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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

By C. Ernest Birchenall

TWO recent papers1,2 cite measurements of surface contour changes on copper which, when attributed to surface self-diffusion, can be interpreted to yield activation energies for surface self-diffusion that approach1 or exceed2 those reported for volume self-diffusion in the same metal.3 It is acknowledged2 that AS must be assigned much too large a value to be physically reasonable in order to make the theoretical Do's agree with the experimental values, if the jump distance is of the order of the interatomic distance. However, long jumps would probably lead to marked anisotropy on planes that consist of ridges and valleys (like (110) in fcc) whereas only mild

Jan 1, 1963

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By Michael Hoch, Walter C. Wyder

The Cr-Ni system was investigated between 900" and 1400°C and 45 to 100 wt pct Cr. The Cr-Fe system was studied between 1200" and 1385°C and 70 to 100 wt pct Cr. Powdered alloy compacts were produced from high-purity chromium, nickel, and iron poulders. The compacts were sintered in an argon atmosphere and then machined into small, 0.030-in. diam cylindrical specimens. These were then heated by induction in the high-temperature X-ray diJfractwn camem under a helium atmosphere and irradiated with copper Ka radiation. From the results of the high-temperature X-ray diffraction patterns it can be concluded that chromium exists only in the bcc form, and that no eutectoid reaction occurs in the Cr-Ni system in the temperature interval 900" to 1400°C. The X-ray diffraction patterns are in agreement with the Cr-Ni phase diagram of Bechtoldt and Vacher, and Williams. It is possible that chromium undergoes one or more allotropic transformations between room temperature and its melting point. Most of the evidence was gathered from the study of the chromium-rich ends of the Cr-Ni and Cr-Fe binary systems. All the investigations rely heavily on indirect methods: thermal analysis, electrical resistivity, and micro-graphic inspection of quenched samples. In the present work the chromium-rich side of the Cr-Ni and Cr-Fe binary systems is studied, using high-temperature X-ray diffraction techniques. Thus the coexistent structures can be observed directly at temperature. PREVIOUS INVESTIGATIONS ~ansenl shows two possible Cr-Ni phase diagrams 1) a simple eutectic [Liquid =a-Cr(bcc) + y-Ni(fcc)], 2) a eutectic [Liquid+ P-Cr(fcc) + y-Ni(fcc)] and euctectoid [p-Cr(fcc) ==a-Cr(bcc) + yNi(fcc)]. The latter is based on the work of Grant and co-workers.2 Stein and rant'" placed the eutectoid composition at 1215°C and 68 wt pct Cr; their diagram is shown in Fig. l. Similarly, Sully3 also discusses the two proposed diagrams. Price and Grant,4 working on an isothermal section of the Cr-Ni- Fe ternary diagram at 1300°C, made no mention of a ß-chromium phase (fcc). The ß-chromium structure was also reported by Misencik 5 in the Cr-Nb(Cb) system. Williams 6 studied the Cr-Ni system using precipitation techniques. His work included the chromium and nickel solvus lines below 1250°C. He reported no ß structure nor any eutectoid reaction. The solvus lines which he produced were very similar to those of Jette, et al 7 below 1000°C. He concluded that Grant and coworkers2 had misinterpreted their data, and that effects which they had reported were actually due to the rapid and extensive precipitation of the nickel-rich phase. Bechtoldt and vacher8 used sintered powdered alloy compacts in an attempt to find the ß phase. They used metallographic and room-temperature X-ray diffraction techniques and also failed to detect the fcc chromium phase. They attributed the low slope of the chromium solvus at approximately 1150°C as the probable cause of the abundant precipitation obtained. They also stated that the precipitation was the probable cause for the abrupt discontinuities in the thermal analysis and electrical resistivity data which led to the conclusion that a eutectoid reaction existed. Fig. 1 also shows their diagram. Grigor'ev and coworkers9 investigated the polymorphic changes of chromium in the Cr-Ni phase diagram. Using standard microstructural and thermal analysis techniques, they published a phase diagram which contained five polymorphic forms of pure chromium and four eutectoid reactions. They stated that the room-temperature bcc chromium transformed to a fcc structure at 930°C, to bcc at 1300°C, to hcp at 1650oC, and then finally to bcc at 1830°C. The eutectoid reactions were placed at 850°, 960o, 1140°, and 1220°C. Also to be noted was the fact that the uppermost phase, the bcc above 1830°C, was different from the upper phase of Grant and coworkers,2 the fcc above 1840°C. Their eutectoid reactions, temperatures and compositions fall

Jan 1, 1963

By W. R. Hardwick

This Information Circular describes copper mining and concentrating methods, practices, and costs at the Silver Bell Unit of American Smelting and Refining Co., Pima County, Ariz. It is one of a series being prepared by the Bureau of Mines on mining methods, practices, and costs in various mining districts of the United States. The Silver Bell mining district, one of the older districts in Arizona, is in the western part of the Silver Bell Mountains in Pima County, about 40 miles west of Tucson and about 20 miles southwest of Red Rock, a station on the main line railroad of the Southern Pacific Co. The Oxide and the El Tiro open-pit mines of the American Smelting and Refining Co. are in the district (fig. 1. The principal ore deposits are in T. 12S., R.8E., Gila and Salt River base line, at an altitude of about 3,000 feet. The present town of Silver Bell, established in 1952, is reached by a paved highway, the Avra Valley road, that turns west from Highway 84 at Plata siding near Rillito and extends westward 25 miles to the townsite (fig. 2). The present town is about 5 miles southeast of the old town of Silver Bell that flourished from 1900 to 1930.

Jan 1, 1963

By M. Weinstein, J. F. Elliott

IN conjunction with a study on the solubility of hydrogen in liquid pure iron and iron alloys, new and

Jan 1, 1963

By A. A. Berk

Other Federal agencies have been coming to the Bureau of Mines for help with the purchase and utilization of fuel, largely coal, almost since the day the Bureau was created in 1910. The requests covered a wide range of fuel- economy problems and included boiler-water treatment after it became apparent that water-formed deposits on heating surfaces acted as insulators, decreasing heat transfer and impairing fuel efficiency. Dr. Ralph E. Hall, a Bureau of Mines physical chemist determined the 3 reactions that cause adhering scale to form in boilers (7)2 and went on to introduce scientific principles into water treatment for scale prevention (8). Widespread publicity of these achievements increased the requests for help from Federal steam-generating plants. Since no other Federal agency (even those which were more directly concerned with testing water) wanted to provide boiler-feedwater service, the Bureau decided to continue to give requested help to Federal agencies, Later, the Congress endorsed such agency cooperation as an economy measure,

Jan 1, 1963