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By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE large difference in the X-ray scattering factors for molybdenum and manganese makes the o- phase in the Mn-Mo system an interesting one to study with respect to ordering of the atoms. Such a study has been carried out using data obtained from a powder sample, and the resulting evidence for ordering in this compound is presented here. It is not possible, of course, to obtain all the details of structure for a u phase from powder data only. Most difficult of all would be the determination of precise atomic parameters. There is reason to believe, however, that the atomic parameters do not vary greatly in the different s'S and that the precise values obtained from one s structure would then allow decisions as to the ordering of atoms to be made when there is a large difference in scattering factors. In particular, the powder intensities for Mn-Mo s are for the most part in good agreement with those observed for Co-Cr, for which single crystal studies have been made by the authors.' There are a few marked discrepancies in the intensity comparison of the two s's, and these cannot be removed by adjustment of the parameters. They are interpreted as resulting from a more pronounced effect of ordering of the atoms. Accordingly, the parameters of Co-Cr s' have been used for the calculations of the Mn-Mo intensities. For Co-Cr, the space group is D4h14-P4/mnm with atoms in the following positions: 1—2 in (b); 11—4 in (f), with x=0.1031; 111—8 in (i), with x= 0.3713 and y=0.0370; IV—8 in (i), with x=0.5662 and y=0.2396; and V—8 in (j), with x=0.3160Y and y — -0.250. The unit cell is tetragonal, with an==9.10A and cn=4.74A for the Mn-Mo u phase studied here.

Jan 1, 1955

By M. A. Torcaso, P. Raimondi

To study mass transport in systems simulating oil recovery processes, different porous media were saturated with a mobile (carrier phase) and a stationary phase. Slugs of carrier phase containing a small amount of solute were displaced with pure carrier phase. By analogy to the chromato-graphic processes, the velocity of the solute can be predicted from a knowledge of the partition coefficient and the saturation provided that equilibrium between the two phases exists. Equilibrium was found to exist for different porous media, solutes and rates. The conditions were varied over the range normally encountered in the laboratory and in the field. The longitudinal dispersion of a solute undergoing interphase mass transfer was also investigated. INTRODUCTION The production of hydrocarbons by gas cycling, enriched gas drive and C02 or alcohol displacement involves, among other factors, relative motion between two phases and compounds, hereafter called solute, which are soluble in both phases. The solute is carried forward by the faster flowing phase at a lower velocity than the average velocity of that phase. Retardation of the solute is caused by chromatographic absorption and desorption in the slower flowing phase and by the degree of departure from equilibrium. At equilibrium the concentration of solute in the two phases can be related by the equation* CSw = K Cso ,............(1) where C, and C are the concentration of solute in the aqueous and oleic phases respectively and K is the equilibrium ratio, or partition coefficient. Displacement theories must contain an explicit assumption with regard to equilibrium, i.e., whether the compositions can be related by Eq. 1. The existance of equilibrium depends, in general, on the relative velocity between the phases. Unfortunately, other factors such as gravity segregation and viscous fingering, also depend on velocity. For this reason, whenever effects of rate on displacement were observed,2-4 it was practically impossible to discern what caused them — lack of equilibrium or the factors mentioned above. Equilibrium between phases has been the subject of extensive studies in fields such as extraction or chroma to graphy. It has received only small attention in flow through the type of porous media encountered in oil production.5 For this reason a method was developed which makes it possible to study the movement of a solute as it is affected by rate, type of porous media, partition coefficient and carrier phase, but in the absence of segregation or fingering. The information obtained enables one to determine when the assumption of equilibrium can be made. Briefly, the method consists of (1) saturating the core with a mobile and an immobile phase, (2) injecting a slug made up of the same fluid as the mobile phase and a small concentration of mutually soluble solute, (3) measuring the lag and the peak height of the slug at arrival and (4) correlating these variables with fluid properties such as partition coefficient and mixing constants of the medium. PROPOSED MECHANISM The principles of chromatography are combined with the equation of longitudinal mixing to predict the velocity of a solute slug compared to the bulk velocity and the peak height of a slug.6-9 The equation so obtained is valid under equilibrium conditions only. Therefore, a comparison between experimental and predicted results will give a measure of departure from equilibrium. This work was done with either the oleic or the aqueous phase being immobile. For simplicity, the following development is based on the case where the oleic phase is immobile. However, the treatment is the same in either case.

Jan 1, 1966

By M. J. Marcinkowski, D. B. Crittenden, A. S. Sastri

A study co.mbining stress-strain .measurements in conjunction with transmission electron microscoPy has been made with near equiatomic Fe-Cr alloys which were aged for various times at 500°C. Associated with this aging is a marked increase in deformation twinning. The outstanding feature of these twins is that they generate stress fields sufficiently great so as to give rise to spontaneous dislocation loop nucleation nearly normal to the propagating twin. This observation is in agreement with the theoretically predicted elongation of the stress field of a dislocation Perpendicular to its direction of motion as it moves near the speed of sound. Dislocation loop nucleation is more difficult in the longer aged alloys so that this energy absorption mechanism is not effective in hindering twin propagation. Since crack nucleation can readily occur near the tip of a twin, the aged alloys become extremely brittle when deformed in tension. Iron-chromium alloys in the vicinity of the equiatomic compositions become severely embrittled when aged at about 500°C. Fisher et 01.' have shown that this embrittlement is related to the decomposition of the original random Fe-Cr solid solution into a chromium-rich and an iron-rich phase. In addition, Mar-cinkowski et a1.' have shown that twinning becomes an increasingly more important mode of deformation as the aging time is increased. These results have been recently corroborated by the transmission electron microscopy study of Mima and amauchi . The Fe-Cr alloy thus seems ideal for verifying the predictions made in Parts I4 and 115 of this investigation where the behavior of large static or blocked twins and those of large dynamic or propagating twins, respectively, were investigated numerically. It was thus decided to measure the stress-strain curves generated by embrittled alloys that were aged for various times and to examine sections by transmission electron microscopy. EXPERIMENTAL PROCEDURE Electrolytic iron and electrolytic chromium were vacuum-melted and poured into ingot form. The composition of the resulting alloy was found to contain 46.0 wt pct Cr (47.8 at. pct), the remainder being iron. The resulting ingot was swaged above 850°C into 0.250-and 0.400-in.-diam rounds. Compression samples of 0.250 in. diam and 0.400 in. long were cut from the smaller-diameter rounds. These samples were then sealed in evacuated quartz tubes and annealed for 30 min at 1150°C to produce a uniform and equiaxed grain size of mean diameter equal to 1.73 mm. They in turn were rapidly quenched from 850°C so as to preserve the condition of random solid-solution characteristic of the elevated temperature. The samples were then aged for various times up to 300 hr at 500°C in a massive Pb-Bi alloy bath. The samples were next polished and tested in compression at room temperature as described in Ref. 6 using an Instron tensile testing machine. The strain rate used was 0.05 in. per in. per min. The remaining larger round was converted into compression specimens of 0.325 in. diam and 0.500 in. long. This larger diameter enabled wafers of sufficient size to be prepared for examination by trans-mission electron microscopy techniques after subjecting them to a suitable strain. Foil preparation is described in some detail in Ref. 6. All foils were examined in a type HU-11A Hitachi electron microscope operating at 100 kv. RESULTS AND DISCUSSION Fig. 1 shows the effect of aging at 500°C on the room-temperature stress-strain curves of the FeCr alloys. For greater clarity the origin of each curve has been displaced upward. The same origin has been used for both the 0 and the 0.1 curves. It is apparent that with increased aging times a sharp drop in load is observed at the yield stress which becomes more pronounced as aging proceeds. A loud sonic burst accompanies this drop and subsequent metallographic examination shows the sample to contain numerous twins. For intermediate aging times, a number of smaller twin bursts follow the initial large one. The total plastic strain associated with the twinning mode of deformation can be obtained by adding up the contributions AE~ from all i twin bursts, i.e., £,¦££,-, in the manner illustrated schematically in Fig. 2. The contraction of the specimen, as measured from the strip chart of the Instron, after suitably correcting for the elasticity of the machine, was converted into true strain using the assumption that there was no volume change and that the sample remained cylindrical. The dashed lines are all drawn parallel to the

Jan 1, 1970

By AIME

ENGINEERS have long pondered the answer to the question of "How am I doing?" and in large measure the answer from the economics angle is provided by the 1946 survey of the engineering profession now being published by the Engineers Joint Council as an eighty-page bulletin entitled "The Engineering Profession in Transition." The survey, based upon a completely precoded mail questionnaire, aimed at three major objectives: (1) to determine the general impact of World War II upon the profession in the period 1939 through 1946; (2) to obtain re- R liable data from which valid findings could be derived to predict how active the profession would be after 1946; and (3) to determine if the war's upheaval had changed materially the pattern of professional activities, education, background, and earnings from those which existed prior to 1939. Abundant data on the economic status of the engineer based upon years of experience in his particular field, the specific branch of the industry in which he served, and his educational background are presented. Relationships between years of experience

Jan 1, 1947

By E. A. Nesbitt

A new permanent-magnet material has been developed with unusual mechanical as well as magnetic properties. Specimens that have been cast or subjected to a small amount of hot reduction by rolling or swaging may be machined, punched, tapped or drilled. The composition range of the alloys is 30 to 52 per cent iron, 36 to 62 per cent cobalt and 4 to 16 per cent vanadium. After being either quenched, annealed or given the usual cold finishing passes and then heated for 2 hr. at 600°C., such materials have a magnetic energy product of 1.0 X 106 gauss-oersteds. This product is equivalent to that of the well-known Honda steel (36 per cent Co, 4W, 2 Cr, 0.8 C. 0.3 Mn, balance Fe). Material handled in the manner just described does not depend on cold-working for its magnetic properties, and is known as Vicalloy I. The preferred composition for Vicalloy I is 38.5 per cent iron, 52 per cent cobalt and 9.5 per cent vanadium. When the alloys are first hot-worked, then considerably reduced in area by cold-swaging, drawing or groove rolling and then heat-treated, the magnetic energy product measured in the direction of previous extension is increased to 2.0 to 3.5 X 106 gauss-oersteds. These higher values have been obtained only after cold reductions in area of 75 to 95 per cent. Material handled in this manner is known as Vicalloy II and the preferred composi-

Jan 1, 1947

By E. A. Nesbitt

A new permanent-magnet material has been developed with unusual mechanical as well as magnetic properties. Specimens that have been cast or subjected to a small amount of hot reduction by rolling or swaging may be machined, punched, tapped or drilled. The composition range of the alloys is 30 to 52 per cent iron, 36 to 62 per cent cobalt and 4 to 16 per cent vanadium. After being either quenched, annealed or given the usual cold finishing passes and then heated for 2 hr. at 600°C., such materials have a magnetic energy product of 1.0 X 106 gauss-oersteds. This product is equivalent to that of the well-known Honda steel (36 per cent Co, 4W, 2 Cr, 0.8 C. 0.3 Mn, balance Fe). Material handled in the manner just described does not depend on cold-working for its magnetic properties, and is known as Vicalloy I. The preferred composition for Vicalloy I is 38.5 per cent iron, 52 per cent cobalt and 9.5 per cent vanadium. When the alloys are first hot-worked, then considerably reduced in area by cold-swaging, drawing or groove rolling and then heat-treated, the magnetic energy product measured in the direction of previous extension is increased to 2.0 to 3.5 X 106 gauss-oersteds. These higher values have been obtained only after cold reductions in area of 75 to 95 per cent. Material handled in this manner is known as Vicalloy II and the preferred composi-

Jan 1, 1947

By David W. Brunton

(San Francisco Meeting, October, 1911.) MINE-DRAINAGE and the ever-increasing demand for water on the plains have within the past few years necessitated the driving of a great number of adits and tunnels, including many of considerable size and great length. In most instances, ex isting conditions have called for extreme rapidity of execution; and this necessity, coupled with the high altitudes at which most of the work has been carried on, excessive freight-rates, and difficulty -of access, has involved many complex and interesting problems. One of the most rapidly executed undertakings of this class is the Laramie tunnel, recently completed for the Laramie-Poudre Reservoirs & Irrigation Co. This tunnel is driven through Green ridge, a spur of the Continental Divide, which separates the Laramie river from the Cache-la-Poudre in Laramie county, Colo. Green ridge is extremely persistent, and further northward in Wyoming is known as Sherman hill, the highest point on the Union Pacific railway. At the point where the tunnel is driven, two opposing bends bring these streams within 2.5 miles of each other, with a difference in elevation of 500 ft. The rock exposed on the banks of the two rivers does not differ materially in hardness; and, without a geological study of the conditions involved, it would appear that the difference in the depth of erosion of the two streams is due principally to the greater volume of water at this point in the Cache-la-Poudre, which has a drainage-area above the tunnel-portal of 110 sq. miles, as against 30 sq. miles of natural drainage for the Laramie. To increase the water-supply at the tunnel, however, this latter amount has been augmented by two side collection-canals, which bring the available drainage-area up to 84 square miles. The nearest railroad shipping-point to the eastern portal is

Apr 1, 1912

By A. Berghezan, E. Bull Simonsen

A simple and general method is described for melting and zone refining refractory metals by induction heating on a specially shaped water-cooled copper crucible. The crucible is the essential part of the apparatus and is placed horizontally. It consists of either a copper plate, or a flattened tube, or of several parallel small diameter tubes all water cooled. The charge lies on the crucible, or whenever possible, is suspended above it. This assembly goes into a transparent quartz tube and the whole is passed through the coil of a radio frequency generator. Vaarious atmospheres can be used. No contamination is detected from the copper crucible. purification is obtained both by selective evaporation of impurities and by zone refining. METHODS of melting and refining relatively large ingots of all reactive and refractory metals as well as some semiconductor materials have been developed in this laboratory during the past several years using induction heating and cold crucibles. These methods are simple and permit the use of a variety of starting materials in preparing ingots of suitable shapes. Among these methods, two are of particular interest. One deals only with the problem of melting without contamination. In this method the induction coil has a specially designed shape and acts simultaneously as heating element and crucible. The second goes one step further, being designed for both melting and further purification of the refractory metals. The aim of this paper is to describe the second method which is of more general interest and of greater applicability to metallurgical problems. A) THE PRINCIPLE OF THE MELTING AND PURIFICATION METHOD As originally proposed by one of us1 the method consists of heating a charge of any refractory metal or semiconductor material to the melting point on a water-cooled copper crucible by passing both the charge and the crucible through the induction coil of a radiofrequency generator. Although both are subjected to the same induction field, one achieves the melting of a refractory metal on a copper crucible even when the refractory metal has a melting point of more than 2000°C above that of the crucible. This seemingly "odd" method works effectively for the following reasons. Because of its high electrical and thermal conductivity as compared with the material being melted, copper can be used as the crucible and kept at a low temperature while the material is heated by induction to its melting point. With water Silver and other highly conducting materials can also be used. If a nonconducting material is contemplated, e.g. SiO or a high polymer, a very thin wall should provide efficient cooling. cooling through ducts in the crucible its temperature can be kept between 40" to 70°C; thus its electrical resistivity is kept low, while the resistivity of the charge increases rapidly as its temperature is increased. B) APPARATUS The crucible is the essential part of the apparatus. It has been designed in various shapes depending on the atmosphere used, whether vacuum or an inert gas or hydrogen. In all crucible designs an effort was made to reduce its volume to "nothing but the cooling water" in order to avoid shielding the ingot from the induction field. In practice it is either a

Jan 1, 1962

By N. W. Johnson

Mount Isa Mines Limited (Isamine) has process control computers in the major surface plants -- lead smelter, copper smelter, lead/zinc concentrator, and copper concentrator. HP computers are used to implement the more complex stabilizing control loops and control schemes aimed at optimizing plant performance. The choice of control strategies is discussed with particular reference to long-term performance in metallurgical plants. These control schemes must be understood by the process metallurgists who are responsible for the performance and initial fault finding. Major emphasis has been placed on the ability of the control systems to handle most of the common plant upset conditions as well as providing improved performance under normal operating conditions. To illustrate the approaches adopted, the lead/zinc concentrator crushing system and the process bag- house control system for lead smelter off-gas handling are reviewed in detail. The improvements in both of these areas resulting from control systems implementation are discussed.

Jan 1, 1984

By Robert Anderson

ROUGHLY, a crack in a casting may be considered, for the moment, to be due to fracture of the alloy resulting from the stress set up by the contraction in volume on passing from the liquid to the solid state. Cracks may be external or surface, internal or deep-seated, or incipient or so-called strain cracks. Draws may appear as depressions, unevenness, and "pinching in" of the surface of a casting. Roughly, draws are due to contraction in volume and are governed largely by the same factors as cracks. A casting may be cracked, however, without being drawn. Shrinkage is a foundry term; it connotes the contraction in volume of a metal or alloy on passing from the liquid to the solid state. Pattern-makers' shrinkage is the total contraction in volume (including liquid, solidification, and solid shrinkage) that occurs when an alloy is poured into a mold. The contraction in volume of aluminum is one of the principal factors affecting the occurrence of cracks, as will be shown later, and the question of shrinkage and its control requires careful study in any treatment of cracking in castings. In the case of, sand and die castings, cracks have been attributed to a number of causes, but in the case of most light aluminum alloys, they are due to the large contraction in volume on freezing and the lack of its regulation or control. The most important factors are: (1) Contraction in volume; (2) composition of alloy; (3) quality of melting charge; (4) design of casting; (5) method of molding; (6) hardness of ramming; (7) method of gating; (8) hardness and characteristics of cores; (9) chills; (10) risers; (11) melting temperatures; (12) furnace used for melting; (13) pouring tempera-tures; (14) inclusions in alloys; (15) hot shortness of alloys; and (16) physical properties of alloys at high temperatures. Of these, the first, second, third, and eleventh to sixteenth involve ascertainable metallurgical facts; the remainder are largely matters of opinion, judgment and technical knowledge of men experienced in the production of castings.

Jan 10, 1921

By Paul R. Smith

Preparation for flotation begins with dragline mining, pumping, washing, screening, and desliming. Slimes, nominally -150 mesh material, constitute large quantities of phosphate and water which are a disposal problem. Older techniques involve sizing at about 35 mesh for separate coarse and fine treatment. The plus 14 mesh fraction does not require concentration. Coarse treatment includes agglomerate spiralling, belt flotation, thickening, scrubbing with sulfuric acid, de-oiling for reagent removal, and cationic flotation of fine quartz. A recent trend is to screen at coarser than 35 mesh size and eliminate coarse particle treatment, sacrificing some grade of this product. Techniques for flotation concentration of the fine size fraction are discussed.

Jan 1, 1976

By L. L. Handy

The most common method of identifying hydrocarbon-bearing strata in a well that penetrates many different formations involves measurement and interpretation of the electrical properties of the formations as determined by electrical logs. Even though this method is used extensively, and even though in a great many instances it is capable of indicating presence of oil or gas, situations arise for which it is extremely difficult, if not impossible, to deduce the presence of hydrocarbons. These situations may involve the following. 1. A thin formation, bounded by highly resistive formations, in which it is impossible to obtain the actual resistivity of the uninvaded zone with existing logging devices. 2. A formation in which invasion has been so extensive that a value for the uninvaded zone resistivity cannot be obtained. 3. A very shaly formation in which the resistivity index, I, is lower than that usually associated with productive formations. 4. Laminated formations comprised of thin productive sands separated by thin shale streaks in which the individual sand and shale streaks are too thin to permit measurement of uninvaded-zone resistivity with existing logging devices. 5. Productive formations in which the water saturation is high. To extend the utility of electric log interpretation to identification of hydrocarbons in all types of formations, there is strong incentive to find a method not subject to these limitations. Some time ago, in connection with research on the wettability of reservoir rock, an investigation was conducted in which the resistivities of cores were measured shortly after they were removed from a core barrel, and again after they had been extracted and restored to their original oil and brine saturation.' The resistivities after extraction were generally lower. Other tests made on the cores indicated that they were more nearly water wet after they were extracted; thus, it was assumed that the observed changes in resistivities were due to a change in wettability of the cores. Other experiments'," have shown that resistivities of rock samples are sharply dependent on wettability. These experiments have shown that oil-wet samples are more resistive than water-wet samples. To obtain an understanding of how the wetting properties of the surfaces of core material affect electrical resistivity, a series of experiments was conducted. Two groups of core samples were prepared for testing. One group contained brine, but no residual oil. The other group was saturated with brine, flooded with oil to a low water saturation, then flooded with brine to a final residual oil saturation. Resistivity measurements were made on each group. Both groups were then flooded with the original brine to which a chemical had been added that renders sand and clay surfaces preferentially oil wet, a so-called reverse-wetting agent. very little change in resistivity was observed in cores containing only water. The group containing residual oil, however, showed resistivity increases of 100 to 200 per cent. These experiments showed that the resistivity of a core containing oil could be altered by changing wet-tability of the core. Moreover, the possibility was introduced that reverse-wetting agents might be employed as the basis for a logging method for identification of oil-bearing strata. Since behavior of a porous rock containing gas and water might be expected to be similar to that of a rock containing oil and water, such a method should also be applicable to identification of gas-bearing zones. In principle the wettability of the invaded zone could be reversed without altering conductivity of the interstitial water or the hydrocarbon saturation therein. Those strata showing significantly increased invaded-zone resistivities would, therefore, contain hydrocarbons; those with no significant change would be filled only with water. Addition of a reverse-wetting agent to a hydro carbon -bearing zone which is, by nature, already preferentially oil wet would not result in an enhancement of its resistivity. It is generally believed, however, that most hydrocarbon-bearing strata are preferentially water wet.

By K. D. Sheffler, R. W. Hertzberg, R. W. Kraft

The Ni-Ni,Ti lamellar eutectic alloy responds to unidirectional solidification by alig-nment of the platelets of the two phases roilghly perpendicular to the moving solid-liquid interface. X-ray diffraction and zetallographic experimenls show that the following cryslallographic relationships exist in the directionally solidified ingots: lamellar interface w [0001] Ni3Ti 11 (111 }Ni local growth direction (1120) Ni3Ti n (110) Ni These relationships are rationalized on the basis of the crystallography of the constituent phases. In recent years researchers in several laboratories have shown that an aligned or "controlled" micro-structure can be produced in many binary eutectic alloys by forcing the alloy to solidify unidirectionally in an elongated crucible.'-3 It also has been found that a unique crystallographic relationship often develops between the two phases in such a structure.4, 5 Since a parallel arrangement of phase particles in an alloy should, and, in many cases, does, produce unique and highly anisotropic properties, the alloys so produced are of potential interest in a variety of applications. Studies of these alloys are also of interest at the academic level because they help to improve our basic understanding of the way in which metals solidify. This paper reports the metallographic and crystallographic structure of another of these alloys—that between nickel and Ni3Ti. In a separate paper, hot tensile and stress rupture properties as well as deformation and fracture behavior of the same alloy are discussed.19 EXPERIMENTAL DETAILS AND RESULTS General Characteristics of the Eutectic Reaction. Several small exploratory Ni-Ti melts were made to resolve a conflict in Hansen6 over the eutectic composition. The alloy containing 16.4 at. pct Ti, Fig. 1, appeared metallographically to be closest to the eutectic composition, although small dendritic patches of proeutectic nickel are present. The eutectic morphology is lamellar and appears quite sharp and angular, indicating a strong influence of crystallographic factors upon the microstructure. Some of the eutectic nickel platelets are continuous with the primary phase, whereas in hyper eutectic melts a "halo" of nickel generally surrounded the proeutectic inter-metallic platelets, indicating that nickel is the nucleating phase in this eutectic reaction. Extensive precipitation of Ni3Ti has occurred in the primary nickel phase in a Widmanstatten pattern which makes the dendrites difficult to differentiate from the eutectic mixture. This phenomenon may account for discrepancies among the eutectic compositions reported in the literature. The sloping solvus line bounding the nickel primary solid solution explains the presence of the intermetallic precipitate. Poole and Hume-Rothery7 report that the solubility of titanium in nickel drops from 13.8 at. pct at the eutectic temperature (1304°C) to approximately 9 at. pct at 700°C (Ni3Ti, on the other hand, melts con-gruently and exhibits essentially no solubility for nickel or titanium). Lever rule calculations based upon Poole and Hume-Rothery's phase diagram indicate an increase from 21 vol pct Ni3Ti in the eutectic mixture at the eutectic temperature to 61 pct at room temperature. Selective point count measurements of the volume fraction of eutectic Ni3Ti platelets in the eutectic microstructure yielded a value of 46 i 2 vol pct, which required extensive precipitation of Ni3Ti from the nickel solid solution onto the eutectic intermetallic platelets during cooling from the solidification temperature. Influence of Directional Solidification. Nickel bar and titanium sponge of 99.9 pct purity were induction-melted in zirconia crucibles under argon in the proportion of 13.8 wt pct (16.4 at. pct) Ti to produce 14-lb master heats which were cast into investment molds yielding 5/8-in.-diam pins approximately 10 in. long. These pins were remelted under argon in horizontal zirconia boats and unidirectionally solidified to produce 1/2-in.-sq ingots approximately 44 in. long. Details of the experimental techniques and apparatus are described elsewhere.'

Jan 1, 1970

By H. A. Wahl, J. M. Campbell

This study extends our information on solid-liquid slurries to the flow of sand in horizontal fractures. Inasmuch as this is basically an unsteady-state process, a comprehensive photographic study was undertaken in a 10-ft windowed cell to determine if the basic flow regimes described for steady-state flow in pipes applied to the subject process. Since the number of potential variables far exceeds the capacity of a single study, emphasis has been placed on the effects of sand concentration, oil viscosity and oil flow rate. The extensive photographic evidence obtained has proven very valuable in gaining an insight into the basic flow mechanisms. Being able to follow visually the flow characteristics that accompany the quantitative data is valuable in the application of the results. Although the use of dimensionless parameters was carefully investigated. it was found that the data obtained could be more easily, and as accurately, correlated by judicious use of the dimensional variables investigated. However, a study into the feasibility of scaling slurry flow was made in the event this technique is justified in future investigations. The data presented show that the pressure behavior observed in solids transport in pipes basically applies to slurry flow in horizontal fractures. The roles of the parameters are altered but a basic equivalence exists. The most significant correlating parameter was the oil viscosity (µo) and the bulk velocity of the slurry (vn), expressed as ''µv" product. The most significant correlation expresses the rate of advance of the sand as a function of the variables investigated. There are many practical ramifications of this phase of the investigation that should aid in better treatment design. Evaluation of sand advance rates provides a means of estimating sand placement efficiencies during a treatment and the resulting sand distribution in the fracture. The results show that sand placement efficiencies are low under typical treatment conditions. A brief description of the effects of overflushing is also included. INTRODUCTION The flow of sand-oil slurries in fractures is an area in which little basic knowledge is available. This stems to some degree from the fact that it is impossible to duplicate fractures at the surface. They occur in various shapes and sizes with an infinite combination of irregularities. Unfortunately, we can never "see" these fractures except in cores and by indirect means of measurement. In spite of this inherent difficulty, it is desirable to develop some basic concepts that will provide a better understanding of the sand transport mechanism. An insight into the problem is provided by investigations of fluid flow in rectangular conduits. Several studies on the flow of liquids in non-circular conduits1,13 show that a Reynolds number-Fanning friction factor relationship can be written if the hydraulic diameter is substituted for the regular diameter in a circular pipe. This hydraulic, or equivalent, diameter is taken as four times the cross-sectional area occupied by the flowing fluid divided by the wetted perimeter. Eq. 1 expresses an extension of this same work when applied to infinite parallel planes b distance apart.' Eq. 1 is a theoretical equation expressing the friction factor as a function of the Reynolds number for laminar single-phase fluid flow. This expression has been verified experimentally. The equivalent expression for a smooth circular conduit differs only in that the value of the constant is 16 instead of 24. Numerous studies have related friction losses to Reynolds number in both circular and non-circular conduits. These results are widely used and are not reviewed here. Huitt' investigated the effect of surface roughness on fluid flow in simulated fractures. He concluded that fluid flow in fractures may be treated similarly to fluid flow in circular conduits. This work, together with that of Nikuradse,' shows that surface roughness has no appreciative effect upon the resistance to flow in the viscous flow region. In the region of turbulent flow, surface roughness is a prominent factor. Hydraulic conveyance literature is another important source of information. Durand3 has attempted to organize systematically the variables involved in hydraulic-solid transport in pipes. He has classified the modes of flow into three types according to the size of the particles in the mixture— homogeneous mixtures, intermediary mixtures and heterogeneous mixtures. With the usual concentrations and flow rates used in hydraulic transportation, particles with diameters of less than 20 or 30 microns form eszentially homogeneous mixtures with water. The data show, however, that even small materials will tend to settle out under laminar flow conditions. Mixtures containing solids over 50 microns in diameter do not achieve total homogeneity even under turbulent flow conditions. Particles from 50 microns to 0.2 mm in diameter may be transported in fully suspended flow at normal transport velocities although the concentration in the vertical plane is not uniform. Above 2 mm in diameter solid materials are transported along the bottom of the conduit at a velocity substantially less than that of the liquid itself. Between 0.2 and 2 mm in diameter, the particles tend to be in a transition zone between heterogeneous suspended flow and deposit flow at normal hydraulic transport velocities. The sand sizes used in fracturing usually fall in this size range. It is interesting to note that the grain size range designated by Durand for this transition zone corresponds closely to the transition zone between

By W. J. Nelson, R. B. Nance

Detailed underground geologic mapping at a scale of 1:1200 has been carried out at the Crown II Mine of Freeman United Coal Mining Co., which operates in the Herrin (No. 6) Coal Member. The roof sequence, upward from the coal, includes (1) soft, medium -to dark-gray shale; (2) hard, black, fissile shale; (3) argillaceous nodular- bedded limestone, and (4) fine-pined, shaly, water-bearing sandstone. The first unit is highly lenticular, and any or all may be missing at a given locality. The sandstone has a sheet facies and a channel facies. The Herrin Coal is eroded in channels near the Crown II Mine. Structural features mapped at Crown II include normal and strike-slip faults and limestone "bosses." Less stable roof and wet conditions are encountered where the limestone is thin or missing or where it is broken by natural fractures or by artificial openings that intersect the water-bearing strata above the limestone. Geologic mapping of the underground workings has allowed us to predict faults, fracture zones, and channels ahead of the face for this mine. Some lithologic and structural pattern apparently are random and cannot now be projected. Conventional exploratory drilling is entirely inadequate to map faults or lithology of the roof, but it does indicate the range of lithologic variability, which can be used to project needs for roof supports. Drilling also is useful in locating channels and in mapping regional variation in thickness and facies of the sandstone.

Jan 1, 1983

By J. W. Eckerd, P. S. Lewis, N. H. Coates

USBM designed, constructed, and operated an 18-in.-diam fluidized-bed combustor for highly caking coals to evaluate the method for possible application to power generation. In initial tests, combustion was carried on successfully, with carbon losses as low as 0.8%+ Coal ash was not satisfactory as a bed material, but mullite proved to be acceptable. Overall heat-transfer coeffients from the bed (-20 t 50 mesh mullite) to a water-cooled tube were about 75 Btuper hr-sq ft. Fluidized-bed combustion is being investigated by the U. S. Bureau of Mines (USBM) as a potentially cheaper method of firing power plant boilers. Lower combustion temperatures in fluidized beds—only 1400" to 1800°F-—should reduce fireside deposition and corrosion and nitrogen oxides production. Fluidized-bed combustion also offers possible advantages in the use of additives to control SO, emissions and amenability to processing of high-ash, high-moisture coals without special preparation. This paper describes development of a fluidized-bed combustor and the results of preliminary tests. Equipment and Procedure Fig. 1 shows the 8-ft-high combustor. A cone-shaped plate perforated by I/8-in.-diam holes supports the fuel bed and admits the fluidizing air; water passing through the 3/4-in. pipe extracts heat from the combustion bed. Fig. 2 is a flow diagram of the system. Coal is fed pneumatically to the base of the fuel bed. Combustion products are passed through two centrifugal separators to remove most of the entrained solids, then to a water

Jan 1, 1971

By Clarence G. Merritt

Stainless iron, as mild stainless steel is usually called, an alloy ranging from 11.50 to 15.00 per cent chromium with carbon under 0.12 per cent, has been considered to be not appreciably affected in respect to corrosion resistance by heat treatment. This metal, while one of the most widely used of the "straight" chromium stainless alloys, has failed in many applications because of insufficient information regarding heat treatment. These failures have been attributed to many possible causes from an inherent lack of resistance to corrosion and misapplication to mlysterious electrolytic effects or comparatively minute non metallic inclusions. Many uses for a steel with such excellent physical properties as are latent in this alloy have been lost on account of corrosion failures which could have been avoided by applying proper heat treatment. The alloy has not received the recognition or attention it should because of the fact that the details of its metallurgical behavior were not thoroughly understood. Response to heat treatment of the steel is well known as regards tensile properties,1-2 but its application has been for improvement in tensile characteristics or on account of machining considerations rather than for corrosion prevention. The potential user of this steel has not been clearly advised in papers, either technical or commercial, that have been written about it in the last 10 years or more, of particular features that are of prime importance in developing the excellent properties of this metal. The data to be presented in this paper are concerned mainly with the effect of heat treatment on the corrosion resistance, but a study has also been made of the concurrent microstructural changes and an explanation developed for the phenomena revealed, as well as a correlation to the other physical properties—hardness, tensile characteristics and impact strength. Stainless steel, largely used for cutlery purposes, an alloy of approximately 13.00 per cent Cr with 0.30 per cent C;, must be hardened and the surface prepared by polishing or pickling for best resistance to staining and corrosion. Monypenny reports that a loss of hardness is

Jan 1, 1932

By D. A. Elgillani, M. C. Fuerstenau

In this paper, oxidation potentials measured in the presence of various concentrations of cyanide, ferro-cyanide, and ferricyanide and ethyl xanthate at various values of pH are related to flotation response. Eh-pH diagrams are presented to show that the formation of surface ferric ferrocyanide is probably responsible for depression when cyanide is added. The influence of cyanide on the depression of pyrite with xanthates as collector has been the subject of a number of investigations,'-6 and several theories on the mechanism of depression have evolved from these studies. Wark and Cox7 and Gaudin8 have suggested that the depressing effect is due to a competition of cyanide ion with xanthate ion for the surface. Cook and his colleagues9-11 have explained this phenomenon in terms of competition between hydrocyanic acid and xanthic acid. Sutherland 12 has shown that although both of these theories accurately describe the relation between pH value and cyanide addition at constant collector addition, they fail to describe the relation between pH value and the amount of collector required to cause flotation. Taggart 13 suggested that depression in these systems is due to the formation of a reaction product between ferric ion at the pyrite surface and ferrocyanide ion derived from solution. Majumdar4,6 has attempted to prove this hypothesis by measuring the contact angles of pyrite in the presence of 25 mg per liter ethyl xanthate and different concentrations of potassium ferrocyanide and ferricyanide. In all cases the contact angles were quite high up to pH 10. These results indicate that pyrite should not be depressed by either potassium ferrocyanide or ferricyanide. In view of these facts, Majumdar has assumed that the compound Fe(CN)2 forms at the surface. Gründer and Bornl4 have stated that depression may be due to the formation of the compound K2Fe(II)Fe(CN)6 at the pyrite-solution interface. This compound is thought to be an interaction product between the K2Fe(CN)6-2 ion from solution and the Fe++ ion at the pyrite surface and, accordingly, K4Fe(CN)6 should depress pyrite at least as effectively as KCN. This was proven experimentally, but there was no simple relation between the depression of pyrite and the concentration of either KCN or K4Fe(CN)6 in solution. In view of the many mechanisms that have been proposed for pyrite depression by cyanide, it is apparent that a clear understanding of the phenomena occurring in these systems is lacking. One reason for this may be the fact that the species responsible for pyrite flotation in the presence of xanthate is not the xan-thate ion but rather dixanthogen.15 Since the oxidation of xanthate to dixanthogen is dependent on the oxidation potential of the solution, it would seem that knowledge of these potentials would be a requisite to understanding the pyrite-xanthate-cyanide system. It is the object of this paper to measure both the oxidation potential and pH of the pyrite systems in the presence of various concentrations of cyanide, ferrocyanide, and ferricyanide and xanthate and to relate these values to flotation response. EXPERIMENTAL MATERIALS AND 'TECHNIQUES In the experiments discussed here, pure potassium ethyl xanthate was used as collector, and reagent grade potassium cyanide, potassium ferrocyanide, and potassium ferricyanide were used as depressants. Reagent grade HC1 and KOH were added for pH adjustment. Conductivity water, made by passing distilled water through an ion exchange column, was used in all experimental work. Two natural samples of pyrite were used in the investigation. Sample preparation for flotation included dry grinding with a mortar and pestle and sizing the product to 100 x 200 mesh. Prior to flotation, a 0.75-gm sample of pyrite was added to a solution containing a known amount of depressant at the desired pH value, and the system was conditioned for 4 min. Following this, a known amount of collector was added and the system was conditioned for another 4 min. The pH — termed flotation pH - was measured; the pulp was transferred to a Hallimond cell, and flo-

Jan 1, 1969

By M. J. Pool

The partial molar heats of solution in liquid tin of cadmium, silver, tellurium, and zinc have been measured at 655°. 700°, and 750°K by liquid-metal solution calorimetry. Silver, cadmium, and zinc are endothermic at these temperatures while tellurium is exothermic. Only the heat of solution of silver depends on composition while all four elements show a temperature-de pendent heat of solution. The heat of solution of tellurium is constant up to 0.6 g-at. pct, becomes increasingly more exothermic, and reaches a limiting value at 1 g-at. pct Te. The limiting value has been used to calculate the heat of formation of SnTe at 750°K. The heat effects associated with the dissolution of the compounds Ag2 Te, CdTe, and ZnTe in liquid tin were measured at 750°K. These values are cotnOined with the measured hat effects at 750°Kfor silver, cadmium, tellurium, and zinc to detertrline the heats of formation of the telluride compounds. Cadmium lelluride exhibits a heat of dissolution which has a compositional dependence. THERE is a considerable amount of interest in the compounds of tellurium because of their electronic properties. Both cadmium and zinc tellurides are thermoelectric materials and considerable work has been done on their electronic properties but a limited amount of data is available on their ther-modynamic properties. This work was undertaken to elucidate the heat of formation data on cadmium and zinc telluride. Since both cadmium and zinc are in Group II it seemed to be of interest to compare the values obtained for them with the heat of formation of a Group I telluride. Silver telluride was selected for this comparison. In the course of the work it was also possible to determine the heat of formation of tin telluride and therefore to make a comparison of some of the Group I, 11, and lV tellurides with the metallic elements silver, cadmium, and tin being in the same period. There is also a great deal of interest in the energetic changes which occur upon addition of solute elements to a common solvent. This investigation provided an opportunity to study the partial molar heats of solution of silver, cadmium, tellurium, and zinc in liquid tin. The partial molar heats of solution are of theoretical interest because solute-solute interactions are a minimum in dilute solutions and application of solution models is simpli- fied. In order to complete the analysis of solute-solute and solute-solvent interactions the temperature dependence of the partial molar heats of solution was also measured. MATERIALS AND EXPERIMENTAL PROCEDURE All materials were of the highest purity available. The silver, zinc, cadmium, and tellurium were obtained from American Smelting and Refining Co. and were reported to be 99.999 pct pure. The silver telluride, zinc telluride, and cadmium telluride were obtained from Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp., and were electronic-grade material of 99.999 pct purity. Tin used for the solvent bath and for calibration was obtained from the Vulcan Manufacturing Co. and was reported as being 99.99 pct pure. The liquid-tin solution calorimeter used in this work is similar in principle to the differential twin-type calorimeter described by K1eppa.l Two of three identical calorimeter wells are used together during any set of experiments, one well being active and the other being passive. The wells are positioned 120 deg apart in an aluminum calorimeter block. Each well contains a multijunction thermopile and a Pyrex test tube to hold the liquid metal bath. Forty-eight of the thermopile junctions are distributed over the surface of each calorimeter well adjacent to the test tube and serve to integrate the heat effects occurring. The other forty-eight are next to the aluminum calorimeter block. The thermopiles for the three wells are connected differentially so that any change in temperature at the outer junctions (which will be the same for both wells because of the high conductivity of the aluminum block) will oppose for the two wells and result in no shift of the zero. The electrical output represents the true temperature difference between the two reaction vessels. A reaction occurring in the active well gives a comparison with another body of very similar thermal properties. In this way, any spurious heat effects due to slight temperature drifts within the entire calorimeter block are eliminated. The output of the differential thermopile goes to a dc amplifier with multiple ranges of from * 10 pv to 1 30 mv. The output of the amplifier is then fed into a Leeds and Northrup strip-chart recorder. The adiabatic temperature change is then calculated using the technique of Howlett, Leach, Ticknor, and ever.' The aluminum calorimeter block is contained in a cylindrical furnace with main and control heaters

Jan 1, 1965

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967