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By L. J. E. Hofer

This Bureau of Mines study, part of a broad program of research in air pollution related to minerals, was conducted to determine the nature and extent of the poisoning of catalysts when used to remove certain air pollutants from exhaust gases. The poisoning examined in this investigation occurs when leaded gasoline is used as a fuel for automotive engines. This research was conducted in cooperation with the Public Health Service. The smog in the Los Angeles area is attributed to the effect of radiant energy on the mixture of hydrocarbons and nitrogen oxides found in the atmosphere there. A large portion of the hydrocarbons is believed to originate in the exhaust gases of automobiles. To prevent the escape of these hydrocarbons into the atmosphere catalytic mufflers have been proposed. In principle, these are simple and nonmechanical, consisting of a vessel charged with a catalyst capable of destroying the exhaust hydrocarbons by catalyzing their oxidation. However, these catalysts are severely affected by the particulate matter, mainly in the form of lead sulfate (PbS04), lead oxysulfate (PbS04.Pb0), and Lead chlorobromide (Pb(Cl,Br)2), contained in the exhaust gas. Deposition of lead on the catalyst as PbS04, PbS04, PbS0, and Pb(Cl,Br)2 restricts catalytic activity. As a result,after 20,000 miles of operation the temperature necessary to achieve 50-percent conversion of isopentane in a mixture of 0.2 percent isopentane, 2 percent carbon monoxide and 4 percent oxygen, and the balance nitrogen at 10,000 hourly space velocity has risen from 400° C. to 500° C. even with a catalyst taken from the exit portion of the catalyst bed. The rest of the catalyst was more severely affected. Therefore, it would appear that operation for 20,000 miles is near the limit for a catalyst.

Jan 1, 1963

By R. F. Abernethy

Recent investigations in the United States and in other countries have produced considerable information on the nature and occurrence of minor elements in coal. The possibility of recovering certain elements, particularly germanium and uranium, from coal ash and other coal products has received considerable attention. Some flue dusts are potential sources of germanium, and certain lignite deposits are potential sources of uranium, but industrial recovery of these elements has been limited to small quantities for technical and economic reasons. Considering the large amount of coal mined annually, a small percentage of a rare element may have industrial significance if an economical method of recovery can be developed. In 1944 information on the occurrence of rare elements in coal was reviewed in Bureau of Mines Technical Paper 669 (46).3 This report is a revision of that paper with the view of summarizing published information available for United States coals, and pertinent information concerning coals of other countries. Selected references from the original paper are retained. New references do not include all preliminary reports when more permanent literature describing complete projects is available. Consequently, the list of references should not be considered complete.

Jan 1, 1963

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria 'Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By R. Sporcic, P. J. Mudra

During the past year personnel of the Roof Control Research Group of the Bureau of Mines designed and developed encapsulated hydraulic cells for measuring pressure changes in coal in situ. Preliminary results from feasibility tests in progress in the laboratory and field indicate that the cells respond favorably to changes in pressures associated with a coal-mining environment. The ultimate objective is to use these cells to obtain engineering information relating to coal bump or coal outburst phenomena. Mining research has experienced a remarkable growth during the past decade and from all indications should surge forward at even a greater pace in the future. This increased interest in mining research has been brought about by the ever-multiplying number of technical problems being encountered by the mining industry in its effort to produce pay-dirt tonnages safely and economically from greater underground and surface pit depths. Among the various divisions in the field of mining research, the study of ground stress has received a large part of the overall attention. Numerous technical papers have been written with regard to ground stress conditions around mine openings and yet the total usable knowledge concerning this subject is extremely limited. Research teams around the world are endeavoring to bridge the gap between theoretical and laboratory approaches and the solution to design problems in the field. The problem of ground stress is not a new one for the coal mining industry. Operators in both eastern and western coal fields of the United States as well as in many foreign countries have long been plagued with a number of ground stress problems, one of which is commonly referred to as the coal-mine bump. This term or phenomenon has been aptly defined by earlier investigators as the violent and sudden failure of coal and adjacent rock. Direct results of such failures have been the loss of human lives and thou- sands upon thousands of dollars of sustained mine damages. In an effort to alleviate the magnitude and frequency of these failures, mine operators have employed and are presently employing various corrective techniques. These include: Inducing failure in heavily stressed areas by augering large-diameter holes into stressed pillars, using extensively yield-able steel arches in both long-term haulage and short-term face entries, backfilling unused or abandoned entries with mine waste to gain additional support, and using systematic pillar coal panel extraction techniques including mechanized longwall mining. The Health and Safety Activity of the Bureau of Mines has for a number of years contributed considerable time, funds, and talent in an effort to define better the ground stress problems associated with coal-mine bumps. As a part of this investigative program, in situ ground pressures are presently being studied in coal mines located in West Virginia and Utah. The description and development of the device being used to measure these pressures is the specific topic of this paper. CHOICE OF INSTRUMENTATION After consideration and evaluation of the various instruments and techniques that are being used by researchers in the field of rock mechanics to detetmine in situ stresses, a simple hydraulic system was selected for detailed investigation. Aside from simplicity, a hydraulic system is relatively inexpensive and also eliminates the need for electricity in its installation and operation. The hydraulic device referred to is, in essence, a simple unidirectional pressure-measuring cell. Hydraulic cells, which had been used for measurement of pressures in hard rock, were investigated but found not entirely suitable for use in coal, particularly since they involved (1) preparation and emplacement of cement grout at the test site, and (2) a waiting period before the cells became operational. At the outset, it was decided that certain design parameters be established. The cell should be simple and inexpensive, constructed of materials readily obtainable and easily built in the laboratory or field by unskilled labor. It was further decided that it was desirable to encapsulate the cell in a suitable mate-

Jan 1, 1963

By Donald R. Irving

ALTHOUGH the quantity of material handled at metal and nonmetal mines in the United States in 1962 was 2.7 billion tons, the same as in 1961, a larger proportion was waste. At metal mines, crude ore production declined 1 million tons and waste output rose more than 18 million tons; at nonmetal mines crude ore production declined 6 million tons and waste output rose 36 million tons. Copper and iron ore producers increased their share of crude ore and material handled from about three-fourths to four-fifths of the national metals total, and sand and gravel and stone producers in-creased their share of the nonmetals total, also from three-fourths to four-fifths. Six States-Arizona, California, Florida, Michigan, Minnesota, and Utah-each handled more than 100 million tons of ore and waste, and together they accounted for 43 percent of the U.S. total. When the large-volume construction materials (sand and gravel and stone) were excluded from the totals, four States-Arizona, Florida, Minnesota, and Utah-supplied over half of the material handled.

Jan 1, 1963

In Mount Isa voltage and frequency fluctuations caused. by haulage shaft operation gave considerable difficulties with the initial application of Atomic Absorption Spectro-photometry.The methods used to stabilise the various units ' have been described.- Some other difficulties and the means used to eliminate or reduce them together with a-modified burner design are also discussed.

Jan 1, 1963

By Kenneth H. Johnston

This report describes in detail three waterflooding projects and a pres-sure-maintenance project in Butler and Cowley Counties, Kans., that will be visited on the 1963 annual spring tour of the Kansas-Oklahoma Waterflood Association. Among the unique features of the projects are the flooding of five oil-producing horizons separately with injection water furnished by two water treating plants. Discussion of the individual projects includes information on their early history, the source and treatment of the injection fluids, oil production decline curves, and the results of water injection on oil production.

Jan 1, 1963

By James A. Wasson

This report summarizes the results and conclusions reached by various investigators who have attempted to determine the extent to which hydraulic fracturing will affect the secondary recovery of crude oil by waterflooding. It also discusses the most advantageous use of this well-stimulation method in waterflood projects. A thorough search of the literature was made, and pertinent information was abstracted from appropriate reports. A carefully designed and controlled program of formation fracturing is an effective aid in waterflooding because it increases water-injection and oil-production rates. Generally, fracturing has resulted in little or no reduction in ultimate oil recovery, but under certain circumstances recovery has been substantially increased.

Jan 1, 1963

By B. C. Allen, R. I. Jaffee, D. J. Maykuth

Wrought unalloyed iodide chromium, containing 39 to 95 ppm total interstitials, has a tensile transition temperature of —15°C. Re crystallizing at 1100°C causes the transition to rise to 90° to 390°C, depending on the purity, grain size, and cooling rate after annealing. At about the 100 ppm level, individual additions of carbon or nitrogen raise the transition of both wrought and recrystallized chromium by as much as 210°C, while oxygen has a lesser effect, and sulfur essentially no effect. High transitzon temperatures are exhibited by recrystallized and quenched chromium, and appear to be associated with the amount and distribution of inter-stitials. The latter cm be either in solid solution or in the form of precipitates within the grains or at the grain boundaries. Quench hardening in chromium is primarily caused by nitrogen. The hardness, re crystallization, and grain growth behavior of chromium with and without impurity additions were also investigated. BECAUSE of low density and good oxidation resistance, chromium-base alloys are potentially useful for elevated-temperature applications. The main deterrent to the use of chromium in structural applications is its lack of low-temperature ductility, especially in the recrystallized condition. Accumulated evidence has shown that the ductility of chromium is sensitive to purity. The objective of the current study was to determine the effect of common nonmetallic impurities on the tensile properties of high purity chromium. The separate effects of carbon, oxygen, nitrogen, and sulfur additions on the ductile-to-brittle transition were evaluated for wrought and recrystallized material after various cooling rates. EXPERIMENTAL WORK Unalloyed iodide chromium and seven impurity alloys containing individual carbon, oxygen, nitrogen, or sulfur additions were prepared in rod form. Nominal additions were 100 ppm C, N, and S, and 100 to 500 ppm O. The additions were about a factor of ten greater than the residual amounts in the unalloyed material. The seven alloys and two unalloyed compositions were consolidated into four-pound ingots by conventional consumable arc melting of pressed and welded electrodes under 0.5 atm of helium. Impurity additions were made to the electrode in the form of crushed master alloys. The impurity alloys were double melted to improve homogeneity. The ingots were broken down by extrusion at 1200°C in evacuated steel cans at a reduction ratio of 18 :1, using a molten borosilicate glass lubricant and a ram speed of 80 in. per min. The cans were removed by acid pickling, and the chromium core ground free of surface undulations. Cut lengths were sheathed in mild steel and swaged at 900°C until the core was about 1/4 in. in diam. Two additional 15-lb ingots of unalloyed chromium (ICr-3, ICr-4) were prepared by arc melting and broken down by 26:1 extrusion at 1250°C without a steel can. The billet was lubricated and protected from contamination by a coating of molten glass. The resulting extrusion was then sheath swaged as described previously. Representative chemical analyses of each of the materials, after removal of a 10-mil surface layer

Jan 1, 1963

By M. M. Wong

Electrolysis of titanium carbide and a material consisting of titanium, carbon, nitrogen, and oxygen as soluble anodes in Used electrolytes was investigated by the Bureau of Mines for the preparation of crude titanium metal. Tests made in all-chloride electrolytes showed only a low recovery of titanium as well as a substantial volatilization of titanium trichloride (TiC13) when present in the electrolyte. Electrolysis at 750° to 850° C in a mixture containing 85 percent NaC1-15 percent potassium floutitanate (K2TiF6) yielded as high as 91 percent recovery of titanium from titanium carbide and 62 percent recovery of titanium from the titanium-carbon-nitrogen-oxygen material. Problems associated with the preparation of crude metal by fused-salt electrolysis are discussed. The crude metals produced from both anode materials were electrorefined in a sodium chloride-titanium chloride (NaCl-TiC12) electrolyte, and ductile titanium metal was obtained.

Jan 1, 1963

By Martin H. Stanczyk

Acid leaching of selected copper sulfide minerals, impure copper sulfide flotation concentrates, and a cement copper precipitate at elevated temperatures and pressures was investigated. Copper extractions of 97 to 99 pct were obtained by leaching chalcopyrite and the flotation concentrates with water under oxidizing conditions at 200° C for 30 to 60 min. In tests with bornite, chalcocite,and cement copper, addition of sulfuric acid or pyrite to the autoclave was required to obtain similar copper extractions. The chemistry of leaching copper minerals was studied. It was determined that different copper sulfides altered to covellite as one step in their dissolution.

Jan 1, 1963

Australian rutile and zircon concentrates are refined raw materials and not manufactured products. The composition and properties of the grains are therefore fixed by nature. Specifications and assay certificates should take this into account by eliminating unnecessary provisions which only increase the time and cost of analysis.INTRODUCTIONThe raw material from which Australian rutile and zircon concentrates are isolated is beach sand on the coast of New South Wales and Southern Queensland. The principal current operations are in an area between Sydney and Brisbane.The sands consist principally of quartz particles, but they contain from 1 per cent to 50 per cent of a mixture of heavy minerals, including zircon, rutile, ilmenite, monazite, leucoxenic grains, chrome spinel, chromite, garnets, corundum, topaz, brown spinel, olivine, epidote, clinozoisite, tourmaline, magnetite, hematite, and cassiterite. The major components are zircon (25 to 60 per cent), rutile (25 to 50 per cent), and ilmenite (5 to 50 per cent).The so-called leucoxenic grains are not a definite mineral species but an alteration product of which the major components are titanium oxides and silica in varying proportions.Primary concentration is by gravity, using spirals or various forms of pinched sluice (Pullar, 1962), the resulting concentrates being redressed on wet tables. During these processes, some of the lighter heavy minerals including leucoxene and impure rutile, which tend to degrade the final rutile and zircon concentrates, are eliminated.The separation of heavy minerals from each other is...

Jan 1, 1963

By Ronald C. Koo

THE effect of grain size on the mechanical properties of the bcc metals has been a subject of intensive theoretical and experimental study.'-l5 Quantitative relationships have been established experimentally between yield stress and grain size and between the ductile-brittle transition temperature and grain size in a number of metals.6"15 Much significance has therefore been attached theoretically to the grain size dependence. In all these experiments, different grain sizes were always achieved by annealing specimens at various temperatures. The implicit assumption was that any change in the dislocation substructure or in the distribution of impurities which might occur simultaneously with the production of various grain sizes had only a negligible effect on the mechanical properties. The validity of this assumption, however, is questionable. transformation in iron-nickel alloys is actually an extraneous phenomenon due to inadvertent compositional changes in the martensite if the heating rate is not sufficiently rapid. This complication can be avoided by up-quenching for the reversal treatment,5 and then the stabilization does not appear. Clearly, the lattice imperfections and strengthening produced by the reverse transformation are not responsible for the marked stabilization which has been observed by other investigators in these alloys. Data will be presented in this note to show that, at least in recrystallized tungsten of commercial purity, the difference in the ductile-brittle transition temperature of specimens annealed at various temperatures is more a result of a variation in the distribution of impurities rather than of the difference in grain size produced by the anneal. Ductile-brittle transition temperatures in tension were determined on powder-metallurgy tungsten specimens recrystallized at various temperatures. Tensile specimens having a gage length of 1.50 in. and gage diam of 0.18 in. were recrystallized at 1450°, 2000°, 2350°, 2550°, 2750°, or 2800" for 30 min in a vacuum furnace at a pressure of 1 x 10"5 mm of Hg and then tested at a constant extension rate of 8 x 10 per sec in an argon atmosphere from 100" to 800". Typical quantitative analyses of impurities are given in the Table. These results show that, within the precision of the analyses, see Table, annealing did not result in any detectable change in the impurity contents of the specimens, nor was there any detectable difference in purity between specimens having large differences in grain size annealed at the same temperatures . The results of the tensile tests yielded three distinct ductile-brittle transition curves approximately 225' apart. As shown in Fig. 1, data of specimens annealed at 1450°C and those of specimens annealed at 2000°C (O) fell on Curve A. Data of specimens annealed at 2350" and 2550°C fell on Curve B, and those of specimens annealed at 2750" and 2800°C fell on Curve C. The decrease in ductility with increase in annealing temperature became so pronounced that one third of the specimens annealed at 2750" and two thirds of the specimens

Jan 1, 1963

By H. C. Carpenter

Lignite tar made by low-temperature Lurgi-Spülgas carbonization of North Dakota lignite was hydrocracked in single-pass, fixed-bed operation at 3,000 pounds per square inch over cobalt molybdate catalyst to produce gasoline, and at the same pressure, over zinc chromite catalyst to crack the high-boiling phenolic compounds to low-boiling phenolics. Hydrocracking the raw tar or the creosote-oil fraction from the tar over cobalt molybdate removed most of the oxygen, sulfur, and nitrogen in the forms of water, hydrogen sulfide, and ammonia, and produced gasoline yields from 31 to 59 volume-percent. The gasoline fractions contained from 0.1 to 7.7 volume-percent tar acids, but tar-base percentages were too low for reliable measurement; removal of these materials with dilute caustic and acid solutions also reduced the sulfur and nitrogen to 0.01 weight-percent or less.

Jan 1, 1963

By Robert Stefanko

Longwall mining appears very attractive from an engineering standpoint because of its simplicity. The use of one long, continuous face can simplify power distribution, ventilation, and supervision, and minimizes or prevents lost time associated with the tramming of equipment in room-and-pillar systems. Since the longwall system is more amenable to automation, it is inherently safer than room and pillar. Remote control of all face equipment from gate roads will obviate the exposure of men in the face area. Considering what has been said, it seems a paradox that more longwall installations are not found in the United States. However, with favorable mining conditions in relatively level seams of adequate height under shallow cover, it has been possible to develop highly productive, mechanized, room-and-pillar systems. Thus there has been no real incentive to employ longwall in the United States. In Europe, mining companies usually have very little choice between the two systems. Pitching seams of low height located at great depth dictate the use of longwall methods. With depletion of its readily accessible reserves, mining conditions will be similar to those now prevailing in Europe, and an increase in the use of longwall in the United States can be anticipated.

Jan 1, 1963

Consideration was given to the.applicab on of a solvent extraction circuit to be'included in the process'for the-recovery of a high grade product from.:-the Rum Jungle Creek.South uranium ore body.The economics of two alternative processes, firstly the Eluex process which uses an ion exchange process followed by solvent extraction.-of a.high grade sulphuric acid eluate, and secondly a process using direct solvent' extractioh of pregnant leach liquor, were studied. There was a small cost advantage favouring the Eluex process but when other factors were considered, the installation of a direct solvent extraction process appeared the better long term investment. A solvent extraction plant was installed at Rum Jungle in 1962.

Jan 1, 1963

By S. Ramachandran, R. A. Walsh, J. C. Fulton

A method has been developed for calculating the oxygen content of commercially melted stainless steels. Application of thermodynamics to the de-oxidation reaction in straight chromium and Cr-Ni stainless steels has resulted in a set of equations DURING the past 30 years, many rewarding developments have resulted from the application of physical chemistry to steelmaking. A need still ex- which permits the calculation of oxygen contents. The model was programmed for computer calc~ilations. The validity of the method was demonstrated on routine oxygen samples from numerous commercially melted heats of stainless steel. ists for further progress in the use of thermodynamics to meet the more stringent requirements for cleaner steel. Current electric furnace practices have been developed around minimizing residual-oxygen content, one of the most important factors controlling the inclusion content of stainless steels. The residual oxygen is controlled by the use of deoxidizers during the finishing period and a number of empirical rules have been evolved. Although this feature of electric furnace practice has long been in use, only in recent years has funda-

Jan 1, 1963

By D. R. Bomberger

An automatic microscope has been developed to .measure the size and populations of macerals and minerals in fine coal particles. Differentiations are made on the basis of reflectance. This study is concerned with the size distribution of pyrite inclusions. Most fine coal cleaning processes do not remove pyrite as completely as a straight density separation. Consideration of the pyrite size distribution is suggested as a more accurate method of predicting sulfur reduction by a cleaning process. Analyses of float-sink results and Deister Table operation in terms of pyrite particle sizes are made. Other potential applications of automatic microscopy are also discussed.

Jan 1, 1963

By Alla D. Mah

Energies of combustion of vanadium nitride (VN) and vanadium carbide (VC) were measured. Correcting to vanadium tetroxide (V204) as the final state, the heats of combustion were ?H298.15=-118,700±100 cal/mole of vanadium nitride and ?H298.15=-240,270±360 cal/mole of vanadium carbide. With vanadium pentoxide (V205) as the final state, the heats of combustion were ?H298.15= -133.440±100 cal/mole of vanadium nitride and ?H298.15=-255,020±360 cal/mole of vanadium carbide. Combining these results with vanadium oxide data, the heats of formation obtained were ?298.15=-51,880±200 cal/mole of vanadium nitride and ?H298.15=-24,350±400 cal/mole of vanadium carbide. Heats and free energies of formation of vanadium nitride and carbide were calculated to 2,000° K.

Jan 1, 1963

By John M. Dealy, Robert D. Pehlke

Values for interaction parameters in nonferrous systems, as calculated from published data, are tabulated and discussed. The influence of temperature on the parameter is derived and compared with the results of the literature study. Wagner's relationship between the interaction parameter and the self interaction coefficients is compared with the tabulated data. A problem which has been of considerable interest in the field of metallurgy is the prediction of the effect of one alloying element present in dilute concentration on the thermodynamic properties of another dilute alloying element. Ultimately, the prediction may be accomplished entirely from statistical mechanical considerations. At the present, however, the problem remains unsolved since liquid solution models which are simple enough for analytical treatment are inadequate for such purposes. Thus, we desire some means of organizing the information on dilute systems which will serve as a guide for further study on interactions in dilute alloys, and also provide a basis for the utilization of thermodynamic data in the engineering design of alloys.

Jan 1, 1963