storage in reservoirs used for natural gas storage operations. The equation is also applicable to secondary-recovery operations where reservoirs are completely repressured and gas cycled. Using this equation minimized two probable sources of appreciable error in conventional material balance calculations: inaccurate measuring of and accounting for produced gas, and differences between true reservoir pressure and average reservoir pressures as derived from bottom-hole pressure measurements. A new procedure is presented for calculating water encroachment. By solving the conventional material balance equation and the derived equation for gas storage simultaneously, the values for initial oil in place and net water encroachment can both be determined.

Jan 1, 1966

By M. M. Fine

This Bureau of Mines report describes the theory, experimental procedures, and the results obtained to date in the development of the Bureau's process for magnetically roasting iron ores using scrap iron as a means of reduction. Since magnetic separation is an operational step common to magnetic taconite plants, the preliminary research studies emphasized only the novel magnetic roasting step. The studies included the use of automobile scrap, ferrous reductants such as borings and turnings, and prereduced pellets. Technical feasibility of the process was demonstrated both on a bench- and pilot-scale. Quality magnetic concentrates with recoveries of over 90 percent were obtained from a direct shipping ore containing 59.5 percent Fe and from fine grained semitaconites with about 30 percent Fe.

Jan 1, 1966

By R. R. Lowery

The Bureau of Mines developed hypereutectic aluminum-silicon alloys which 11.7.d better mechanical properties than the unmodified hypereutectic alloy. A commercial aluminum-20 weight-percent silicon LIr alloy was selected as a ary base for improvement. The primary silicon. grains were reduced from ASTM 4-5 to ASTM 8.5 by the use of phosphorus and phosphorus compounds. The remaining eutectic matrix was refined by sodium metal additions of 0.2 weight-percent. Solid solution strengthening of the alpha aluminum was obtained by adding 2 percent copper and 0.5 percent magnesium. Also, 1 percent nickel was added to harden the alloy. Optimum thermal treatment consisted of a solution treatment for 10 hour:, at 480° C with hot water quench, followed by aging for 6 hours at 175° C. The final alloy exhibited a Rockwell B hardness of 75 ±2 in the heat-treated condition. The ultimate tensile strength was 39,5O0 psi with no recordable elongation. The coefficient of linear thermal expansion was 20.4 x 10-6 per °C in the temperature range 20° to 300° C. No wear resistance data were collected.

Jan 1, 1966

By H. E. Perlee

The concentration limits of flammability and autoignition temperatures of trichloroethylene in atmospheres of air, oxygen, and nitrogen tetroxide have been determined in a spherical vessel. The autoignition temperatures of TCE in atmospheres of air, oxygen, and nitrogen tetroxide were found to be 419°, 396°, and 221° C, respectively. The flammability zones of TCE-air, TCE-oxygen and TCE-nitrogen tetroxide mixtures at 100° C were found to be 10.5 to 41, 7.5 to 91, and 13.5 to 69 volume percent TCE, respectively. In addition, maxi-mum combustion pressures of 50 ps and 140 were recorded for constant volume combustion of the lower limit mixtures of trichloroethylene in air and oxygen, respectively.

Jan 1, 1966

By Robert S. Warfield

Eight samples of high-volatile bituminous coal, each large enough for a study of its coking properties by the Bureau of Mines, were obtained from a location along the Kukpowruk River, Arctic Northwestern Alaska. Bench scale and pilot plant carbonization studies with several patterns of coal blending were conducted. The data from these tests were compared to data from similar tests on a coking blend used by the Kaiser Steel Corporation at Fontana, Calif. The majority of the samples representing the 20-foot seam was found to have significant coking properties, and produced coke approaching metallurgical quality when blended with selected coking coals. Although oxidation effects were evident in the samples representing upper portions of the seam, it appears that the whole seam could be used.

Jan 1, 1966

By Robert M. Becker

Part 5, the last of this series, deals with the theoretical confirmation and application of results developed in parts 1 and 2. The bulk-sampling variances of Hassialis and Kassel and Guy are compared with those in part 2, both as to formulation and as applied to ores and coal. The results provide confirmation for much of the development in part 2. Examples are presented for determining the reliability of bulk samples with respect to various measurable characteristics. These characteristics include, for example, assays for elements or compounds and particle surface area. The bulk samples considered consist either of a given weight, a given volume, or a given number of particles. In addition to problems of sample reliability, some of these examples may also be applicable to quality control. Several possible applications of results developed in parts 1 and 2 are outlined. These include tests for random data, degree-of-mixing indices, and particle-fineness indices.

Jan 1, 1966

By R. L. Benner

A compound stability diagram was constructed by the Bureau of Mines for the Zn-Fe-S-O system to show the phases that should be thermodynamically stable at various temperatures, oxygen pressures, and SO2 pressures. The diagram was demonstrated to have good qualitative value for predicting stable phases that may, in turn, be related to the recovery of zinc in the leaching phase of the electrolytic zinc process. The study showed that roasting temperature is the most Significant variable in preventing roaster formation of zinc ferrite, which is directly related to subsequent extraction of zinc in the leaching step.

Jan 1, 1966

By Lippe D. Sadwin

A high-speed streak camera method for making equation of state measurements (shock and particle velocities) on samples of rock under dynamic load conditions is described. Experimental data are given for tests on 12 samples representing 5 rock types. Analysis of these data shows that the method is practical and that good reproducibility of results can be obtained. The pressure range covered in the tests was from 1 to 50 kilobars.

Jan 1, 1966

By E. A. Loria

High-quality sheet of electrowon molybdenum was attained by a sequence of procedure on pressed and arc-melted crystalline powders. The procedures included high-temperature, high-vacuum sintering treatments and the use of metal deoxidizers instead of carbon to improve the mechanical properties of the molybdenum sheet. Rolled sheet 60 mils thick was evaluated by tensile and bend tests, hardness measurements, microstructures, and recrystallization treatments. After stress relieving, yield strength ranged from 85,000 to 110,500 psi (0.2- percent offset) and ultimate strength ranged from 87,200 to 117,250 psi with 4.5- to 25-percent elongation observed for arc-melted sheet, and 5.0- to 23- percent elongation observed for powder metallurgy sheet. In room temperature bend tests the sheet yielded plastically, indicating that the ductile-brittle transition point was below room temperature. The diamond pyramid hardness (DPH) of the molybdenum sheet changed from 214 to 293 DPH for the stress-relieved condition to 177 to 185 DPH for the fully recrystallized condition. The brittleness of recrystallized molybdenum, reported by other investigators as characteristic of sheet prepared from commercial-grade hydrogen-reduced powders, was not in evidence. Recrystallized tensile specimens pulled at room temperature had an average elongation of 31 percent.

Jan 1, 1966

By F. E. Griffith

Cost data are given for five methods of secondary backfilling of strip mines previously partially backfilled. The operations were conducted in north-central Pennsylvania; an average of 600 linear feet of highwall were backfilled in each trial. Major obstacles and the relative merits of the methods are discussed.

Jan 1, 1966

By R. W. Van Dolah

An attempt has been made in this investigation to define the conditions under which ammonium nitrate (AN) might detonate as a result of involvement in fire. The initiation of detonation by shocks derived from explosives or from projectile impact was investigated as a function of temperature and charge diameter. A new technique was devised to investigate the burning of raw and contaminated AN under pressure. No transition, to detonation in AN was obtained in the burning experiments. The critical diameter for detonation of fertilizer-grade AN was found to be quite small when the AN was at temperatures just below melting point; this indicates that initiation of detonation may be less difficult at elevated temperatures but such initiation by gas-phase detonation was shown to be unlikely. Transition from burning to detonation was obtained with AN intimately mixed with fuels that included polyethyl-ene, paper, and fuel oil when these were contained in vessels with restricted vents. However, the experimental results supported by an analytical study indicate that the initiation of detonation in AN from fire exposure in normal storage and from transportation incidents is quite improbable. The detonation of AN in recent incidents more likely may have resulted from the effects of adjacent explosions.

Jan 1, 1966