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By Jack I. Paige

The devitrification of lithium silicate glasses was studied to determine the effect of annealing temperature, composition, and additives on nucleation and crystallization. High-purity glasses, prepared from reagent-grade chemicals, had close to optical quality when prepared by a vacuum induction melting method developed during this research, The progress of devitrification was traced by differential thermal analysis and thermal expansion for those lithium metasilicate-silica compositions containing 80 to 90 percent silica. Microscopic studies of glasses partially devitrified at various temperatures and annealing times indicated that the primary initial mode of formation of individual crystals ,vas from densely crystalline zones that filled in as crystallization advanced Of the additives tested, calcium, potassium, and sodium helped promote devitrification with the least cracking or surface deformation. Tin oxide was most effective in reducing volume contrast ion during devitrification, but was not ClS effective in preventing cracking as calcium or potassium additions.

Jan 1, 1965

By S. E. Khalafalla

The Bureau of Mines investigated variations in the activation energy for the carbon monoxide reduction of magnetite and ferrous oxide with respect to the state of aggregation of the oxide material. Reduction phenomena can only be satisfactorily explained by including an adsorption step in the reduction process. Summation of the values of the exothermic heat of chemisorption and the variable apparent activation energy for reduction yields a nearly constant value of about 50 kcal for either ferrous oxide or magnetite regardless of whether they are aggregated in pelletized form or coarsely crystalline particles.

Jan 1, 1965

By R. T. Sorensen

Research and testing in a small scale equivalent of a commercial flota-tion plant was completed on four low-grade, iron-bearing materials from the western Mesabi range. Closed circuit-flotation of calcium-activated silica with fatty acid collector developed data for comparison with the batch process and highlighted problems not evident from previous bench testing. The four ore samples contained from 27 to 39 percent Fe and were equally represented by nonmagnetic taconite and semitaconite type materials. Iron concentrates containing 6.0 percent, or less, SiO2 were made 5, all four samples. Of the two material types, the semitaconite was the ore amenable to treatment, yielding iron recoveries of about 90 percent as cc pared with 70 to 80 percent for the other. Pilot plant tests showed that concentrate grade made in batch tests could be duplicated in the closed circuit and demonstrated that the amount of recoverable middling iron varied considerably between ore samples. The continuous tests also showed that water temperature strongly influenced results in the treatment of one ore but apparently was of indifferent consequence in another. Progress in thickening and filtration of flotation concentrates was made through introduction of tapioca flour to serve the dual role of iron mineral depressant and flocculant.

Jan 1, 1966

By Norman G. Foster

The mass spectra of four tertiary butyl substituted thiophenes are reported. A comparison and contrast with earlier structure correlations made by API-RP48 mass spectroscopists is presented. The fragmentation routes of these types of molecules are discussed and explained in terms of existing theories in mass spectrometry. Low ionization voltage data are presented to support the mechanistic picture developed. Structures are inferred about some of the ions, and these are correlated with existing theories. Metastable peaks in the spectra are used to support the fragmentation paths. The presence of doubly charged ions in the spectra is noted and the possible implications toward mechanisms discussed. The general picture of simple, small fragments leaving the ion moiety upon further fragmentation is developed in detail. Some suggestions are presented for further work utilizing isotopically labeled molecules to establish firmly the general picture of fragmentations of the alkylthiophenes.

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 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 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 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 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

By C. J. Walker

The Bureau of Mines undertook a theoretical and laboratory study to determine the feasibility of using ethylene as a tracer for natural gas in underground gas-storage reservoirs. The study indicated that ethylene was a useful gas tracer in underground gas storages. Tracer losses were not excessive. Laboratory tests were conducted at pressures as high as 500 psia in both wet and dry consolidated-sandstone cores, evaluating tracer loss with gas blends containing natural gas with different concentrations of ethylene tracer. Under certain conditions losses were less than 17 percent.

Jan 1, 1966

By Charles M. Mason

The Bureau of Mines evaluated equipment and procedures for drop-weight testing of explosive liquids as prescribed by Test 4) a widely used method. It was demonstrated that partial ignitions, originally designated as negative results, should be designated positives; it was also shown that wear or erosion of the sample cups and the type of mount used for the apparatus had important effects on the results. Relative sensitivity as measured by Test 4 was found to vary slightly with temperature. The Bureau also designed a fixed 2-kg weight and associated electromagnetic release, which subsequently were incorporated as standard in a revision of Test 4. The original concept that the test involves only adiabatic compression was found to be an oversimplification; an alternate mechanism for the initiation process is proposed in which due consideration is given to the effects of cavitation and microjets.

Jan 1, 1966

By Eliot J. White

The Bureau of Mines tested cores from 35 wells from 14 oil-producing zones in southern Illinois, southern Indiana, and western Kentucky to determine why rates of water injection were apparently low in some zones. Since these zones contain only minor amounts of clay minerals, it is concluded that permeability reduction results from movement of dislodged silica particles and other material, including the clays, that lines the pores. Both single-phase and two-phase permeability measurements, however, indicated that most samples had only low to moderate water sensitivity, so that permeability reduction due to such particle movement should usually not be of practical significance. The effective permeability to water was considerably lower than the effective permeability to oil during two-phase flow measurements, as is typical of most reservoir rocks. It can be concluded, therefore, that relatively high injection pressures will be required in waterflooding thin zones or zones having low permeabilities.

Jan 1, 1966

By H. J. Heinen

The Bureau of Milts studied repetitive batch electrowinning of molybdenum from molybdic oxide ) to determine the effects upon the electrolyte life, purity of metal product , and overall cell performance. The electrolyte consisted of 54.0 weight-percent sodium tetraborate (Na2B407), 23.6 weight-percent sodium chloride (NaC1), 14.9 weight-percent sodium fluoride (NaF), and 7.5 weight-percent Mo03. The feed materials were pure and technical-grade Mo03. Electrolysis was conducted at l,000° C in a graphite cell in an atmosphere of air and carbon oxides. Electrolyte degradation did not occur during repetitive winning of molybdenum from pure Mo03 in an 8-day (5,400-ampere-hour) period of operation. Electrowon metal contained <0.1 percent total impurities. The electrode configuration is a key factor in the direct conversion of technical-grade Mo03 to metal by repetitive cyclic electrolysis. The best configuration found was a cathodic crucible and a central anode. Metal purity of 99.8 percent and a current efficiency of 91 percent were maintained until the combined impurity buildup the electrolyte reached 4.7 percent silicon, l.0 percent aluminum, and 0.6 percent iron. One pound of molybdenum was produced per 1.5 pounds of solvent salts employed. About 25 percent of the initial NaCl and NaF contents of the electrolyte were lost owing to volatilization and crucible penetration.

Jan 1, 1966

By James Paone

The Bureau of Mines studied the behavior of rocks at the initial state of crater formation that results from the stresses created under a drill bit to determine which mechanical properties of rock are important in rock fragmentation by drilling. Although a definite relation between the drilling strength and relevant mechanical properties has not been established, maximum yield strength of rock is apparently a parameter of drillability of rock. The strengths of rock were considered from the Mohr-Coulomb criterion from which the surface of failure was constructed. The results from previous tri-axial tests on Solenhofen limestone were adopted to verify the criterion of failure. Inelastic behavior of some rock types was observed under a low-velocity impact of a hemispherical bit and under static indentation with a similar bit. Quantitative determinations of strengths of Solenhofen limestone) Indiana limestone, and Tennessee marble were made under static indentation. The maximum yield strength estimated from the average stress over the indented area was used as the crushing strength of rock under a drill bit.

Jan 1, 1966

By R. E. Stiles

The modified perchloric--EDTA method devised by the Bureau of Mines for the determination of copper in high-grade samples gives results that are more precise and more accurate than those from the classical sulfuric-iodometric method. Although the perchloric--EDTA method is more costly than the conventional method, the savings in time alone largely offsets this difference. Specifically, the modifications wade in the more conventional procedure comprise (1) use of perchloric acid instead of sulfuric acid for dissolution of copper minerals, (2) precipitation of copper as copper sulfide from dilute perchloric acid solution, (3) wet oxidation and dissolution of the precipitated copper sulfide, (4) use of larger amounts of indicator than those employed in the Schwarzenbach method of titrating low-tenor copper solutions with disodium ethylenedinitri10-tetraacetate and murexide indicator, and (5) use of refrigeration to partially stabilize aqueous solutions of the indicator.

Jan 1, 1966

By Ernest L. Corp

First in a projected series on the use of flexible liners for support of underground mine openings, this report presents information obtained from an extensive review of the literature on this subject. It also includes results of some preliminary test work by the Bureau of Mines. Investigations thus far indicate that flexible liners offer numerous advantages over rigid-type sup-ports, By deforming in the direction of the applied stress, the stresses are redistributed from the liner to the surrounding material. The corresponding buildup of passive resistance in the direction of diametric extension causes an equalization of stresses around the liner, thereby enabling the liner to carry loads in a more efficient manner. However, additional experimental data are needed to establish design criteria that will permit maximum utilization of the flexible liner concept in mining. Testing of small-scale models, accompanied by measurement of free-field stresses in material surrounding the model, is recommended as the most suit-able approach to the problem. The experimental procedures necessary to such an approach are outlined in detail and a statistical design for the experiments is proposed. The report also describes a device developed by the Bureau for measuring free-field soil pressures to 1,000 psi and a technique for evaluating the response of the device.

Jan 1, 1967

By David E. Nicholson

In a Bureau of Mines investigation of the dynamic compaction of mine hydraulic backfills, two basic forms of mechanical vibration inducers were used and compared for effectiveness of compaction. Internal compaction, using concrete probe vibrators of various sizes, and external compaction, using plate vibrators} were studied and evaluated for use in underground stopes. An aluminum plate, which was light and displaced sufficient volume to remain afloat in fluid fill, and a steel plate were both used in the external compaction tests. Efficiency of compaction was better in studies conducted with internal probe vibrators. Tests were conducted in an underground backfilled stope with three different-sized probe vibrators (2-, 4-, and 6-inch-diameter) to determine an approximate area of influence. Results showed the areas of influence to be approximately 3, 4, and 5 feet in diameter, respectively, for the three different probes. Physical properties of hydraulic slurries were determined; preferred grain-size distributions, water exudation properties, and water contents of hydraulic slurries are reported. The best compaction results were obtained with moderately well-graded, fully saturated backfills, with slow rates of water exudation, which were capable of remaining in a semifluid state during the compaction process.

Jan 1, 1967

By John R. Dudo

The Bureau of Mines Morgantown Petroleum Research Laboratory, with the cooperation of the Penn York Oil Company, cored the Dewdrop, Bradford Third, Lewis Run, and Sartwell sands in the Sartwell oilfield, McKean County, Pa. This report contains a review of the geology and depositional history of the field and an evaluation of the feasibility of secondary recovery of oil from the Bradford Third and Sartwell sands by waterflood or gas drive. Core analysis, geologic data, and electrical and radioactivity logs were used to evaluate the reservoir characteristics. Reservoir geometry, rock properties, fluid characteristics and saturations, and relative permeability-saturation relationships were used to assess the floodability of these two sands. The results of this study indicate that between 53,000 and 61,000 barrels of oil can be recovered by water or gas injection. The success of a waterflood or gas drive will depend on the field injection rates of the reservoirs comprising this oilfield. Following an economic evaluation, additional field work is recommended to further test the floodability of the reservoir.

Jan 1, 1967

By A. Gene Collins

The Bureau of Mines undertook research to determine the bromide and iodide content of Mississippi and Alabama oilfield waters of the Tertiary and Cretaceous Period to determine genetic relationships of the ions, to determine their origin, and to determine their genetic relation to petroleum. The 280 samples were analyzed after a pretreatment to remove interferences. The iodide was oxidized to iodate and was titrated with thiosulfate. The bromide was oxidized to bromate and was determined iodometrically. A computer was used to calculate the correlation coefficients of iodide to bromide and to other ions. The other ions are sodium plus potassium, calcium, magnesium, chloride, bicarbonate, and sulfate. The mineral content of the samples ranged from 52 to 1,760 mg/l for bromide and from 2 to 65 mg/l for iodide. The mean bromide-to-chloride and iodide-to-chloride ratios were 0.0065 and 0.0002. The correlation coefficient matrix and linear plots indicated a definite bromide-to-calcium relationship for the brines investigated.

Jan 1, 1967

By Henry M. Harris

A study was made by the Bureau of Mines to determine if shapes of oxide-glass compositions could be roll-formed at high temperatures, and to find the conditions required for adequate formability. A unit with directly connect&apos; furnaces and heated rolls that allowed forming of most of the compositions developed. Glasses of the feldspar type were chemically unreactive with the alumina grains, and allowed the best roll forming. Optimum forming was attained at temperatures of 1,400° to 1,530° C, with compositions containing 30 or 40 percent feldspar and 60 or 70 percent alumina. Formability was better when compositions contained minus 325-mesh materials, rather than coarser or finer powders. In many cases, roll-formed shapes had physical properties equal to or better than the normally sintered shapes of the same composition.

Jan 1, 1967