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By J. T. Norton, Pekka Rautala

The phases and equilibria in the W-Co-C system have been studied by X-ray diffraction methods, metallographic technique, and thermal analysis. In addition to the 7 phase, two double carbides, called 8 and have been revealed. The compositions correspond to CO3 W6C2 and Co3-W10C4. The reactions leading to these phases have been explained and tentative diagrams of stable and metastable equilibria proposed. The basic reactions in sintering cobalt cemented tungsten carbides are discussed. THE W-Co-C system is of fundamental importance in practical carbide manufacturing as well as for the understanding of the sintering mechanism. Surprisingly little is known about this system, for the probable reason that all the important alloys are of two-phase structure and that the diagram Co-WC has been treated as a quasi-binary. This obviously is incorrect, because WC decomposes before melting. One ternary phase, 7, of composition Co3W3C has long been known. It was first studied by Adelskold, Sundelin, and Westgren,1 although the isomorphous iron-tungsten carbide was known earlier. There have been in the literature several reports of two 7 phases.' " Also the 7 phase has been considered unstable by Takeda4 and Westgren.1 The Co-WC diagram has been studied by Wyman and Kelley5 and a quasi-binary diagram has been published by Sandford and Trent.2 Takeda has published a tentative Co-W-C diagram, considering both metastable and stable equilibria. However, the lines of two-fold saturation are shown only partially and it seems impossible to complete the diagram without violating the phase theory. Therefore it seemed desirable to examine the system in more detail. Experimental Procedure The alloys used in the present investigation were made of powders of tungsten, tungsten monocarbide, cobalt, and carbon and were of the grade used in manufacture of commercial cemented carbides. The powders were ground and mixed in small stainless steel ball mills, using balls of the same material. Benzene was used as a dispersing agent. The mixing period was 1 hr, since this was shown to give suffi- ciently good mixing of the powders without too great a contamination from the mill. After ball milling, the specimens were pressed in cylindrical or rectangular dies. No paraffin or other lubricant was used and the small compacts had sufficient green strength to be handled without difficulty. Several sintering furnaces were employed. The most satisfactory arrangement was a vacuum furnace based on the Arsem principle which employed a graphite helix as the resistance heating element. Specimens were placed on graphite stands and there was generally a slight carburization or decarburiza-tion of the specimen surface, depending on the carbon content of the alloy. The evaporation of the cobalt at a sintering temperature of 1400°C was not significant, but became severe at 1500°C and higher. The sintering time was 1 hr at 2000°C and 2 to 4 hr at lower temperatures. It was not possible to quench the specimens, but the cooling rates were rather fast, greater than 300°C in the first minute. In the system under investigation, the reactions are sluggish, and it is believed that the high temperature structures are satisfactorily retained. The principal method of investigating the sintered specimens was X-ray diffraction by the Norelco recording spectrometer. Approximate determinations of the phase boundaries were made by the disappearing phase method. Ternary Phases To study the phase formation in W-Co-C system, a series of specimens was sintered at 1400°C. In this experiment two ternary phases, called here ? and k were formed in addition to the well-known 7 phase. The 7 phase, which has been completely described by Westgren: showed a range of homogeneity from 7 to 20 pct C and from 38 to 48 pct Co. At 1400°C the 7 phase was found to be in equilibrium with monotungsten carbide, 8, tungsten, 8, #?, and liquid. The boundaries toward #? and liquid were difficult to determine and appeared to be very temperature sensitive. The other boundaries are believed to be well fixed. The homogeneity range of 7, as measured in this work, is considerably smaller than the one

Jan 1, 1953

By E. J. Dulis, R. M. Fisher, K. G. Carroll

IT is well known that ferritic steels containing more than 15 pct Cr when subjected to temperatures in the range of 700" to 1000°F exhibit increasing hardness and decreasing ductility. The phenomenon has been widely termed the "885 °F embrittlement," after the temperature of most marked effect.'.' In view of the excellent review articles available in the literature3-6 only a brief account of experimentally established facts need be given here. The extent of changes in physical characteristics during embrittlement depends on chromium concentration and time at temperature, higher alloy content and longer time both promoting more rapid and extensive changes. In a 27 pct Cr steel, changes in impact strength and in angle of fracture in bending can be detected after only a 1 hr exposure at 885°F; after 50 hr this steel becomes quite brittle. Hardness increases slowly with time during thousands of hours exposure and may attain a maximum hardness number twice as large as that of the unexposed steel. Microstructural changes accompanying embrittlement have been described as an initial widening of grain boundaries followed by eventual darkening of ferrite grains. Embrittled steels etch more readily, e.g., the weight loss of a 27 pct Cr steel in acid solution may occur at a rate one hundred fold greater following exposure at 885 OF. Marked changes which accompany embrittlement have been observed in electrical resistivity, specific gravity, and magnetic coercive force. Changes in physical properties may be readily removed by heating at temperatures above the embrittling range, such as a treatment at 1100°F for 1 hr. It has frequently been noted that the 885 °F embrittlement suggests precipitation on a submicro-scopic scale of a chromium-rich constituent, the nature of which has not been revealed by X-ray diffraction. Progressive broadening of the body-centered cubic diffraction lines during embrittlement has been observed," and recent observations by Lena and Hawkes' upon single crystals have shown early asterism in X-ray photographs, disappearing within an hour at 900 °F. Many workers have ascribed8-13 the phenomenon to a precipitation of a phase (FeCr), which is known to cause embrittling effects at temperatures much higher than 885°F. Two general observations, however. suggest that a precipitation cannot be responsible for the 885°F phenomenon: 1—prior cold work greatly enhances a formation, whereas it scarcely affects the 885 °F embrittlement, and 2—the presence of an alloying element such as nickel or manganese may have an effect on the 885 °F embrittlement which is opposed to its effect upon a formation. The slight enhancement of a formation and 885°F embrittlement observed in the presence of elements with strong carbide and nitride forming tendencies' is probably a consequence of lessened chromium depletion of the matrix. The bar graph in Fig. 1 shows a typical example, taken from two 27 pct Cr steels used in this work, of the hardness after exposure for 10,000 hr at 900°, 1050°, and 1200°F. Steel A (0.03 pct C, 3.13 pct Mn) showed marked hardening at 900" and 1200°F, whereas steel B (0.12 pct C, 0.63 pct Mn) exhibited only the 900°F hardening. The cr phase was found in steel A at the higher temperatures but not in steel B. Presumably a formation is enhanced by the low-carbon and high-manganese concentrations in A," Thus there are two distinctly different hardening phenomena present which cannot both be ascribed to v precipitation without invoking a transition phase possessing remarkable properties. Materials A number of chromium steels exposed for long periods (5000 to 34,000 hr) at 900°F, as well as unexposed samples of one of the steels, were available for this investigation. Table I gives the chemical compositions and aging treatments of these steels. In addition to these steels exposed in the elevated temperature test furnaces of the National Tube Division, a number of high-chromium steels were heated for short periods in small laboratory air furnaces and lead baths. Supplementing these commercial steels, a sample of high-purity (0.018 pct C, 0.002 pct N) 28 pct Cr iron, exposed 1000 hr at 887°F. was furnished by the Union Carbide and Carbon Corp. In addition, an alloy of iron and chromium of high purity containing 46 pct Cr was used. This

Jan 1, 1954

By Ralph Hultgren, Bernard York, David W. Mitchell

It is a well-known fact that magnesium-alloy castings are apt to be coarse grained if the melt is not superheated several hundred degrees above the melting point before casting. (The casting temperature varies according to the shape of the mold. A typical casting temperature is perhaps 1400°F.) British practice is to heat to 900°C. (1650°F.) for 15 min., cool rapidly to casting temperature, and cast.' In Germany superheating is carried out at 850' to 900°C. (1560° to I650°F.) depending on the amount of scrap used. It is stated that further refinement will be obtained by prolonging the period of superheating or by increasing the superheat temperature to 950°C. (I740°F.).2 In the United States superheating is carried out at 1600' to 1700°F. (871' to 927°C.), perhaps even higher in some places. It is stated that superheating effects are found as low as 1500°F. (816°C.), but several hours are required.3 These commercial treatments lead to grain sizes in sand castings that may vary from 4 to 8 grains per sq. mm.! in heavy sections and from 60 to IOO in 1/2-in. sections to perhaps 380 in thin sections. It is also generally known that the refining effect of superheating is lost if the melt is held for some time at lower temperatures before casting. Aside from these very qualitative statements, there is little to be found in the literature as to the effect of temperature and time of superheat on the final grain size. Because of the uncertainty of these factors, the Office of Production Research and Development of the War Production Board placed a research contract with the University of California, supervised by the War Metallurgy Committee. This research, which was done under the "Restricted" Project NRC-550, is the basis of this paper, which has been released for publication by the O.P.R.D. The material studied was an alloy prepared from carbothermic magnesium. The temperatures required for grain refinement proved to be widely different from those used in practice, as described in the statements in the first paragraph. This difference is attributed to the fact that the magnesium in the specimens was of carbothermic origin instead of the electrolytic magnesium in common use. Materials and Methods The magnesium alloy studied was one of the most popular sand-casting alloys, with a nominal composition of 9 Per cent aluminum, 2 per cent zinc, and 0.1 per cent (minimum) manganese and the balance magnesium. This is designated

Jan 1, 1945

By Ernest G. Enck

"The Rockets' Red Glare" of the Fourth of July is produced by strontium compounds. However, strontium has a number of less spectacular uses; i.e. in, or in connection with, the manufacture of ceramics, caustic soda, glass, railway and truck signal flares, beet sugar and steel. The principal ore of strontium for use both as the mineral and for production of compounds is celestite (SrSO4). This mineral varies in color from white to pink or blue depending on presence of impurities. It has a hardness of about 3.5 and specific gravity of 3.9. It is brittle and has perfect basal and prismatic cleavages. The high grade ore is obtained from England, hence it has become the standard for all other producing areas. (See analyses, Table 1.) The most objectionable impurity in English celestite is iron, coming mostly from adhering clay. On the other hand, Mexican celestite, while no higher in strontium sulfate content, is extremely low in iron (less than 0.2 pct), hence it is more desirable for certain uses. Most of the celestite in Spain and in the United States is high in calcium and barium, and commonly high in iron, and requires some form of beneficiation in order to be equal to English ore. The natural carbonate (SrCO3), or strontianite, is less important than celestite as a source of strontium, because it is less abundant and is not so widespread in its occurrence. Furthermore, it generally occurs with calcite (CaCO3) and lead sulfide (PbS), and for most uses these impurities are detrimental. This mineral is generally white or yellowish, forming needle-like crystals. It has a hardness of about 3.7 and a specific gravity of 3.68-3.8. The mineral is brittle and has an imperfect cleavage. A typical analysis of German strontianite is shown in Table 1. [ ] Distribution of Deposits UNITED STATES Occurrences of strontium minerals are known in Arkansas, Arizona, California, Illinois, Ohio, Pennsylvania, Tennessee, Texas, and Washington. Celestite occurs in the Vulture Mountains, Maricopa County, Arizona in beds three to ten feet thick associated with sandstone, gypsum, and barite. Because of the low strontium content, approximately 86 pct SrSO4, it has no commercial value. A large deposit of celestite occurs in San Bernardino County, California, in the Cady Mountains near Argus Station, about eight miles west of Ludlow. The celestite here is interbedded with shaly and clayey tuff in a zone about 300 ft thick. Massive, finely crystalline ore has been recovered with an analysis

Jan 1, 1960

By B. C. Allen

Grain-boundary gvoocing was studied irz chronziu?n. molybdenum, tungsten, and the solid-solution alloys, Cr-35Re. Mo-33Re, and W-25Re at 0.6 to 0.9 of the absolute liquidus temperature under an inevt atmosphere , foveign nzetal zlapor, and liquid metal. The controlling mechanism of matter transport was deduced frolr groove size and shape. kinetics of growth, and cotnparisoz with theoretical relatiotzships derived by Mullins. Grooves in chowzizon formed prittzarily by volume diffusion tkrongk kelium or argon at 1 atm pressure and by e1)apovation-condensatiotz in a static vacuum. Groozles in the other nzetals and alloys forrned priniarily by sirface diffusion, the coefficients of which were calculated. Carbon was found to decrease the acti7:ation energy for surface diffusion on molybdenun. Sitrface diffusizities weve sinzilav for iWo-0.0ZC and Mo-33Re. The presence of about 1 -?nm pressure of silver or tin vapor did not affect the neckanis)n of grooz;e formation. In liquid titz or silz:er, pain bolindary gvooves formed by zolume diffusion in the liquid. BASED on theories of ullins," the mechanisms of grain-boundary grooving have been determined for low-melting metals such as copper in an inert atmospheres or in liquid lead.4 The purpose of this investigation was to study grain-boundary grooving in the refractory Group VI-A metals, chromium, molybdenum, and tungsten, and the bcc solid-solution alloys, r-35e, 0-33e,= and -25e,' at 0.6 to 0.9 of included to see whether Mullins' theories were applicable to them as well. EXPERIMENTAL WORK The materials chromium, molybdenum, tungsten, Cr-35Re, Mo-33Re, and W-25Re were in the form of 0.050-cm-thick sheet assaying 99.98 pct or better. The nominal carbon level was generally 30 ppm. The oxygen + nitrogen + hydrogen content was -50 ppm. Mo-33Re and W-25Re were prepared by powder-metallurgy methods and supplied by Chase Brass and Copper Co. The remaining materials were arc-cast. Chromium and Cr-35Re were prepared at Battelle by arc melting, extruding, swaging, and rolling. Mo-0.003C was supplied by Climax Molybdenum Co., and Mo-0.02C and tungsten by Universal Cyclops Corp. As a source of liquid metals, tin and silver granules assaying 99.98 pct were used. Spectrographic analyses indicated the presence of -100 ppm each of iron and silicon. Vacuum melting reduced the combined gas content to c5 ppm (2.60,, 0.9N2, 0.4H2 in tin and l.602, 0.7N2, and c0.04H2 in silver). Specimens were prepared for grain-boundary grooving. Coupons 0.5 by 1.5 cm with a small hole in one end, or substrates 1.5 by 1.5 cm, were cut from sheet. The specimens were annealed in containers of the same material to provide a vapor-solid equilibrium as well as to protect them from gaseous impurities. Outgassing was done at 2 x 10"5 mm for 15 to 30 min at 1150°C for chromium and Cr-35Re, 1750°C for molybdenum and Mo-33Re, and 2600°C for tungsten and W-25Re. Then recrystallization to a stable grain size of about 0.5 mm was accomplished by annealing at least 1 hr at 1600°C for chromium, 1800°C for Cr-35Re, 2350°C for molybdenum, and 2300°C for Mo-33Re in a rhenium-element resistance furnace under 1 atm of static argon or helium. The atmosphere was gettered by tantalum radiation shielding. Tungsten and

Jan 1, 1967

By J. R. Low, D. F. Stein

Single crystals of iron have been grown from three different lots of Ferrovac "E" of somewhat different chemical composition by the strain anneal technique. Using a technique to seed the crystal similar to Dunn's for silicon-iron, it has been possible to orient the crystals grown in both direction and plane of growth. Crystals having the plane of the strip oriented (100) , (110), (111), (112), (123), and (491) have been grown. The growth directions used have been [100], [110], 45 deg from a [110}, and various others of no specific crystal orientation. The usual dimensions of the crystals were 8 by 1 by 0.08 in. Attempts to grow crystals were about 90 pct successful. METHODS of growing single crystals of high purity iron have been reported in the literature.1-4 However, each of these methods was not completely reliable when used on materials having slightly different chemical composition and in some instances a small number of successes were obtained using identical materials. Except for the method used by S. Dohi and T. Yamoshita,1 it has not been possible to reorient single crystals of high purity iron to give any desired orientation. The method to be described has made it possible to grow single crystals from three different lots of material having different compositions, and to orient the crystals with respect to growth direction and surface. STARTING MATERIAL The material used during this investigation was a vacuum melted high purity iron marketed by the Vacuum Metals Corporation designated Ferrovac "E." Three lots of Ferrovac "E" having the following composition were used with equal success: The compositions listed are those of the as-received material; and they may have been modified before the growth of single crystals. Analysis of heat B just before growth and after growth revealed that the heat treatment prior to growth did not change the carbon content, but the oxygen content was changed from 0.0092 pct to 0.0034 pct and the nitrogen content from 0.0003 pct to 0.0001 pct. After growth of the single crystals, the carbon had dropped to 0.001 pct. None of the heat treatments would be expected to change any of the other impurities very markedly. Heat C would be expected to have a metallic impurity content similar to heats A and B. PROCEDURE Ferrovac "E" iron which had been obtained in bar form having a diameter of about 1 in. was rolled into strip for growing single crystals. By passing the 1-in. bar through a cold rolling mill several times, it was reduced to a strip 0.15 in. thick. The strips obtained were then cut into suitable lengths for heat treating (about 9 in. long), annealed at 925°C for 2 hr in dry hydrogen and water quenched. It was then necessary to bake the strip at 200°C for 24 hr in air in order to prevent cracking during further rolling operations. While it was possible to cold roll the 1-in. bar directly to the desired 0.080-in. strip, the intermediate anneal was used because the strip so obtained produced better single crystals. The strip obtained by rolling the 1 -in. bar directly to 0.080-in. strip produced single crystals having a large number of occluded grains. Experiments showed that the optimum reduction in area by rolling prior to the growth of single crystals was about 50 pct. Attempts to grow single crystals from material that had been reduced less than 40 pct were unsuccessful presumably because the matrix did not possess the critical amount of texture necessary for growth. The strip obtained after the rolling operations had very irregular edges which were ground to give a strip with uniform dimensions. The strip was then annealed at 825°C for 3 hr in hydrogen and furnace cooled. Fig. 1 illustrates the grain size obtained. A temperature of 940°C was used for the annealing temperature on one group of strips

Jan 1, 1962

By Henry F. Heblby

HOW often has the thoughtful observer pondered the apparent contradictions experienced in the weather? One can take records of two days, one in the winter and one in the summer. The "degree days1' indicate that space heating and domestic load were present in one case and not in the other. The Business Index may be about the same, indicating that the industrial activity of the area and its concomitant use of fuel were about the same. Thus the volume of the products of combustion released to the atmosphere varied only as related to the space heating demand. Yet on one day in winter the atmosphere may be clear and bracing, while on a summer's day the air is thick and murky and the visibility sharply reduced. The situation may be reversed. What are some of the factors that contribute to the creation of these conditions? These few notes have been prepared to indicate some of the influences that are exerted on the problem. The Sources of Atmospheric PolLution The industrial area of Pittsburgh, Pa., has been a dominant center for the production of iron and steel for over one hundred years. In fact, with the growth of the numerous auxiliary processes Allegheny County which contains Pittsburgh is prob- ably the most industrialized county in the world. In addition, the type of manufacture carried out in this area is predominantly dependent on thermal energy (heat). That energy is supplied from coke and coal produced in the vicinity of Pittsburgh Indicative of the stupendous quantities of fuel that are employed in this industrial area's economy, the following (Table I) taken from the U. S. Census (1940) may be of interest. In tonnage consumed in the area, the figures are equally impressive: Annual Tons oF Coal Metallurgical Industries.... 35,000,000 to 40,000,000 Commercial Installations (Pgh.)................. 1,500,000 Domestic hand-fired) (Pgh.)................. 750,000 An influence that has never been fully appreciated by many individuals is the fact that no matter what adventures the gases of combustion experience as they pass through the various processes, uti-mately the spent gases are discharged through chimneys to the atmosphere.

Jan 1, 1949

By William A. Edmiston, R. E. Grace

A simplified model for the theory of reaction rates near equilibrium has been applied to the reduction of wustite. A linear relationship between the net rate of reaction and the Gibbs free-energy change, ?F, is predicted. The reduction of wustite in H2 -H2O gas mixtures was studied with a microbalance technique at temperatures from 850° to 950 °C. The predicted model was found to be valid to -?F/RT = 0.1 or approximately -200 cal per mole away from equilibrium. ThE theory of reaction rates near equilibrium has been developed by a number of authors. Prigogine, Outer, and Herbo1 have studied the catalytic hydrogena tion of benzene in an attempt to deduce some intrinsic connection between reaction rates near equilibrium and thermodynamics. Manes, Hofer, and weller2 have derived more general expressions for reaction rates near equilibrium from classical thermodynamics. Hollingsworth3,4 has commented briefly on the work of Manes et al. Benson5 has summarized in a general way the results of the earlier contributions. It is the purpose of this paper to apply the theory of reaction rates near equilibrium specifically to the reduction of wustite in H2-H2O gas mixtures. The basic premise is that the reduction of wustite proceeds by a surface reaction, rather than by solid-state diffusion ,or gaseous diffusion. Richardson and Dancy6 and Gellner and Richardson7 have suggested that the reduction of wustite may be governed by iron diffusion in wustite. Mckewan8-11 has proposed that reduced iron layers on various oxides are sufficiently porous to offer a negligible impedance to the reducing gas. The linear motion of interfaces reported by McKewan and discussed by Themelis and Gauvin12 indicates the lack of diffusive control during reduction. The reduction studies of magnetite reported by Quets, Wadsworth, and Lewis13 give additional evidence that reduction rates are linear when the reaction products are porous and nonprotective. The interpretation of measurements reported in this paper is predicated upon a surface-controlled reduction reaction, at least in the earliest stages of reduction when the reduced iron layer is thin.

Jan 1, 1967

By W. A. Backofen, R. L. Fleischer

Single crystal, bicrystal, and polycrystal tensile tests of aluminum at 4.2°K, 77°K, and 300°K have been used to examine the role of grain boundaries in the deformation process. Results indicate that a grain boundary may affect the extent and slope of easy glide. The stage II hardening rate, on the other hand, is independent of the presence or absence of grain boundaries. This conclusion allows the size of the region of multiple slip caused by an incompatible grain boundary to be determined. For the size of bicyystal sample used in this study, multiple slip occurs in about half of the cross section. PREVIOUS studies of the stress-strain characteristics of bicrystals of face-centered-cubic metals have been limited to aluminuml-5 at room temperature. Recent results, however, indicate that the stress-strain curves of single crystals of such metals may be separated into at least three stages6 in which different deformation processes are occurring7 provided testing is done at sufficiently low temperatures.' Since for aluminum a well-defined stage II develops only below room temperature, previous studies have not been able to relate effects of grain boundaries to all of the three stages of deformation. It is therefore to be expected that low-temperature deformation of aluminum single crystals and bicrystals should clarify the effects of grain boundaries on the different processes of deformation. EXPERIMENTAL PROCEDURE Single crystals and bicrystals were grown from the melt by the standard techniqueg with aluminum reported by Alcoa to be 99.993 pct pure. Ridges in the boat were used to guide the grain boundary during growth, assuring that the boundary would bisect the sample.10 The rate of furnace motion during growth was 1.0 cm per hr. During growth zone purification resulted, as evidenced by the ability of the first material to freeze to recrystallize at room temperature following severe deformation. Samples were approximately 4.4 X 6.6 mm in cross section and 103.5 mm in length between grips. Samples were annealed at 635" i 5°C for 40 hr and furnace cooled over a 7-hr period. They were then electropolished in a solution of 5 parts methanol to 1 part perchloric acid at a current density of 15 amp per sq dm for about 30 min at temperatures below 0°C. Tensile testing was performed at 295" (room temperature), 77" (sample in liquid nitrogen), and 4.2"K (sample in liquid helium) on the hard-type machine indicated schematically in Fig. 1. The machine con- sists basically of a tube surrounding a rod; one end of the sample is attached to each member, and the rod is pulled up the tube to extend the sample. The rod is rigidly mounted and is moved vertically by a system described by asinski." The pulling force is measured continuously by an electrical strain gage load cell, and the relative displacement of the tube and rod is also recorded continuously by a soft cantilever beam with electrical strain gages. Maximum stress and strain sensitivities were ±2g per sq mm and * 3-10-5. In all tests the strain rate was approximately 5.10-5 per sec. The thin wires in the tensile apparatus introduce softness, which may be corrected for, however, by measuring load vs displacement with the sample replaced by an elastic member. For loads greater than 15 kg the spring constant is 1.875.106 g per cm. The flexible wires also served to reduce substantially the large shearing forces which may arise in the case of grips having horizontal rigidity.'' As in any gripping system, however, bending moments will arise in the course of deformation by single slip. Engineering stress, s = (load)/(original cross-sectional area), and strain, E = (increase in length)/ (original length), are used for stress-strain curves unless otherwise indicated. Tables list resolved shear stress, T=mo and shear strain ? = dm, where m is the usual Schmid resolved shear stress factor for the primary slip system at the start of deformation. The first group of samples to be described forms an isoaxial set, all of the crystals making up the single crystals or bicrystals having the same tensile axis, the orientation of which is indicated by the cross in Fig. 2. For this orientation the primary slip plane and slip direction make angles of 45 deg with the tensile axis and the Schmid factor m has its maximum possible value of 0.5. Rotations about the tensile axis are indexed by means of an angle 0 between the small-area surface of the samples and the projection of the primary slip direction onto the cross section, as defined in Fig. 3. In single crystals, values of 0 were 0 and 90 deg, while in bicrystals 0 values were (0 deg, 180 deg), (90 deg, 270 deg), and (0 deg, 90 deg) as indicated in Fig. 4.

Jan 1, 1961

By M. H. Harris

A solution has been obtained to the problem of calculating flow into a cased and perforated well. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. Computer experimentation indicated that the results are within 3 per cent of the exact solution. Computed results are presented as an apparent skin effect, on a series of dimensionless working curves. Productivity ratios can be rapidly calculated from these data for the wide range of wellbore and reservoir properties actually encountered in field practice. Any reasonable vertical unisotropy ratio can be included in the computation. Productivities can be calculated for wells perforated in a regular pattern, a single horizontal plane or a vertical line on one side of the casing. Solutions for asymmetrical perforation patterns can he easily obtained from the working curves. Solutions for flow into sells completed with a horizontal notch are also provided. Results show that productivity can be increased by extending perforation penetration. This is especially true for shallow penetrations. The highest productivity is obtained when perforations are arranged in horizontal planes, as opposed to a vertical line on one side of the casing. Four or five perforations in one plane will approach the maximum productivity. The effect of perforation hole diameter is small, and is rioticeable only in shallow penetrations. INTRODUCTION The perforating method of well completion has been successfully and widely used in most producing areas. In the past, the desired perforation results were achieved by simply shooting numerous large holes in the casing. A perforating scheme for an area, or particular well, was established by evaluating two types of experimental data: the well flow index and the productivity ratio.' 3 The well flow index test is a means of determining the relative flow capacity of perforations in a linear system. This test also gives information on the perforation size, shape and hole damage which can be expected under well-bore conditions. However, relative flow data from this test cannot be accurately tarnsformed into the radial wellbore system. Thus, no true indication of the productive capacity of a perforated well can be obtained from the well flow index test. A well productivity ratio is derived from electrolytic models built to simulate perforated wells. Available productivity ratio data 2,3 are limited in that all important variables are not extensively evaluated. For example, data are limited to well radii of 3 and 6 in., and to maximum perforation penetration of 1 ft. Practically no information is available on the pattern of flow into a perforation. The effect of various perforation patterns on well productivity has not yet been determined and the effect of perforation diameter has not been thoroughly studied. Also, it will be shown that this type of electrolytic model data is probably in error by as much as 10 per cent or more. Modern completion techniques such as limited-entry perforating, single-plane fracturing, steam and hot air injection and chemical consolidation of incompetent formations all rely on injection and/or production from a limited type of completion. These completions may consist of several high-capacity perforations or a horizontal notch which is equivalent to an infinite number of perforations in one plane. Proper design of these new completion techniques requires, in part, accurate estimates of a well's productive capacity. Data on perforated and notched well productivity have been determined in this investigation. Results are presented as a function of the pertinent variables. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. DESCRIPTION OF PROBLEM PRACTICAL APPLICATION The computed results can be applied to wells which meet several general specifications. An external drainage radius of the well must be known or assumed, but the well need not be drilled on a regular pattern. The well must be cased and cemented through the entire producing interval. And, the casing must be perforated with one or more horizontal planes of perforations. The perforation pattern itself must conform to three geometrical requirements. 1. The perforations in a plane must divide the plane into equal angular segments (Fig. 1). Four perforations per plane would be 90" apart. 2. Perforations in a plane must be directly above or beneath perforations in adjacent planes. For two shots per plane, perforations would lie in the BB' plane (Fig. 1). 3. Horizontal planes must have equal vertical spacing and be separated from the top and bottom of the formation by one half the spacing interval. Single planes of perforations should be in the middle of the formation. This is shown in Fig. 2 where h is the formation thickness in a single plane conlpletion or the spacnig interval in a multiple plane completion. The spacing interval at the top and bottom of the formation may vary somewhat without causing an appreciable error in the productivity calculation if the formation is reasonably thick and there are many horizontal planes of perforations. A special provision has been made to calculate the productivity ratios of wells with uneven spacing intervals, or for the case where a single plane of perfora-

Jan 1, 1967

By W. T. Turrall, D. Porter

The paper describes a machine developed for the purpose of concentrating clear optical grade fluorspar crystal from a feed material containing less than 1 pct impurities. The principle of concentration is based on the fact that in a liquid having an index of refraction equal to that of fluorite (n — 1.434) clear crystals are invisible, whereas crystals containing occluded impurities absorb a part of the light. As the crystals pass through a light beam, undesired crystals give themselves away by creating a shadow on a photoelectric receiver. .The shadow is converted by the photoelectric cell into an electric pulse. An electronic circuit amplifies this pulse and commands the operation of a mechanical concentrator. Hp HE crystal laboratory, Dept. of Physics, Massa--*- chusetts lnstitute of Technology, was confronted with the problem of obtaining a supply of optical grade calcium fluoride (CaF,) for use in growing synthetic CaF, crystals. A search of the known fluorspar deposits did not indicate that any quantity of optical spar could be obtained. Even the best material had to be sorted by hand to remove impurities. The process for growing CaF, crystals developed by Professor D. C. Stockbarger of the Dept. of Physics, M.I.T., necessitates very pure feed materials. Exclusion of impurities is required, even in amounts detectable only spectrographically. The impurities occurred as minute inclusions of SiO,, BaSO,, CaCO,, FeS2, water or air. Crystals up to 4 in. in diam and weighing several pounds are made by the Harshaw Chemical Co. in Cleveland. Since the time required to grow a 4-in. crystal is about one week, and since the cost of manufacture is high, removal of impurities by any concentration method appeared practical. The mineral engineering section of the Dept. of Metallurgy undertook to investigate the possibility of concentrating clear optical fluorspar, —4 mesh + 10 mesh, from a feed containing over 99 pct CaF,. Various innovations of the known methods of concentration were considered, but in each case the minute amount of impurities associated with the crystal produced such extremely small differences

Jan 1, 1953

By W. T. Turrall, D. Porter

The paper describes a machine developed for the purpose of concentrating clear optical grade fluorspar crystal from a feed material containing less than 1 pct impurities. The principle of concentration is based on the fact that in a liquid having an index of refraction equal to that of fluorite (n — 1.434) clear crystals are invisible, whereas crystals containing occluded impurities absorb a part of the light. As the crystals pass through a light beam, undesired crystals give themselves away by creating a shadow on a photoelectric receiver. .The shadow is converted by the photoelectric cell into an electric pulse. An electronic circuit amplifies this pulse and commands the operation of a mechanical concentrator. Hp HE crystal laboratory, Dept. of Physics, Massa--*- chusetts lnstitute of Technology, was confronted with the problem of obtaining a supply of optical grade calcium fluoride (CaF,) for use in growing synthetic CaF, crystals. A search of the known fluorspar deposits did not indicate that any quantity of optical spar could be obtained. Even the best material had to be sorted by hand to remove impurities. The process for growing CaF, crystals developed by Professor D. C. Stockbarger of the Dept. of Physics, M.I.T., necessitates very pure feed materials. Exclusion of impurities is required, even in amounts detectable only spectrographically. The impurities occurred as minute inclusions of SiO,, BaSO,, CaCO,, FeS2, water or air. Crystals up to 4 in. in diam and weighing several pounds are made by the Harshaw Chemical Co. in Cleveland. Since the time required to grow a 4-in. crystal is about one week, and since the cost of manufacture is high, removal of impurities by any concentration method appeared practical. The mineral engineering section of the Dept. of Metallurgy undertook to investigate the possibility of concentrating clear optical fluorspar, —4 mesh + 10 mesh, from a feed containing over 99 pct CaF,. Various innovations of the known methods of concentration were considered, but in each case the minute amount of impurities associated with the crystal produced such extremely small differences

Jan 1, 1953

By Henry M. Howe

The data which are collected in Table 1 show that the ferrite of low-carbon steel and of electrolytic iron, like the network of hypo- and hyper-eutectoid carbon steel, inherits, either absolutely or relatively, the grain size of the mother austenite from which it is born in cooling through the transformation range. This evidence is so abundant and concordant as to cast doubt on Prof. Jeffries'l hypothesis of what might be called reversed inheritance, by which he explains Mr. Ruder's observation2 that a grain in a "slug of pressed pure electrolytic iron powder" was coarser, perhaps 1,500,000p2, aftcr a 3-hr. exposure to 1000" C. than after a 3-hr. exposure to 1250-1300°, when the grain size was about 35,000µ2. His explanation implies a natural tendency of coarser austenite grains to yield finer ferrite ones than spring from finer austenite grains, so that the inheritance is reversed. What seems to me a simpler explanation is that the enormous grains which followed the 1000" heating were not inherited from the mother austenite, but were formed by the process of natal coarsening, by means of which Stead and Carpenter developed grains of this same order of magnitude in this same kind of material, on heating to 950" or to 1000°, the temperature used by Mr. Ruder, provided the exposure was not unduly prolonged, and it does not seem to have been in Mr. Ruder's case. That their coarsening was natal and not through inheritance is shown first by the fact that their grain coarseness was out of all proportion to their relatively low temperatures and short periods, and hence was very far in excess of the grain size which the mother austenite must have had, and second and more cogently by the fact that the shape of these coarsened grains was evidently determined by the temperature distribution which existed during and immediately after the Ar3 transformation, that during the passage from the gamma to the non-gamma state. In discussing this subject, we must remember that coarse ferrite grains, whether those formed in cooling from the molten or those induced by

Jan 1, 1918

By W. N. Best

Crude oil attracted attention because of its excellence as a fuel for openhearth furnaoes; for making crucible steel and brass; for melting copper, lead, tin, zinc, nickel, silver, malleable iron, gray iron; and for the production of steam in all sizes and types of boilers. For heating furnaces, mold-drying ovens, core ovens, ore roasters, calciners, hotair furnaces, sand drying, asphalt road work, etc., its superiority over other fuels is due to the fact that the heat is at all times under perfect control, so that a constant temperature may be attained and maintained at the will of the operator. This mcans a maximum amount and uniform quality of work. Crude oil is of two kinds, paraffine base and asphaltum base, and varies from 11 to 46 gravity BaumB. The light-gravity oil does not require heating before use; but oil of less than 20 gravity Baumé should be heated to just below its vaporizing point, in order to reduce its viscosity and to obtain the highest efficiency of combustion. Heavy California oil vaporizes at 230". F., Mexican crude oil at from 175" to 210" F., and Beaumont, Texas, oil at 142" F. Fuel oil vaporizes at 130" F. Scientific Installation Essential The burning of oil is an art based on science, and the "rule of thumb" should never be employed, especially in heating heavy crude oil. Thermometers should be used on both suction and supply pipes so that the fireman or smith will at all times know the temperature of the fuel. The indicators on such thermometers should be large enough to be readily seen by the operator, night or day. It is necessary to have an unvarying pressure of steam or air through the burner, to atomize the fuel. Also, the air used to support combustion should be delivered through a nozzle under the burner at a constant pressure. The oil pressure must not fluctuate; under no eircumstances should it vary more than 1 1b. The oil pump, which should be brass-lined, with the aid of the pulsometer and superheater, will insure a constant

Jan 1, 1916

By Helmer Hedstrom

The purpose of this paper is to direct attention to the importance and the usefulness of phase measurements in electrical prospecting for ore, a subject about which virtually nothing has been published. The paper describes a new field method for ore prospecting, the "Turam" method, which makes use of phase measurements, and which has been used with great success for five years. Of the principal geophysical prospecting methods, the gravimetric and magnetic methods determine the direction and strength of the static fields of force of the earth. By seismic and electrical methods, fields of force are applied to the block of ground under investigation. By these methods a third parameter can be measured, besides the direction and strength of the field; namely, the time of arrival of the applied field at the different observation points. This time of arrival has been practically the only parameter measured in seismic work, while in electrical prospecting it has generally not been considered, the measurements having been limited to determination of direction and strength of the applied field. Phase Measurements In the most widely used of the electrical prospecting methods, those using alternating current, the time of arrival of the "electrical vibration" at the different observation points can be carried out as phase measurements. The phase angle measured then expresses, in part of one "vibration," or one cycle, how much the electrical vibrations at the observation point are out of step with those close to the source of the field. A phase lag of 45", for instance, means that the alternating field in the observation point is one-eighth of one complete " vibration," or cycle, out of step behind the field at the source. If the frequency is, say, 500 cycles per second, a frequency often used in electrical prospecting, a phase lag of 45' then means that the time required for the field of force to travel from the source to the observation point is 1/8 ' /500 = 1/4000 sec. Since the phase angle can be measured with an accuracy of a fraction, say one-tenth, of a degree, and the frequency can be considerably higher than 500, it is readily seen that the time of arrival can in this way be measured

Jan 1, 1940

By Helmer Hedstrom

The purpose of this paper is to direct attention to the importance and the usefulness of phase measurements in electrical prospecting for ore, a subject about which virtually nothing has been published. The paper describes a new field method for ore prospecting, the "Turam" method, which makes use of phase measurements, and which has been used with great success for five years. Of the principal geophysical prospecting methods, the gravimetric and magnetic methods determine the direction and strength of the static fields of force of the earth. By seismic and electrical methods, fields of force are applied to the block of ground under investigation. By these methods a third parameter can be measured, besides the direction and strength of the field; namely, the time of arrival of the applied field at the different observation points. This time of arrival has been practically the only parameter measured in seismic work, while in electrical prospecting it has generally not been considered, the measurements having been limited to determination of direction and strength of the applied field. Phase Measurements In the most widely used of the electrical prospecting methods, those using alternating current, the time of arrival of the "electrical vibration" at the different observation points can be carried out as phase measurements. The phase angle measured then expresses, in part of one "vibration," or one cycle, how much the electrical vibrations at the observation point are out of step with those close to the source of the field. A phase lag of 45", for instance, means that the alternating field in the observation point is one-eighth of one complete " vibration," or cycle, out of step behind the field at the source. If the frequency is, say, 500 cycles per second, a frequency often used in electrical prospecting, a phase lag of 45' then means that the time required for the field of force to travel from the source to the observation point is 1/8 ' /500 = 1/4000 sec. Since the phase angle can be measured with an accuracy of a fraction, say one-tenth, of a degree, and the frequency can be considerably higher than 500, it is readily seen that the time of arrival can in this way be measured

Jan 1, 1940

By Reinhardt Thiessen

Under sulfur in coal, is usually understood that form of sulfur which is combined with iron and known as pyrite. It occurs in the form of balls, lenses, nodules, continuous layers, thin sheets, or flakes, both in horizontal planes and vertical cleavage fissures. But pyrites also occur as very fine microscopic particles, or nodules, disseminated through the compact coal. This form has had but very little consideration. Finally, there is sulfur in coal in an amicroscopic form (not visible with an ordinary microscope), probably combined with the organic matter that exists in the coal. This form has had considerable attention from a scientific standpoint, but has probably not been recognized enough on the economic side. One or the other, or both, of these two latter forms may comprise the larger part of the sulfur content of coal, especially after it has been washed or otllerwise prepared for use. Pyrites in Microscopic Particles All coals that have been examined by the author contained a varying amount of sulfur in very small globules, or particles, of pyrite. These particles are seen in a thin [section as roughly rounded opaque dots, Figs. 1 to 10. When isolated, they are generally shown to be approximately spherical in shape, with a rough outer surface. They vary in diameter from a few microns to a hundred microns, the majority messuring from 25 to 40 microns; relatively few exceed the latter diameter. They are, therefore, very small objects. Their size is best appreciated by comparing the illustrations, in which they are shown. at a magnifiea tion of 100 diameters, with some known area like the period used in the ordinary printed page. The period is about 0.6 mm. in diameter, and . when magnified 100 times, will cover a circular area of about 2 1/2 in. in diameter, or all but the corners of the illustrations. The illustrations, therefore, represent an area about as large as an ordinary period, and the pyrite globules form but a small part of the total area. Very frequently a number of these particles are joined together in horizontal rows; oc-

Jan 1, 1920

By V. S. Gupt, W. H. Somerton

Rock may undergo great changes in physical properties when heated to high temperatures and then cooled, The temperature and intensity of reactions causing rock alterntiorl.s can he controlled by introducing certain chemicals during heat treament. Three typical outcrop sandsone samples were saturuted with common salt solutions, then heated to several maximum temperatures. After cooling, it was found that per-rrreuhilities had increased much more for salt-saturated samples than for samples not saturated with salt but heated to the same temperatures. This was only true, however. for samples heated above the melting points of the particrrlar salts. Potassium chloritle was particularly effective with Bandera sandstone. Samples saturated with potassium chlorirlr. solution and heated to 900C showed an 11-fold increa.se in perrrieahility. Samples without potasrirdrn chloritle but heated to the .same temperature. showed only a 2.7-jold incresre in permecahility. In application, it seems possible that injecting chemicalc into the formations from a wellbore followed by applying intensive borehole heating might promote reactions which would greatly improve permeability of the formalions. INTRODUCTION Great changes in the physical properties of rocks which have been heated to temperatures in the range of 600 to 800C have been reported earlier. Permeability increases of 50 per cent, and equivalent decreases in sonic velocity and breaking strength have been observed. Although there might be some suppression of certain reactions responsiblc for these changes when rock samples are heated under simulated reservoir pressure conditions. recent work has shown that these are more than offset by the increased importance of other reactions at high pressures. The reactions considered responsible for alteration of rock properties by heating include differential thermal expansion. dehydration, phase changes and dissociation of mineral constituents. Ceramists have long known that temperatures at which reactions occur can be raised or lowered by the presence of certain impurities in the sys. tcnl. Thus the possibility exists that by saturating rocks with appropriate solutions. desired reactions might be accelerated and unwanted reactions might be suppressec! when the rock is heated. Purpose of the present work was to investigate the effects of several common salts on the thermal alteration of sandstones. Types of reactions which might occur are reviewed and the findings of a number of thernlochemical alteration tests are presented. THEKMOCHEMICAL ALTERATION OF SANDSTONE MINERALS The most abundant constituent of most sandstones is quartz. Quartz can exist in at least eight different forms, but in the temperature range of immediate interest (to 900C) only two forms are of importance—alpha quartz below 573C and beta quartz above this temperature. Although the alpha-beta inversion of quartz is very important in thermal alteration of rocks. it is not particularly important here because the inversion temperature cannot be changed significantly by the presence of impurities or by the application of pressure. The transition temperature of quartz to tridynlite is 867C. but the transition is very sluggish. Tridymite is considered to be a metastable transition phase between two stable phases: quartz?cristobalite. However. the transition temperature for tridymite to cristobalite is 1,470C.4 The quartz-tridymite-cristobalite transition can be accelerated substantially by the presence of fluxing agents. Finely divided calcium, magnesium and titanium oxides accelerate the conversion while A12O may retard it. A Mixture of NaCl and CsCl reduces the temperature for cristobalite formation by as much as 420°C. Feldspars constitute the second most important mineral in sandstones. The melting points of feldspars range between 1,000 and 1,700°C depending upon the variety. No information available indicated any important role of fluxing agents in the thermal alteration of this group of minerals. Carbonate minerals are subject to dissociation at temperatures within the range of the present investigation. The dissociation of magnesite can start at a temperature of 373°C, but the reaction is sluggish and might not occur untll a temperature of 500°C or ,higher is reached. Dolomite dissociates in two stages at 500°C and 890°C, whereas calcite dissociation temperature is about 885C. Because CO2 is released in the dissociation of carbonates, ail such reactions are somewhat dependent upon CO2 partial pressure. In the absence of CO: in the surrounding atmosphere, the dissociation of calcite starts at 500°C.However. when 1 atm of CO surrounds the sample, the dissociation does not start until 900C. The other carbonates are apparently much less sensitive to a change in partial pressure of CO2. The aragonite calcite transformation can occur an!. where within the temperature range of 357 to 488°C. depending upon the presence of impurities such as barium. strontium. lead and perhaps zinc. The differential thermal analysis (DTA) curves of both magnesitc and dolomite vary with the presence of 'impuritics. The presence of iron in particular seems to affect the magnesitc DTA curve

Jan 1, 1966

By T. M. Chance

THe necessity of adopting improved methods of bituminous-coal cleaning at many collieries is recognized by all familiar with the requirements of the various bituminous markets, the approaching exhaustion of the relatively small areas of inherently high-grade coal, and the difficulties encountered in maintaining a uniform grade of shipped coal. Many coals lose much of their market value by degradation in size, and, in any event, if the cleaning .process is to contemplate wetting the coal the minimum amount of fines should be produced to prevent sludge losses and the difficulties resulting from the moisture content of the wet fines. Hence, it is desirable to bypass the finer coal dry, if this can be done without too great increase in impurities in the final product. This procedure has given excellent results at washeries at Steelton and in the Birmingham district. If the raw fines are too impure to permit admixture with the washed coal, it may be desirable to use dry methods, such as the pneumatic table, rather than to wet an excessive amount of such fine material. The bituminous-coal cleaning plant should therefore: (1) Treat the raw coal in as large lump as possible and without sizing; (2) eliminate degradation of pure coal in the washing process; (3) avoid wetting the fines, if possible; (4) produce washed coal practically free from mechanically included impurities; (5) crush the refuse and retreat, if much intergrown coal and refuse are present, rather than precrush the entire feed. Ordinary gravimetric methods of concentration, whether hydraulic or pneumatic, will not meet all of these requirements, as the large lump includes those sizes now sent to the picking tables, if it is desired to treat material of such size. I do not know of any prior commercial method, based on the falling velocity, coefficient of friction or resistance to fracture, that permits the production of clean coal varying in size from, say, 10-in. lump to 1/16-in. mesh. The effect on the specific gravity of any given coal as a result of variations in ash and pyritic sulfur content is well known; in fact, it has been made use of in commercially ascertaining ash content by deter-

Jan 1, 1924

By F. J. Tuck

The Hayden mill of the Ray Mines Division, Kennecott Copper Corporation, is now equipped with two 9 by 12-ft. rod mills having a daily capacity of 6000 tons of coarse-crushing plant product from the mine. These two mills crush a ¾-in. product to approximately 19 per cent on 14 mesh, with only one pass through the mills. Each rod mill has taken the place of four sets of 42-in. Garfield rolls with their attendant screens, and is making a product for the fine-grinding department comparable to that formerly made by rolls in closed circuit with screens. The rod mills are lined with wave-type liners of white iron, varying in thickness from 2 to 3 in. The shell and end liners last approximately 600 to 700 days. Manganese-steel lifter bars, 3? in. thick, are used, spaced about 11 in. apart, and they give a life of 350 to 450 days. Fig. 1 shows the general design and thickness of the wave-type liners and lifter bars; 1½-in. liner bolts are used to fasten the lifter bars to the shell. The shell liners are held in place by the tapered lifter bars. A ¾-in. wood backing is used between the shell and the liners. The rod-mill scoop has removable manganese-steel lips, which last 250 to 300 days. The scoop proper has shown some wear in spots, and these spots have been protected by rubber bolted over them. Water and milk of lime are added to the elevator feeding the mill, but not enough water to cause a pounding of the rods against the shell. Roughly, the water added amounts to 25 to 33 per cent of the ore. Additional water is added to the mill discharge to facilitate distribution to the classifier bowls in the fine-grinding department. Rods are charged to the mill once every four days, the mill being down about 20 min. for this purpose. Other delays are negligible, and usually are due to a loose liner bolt or possibly power trouble. However, these occasions are extremely rare. In charging the mill, a crane is used

Jan 1, 1939