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By Robert K. Steunenberg, Irving Johnson, James B. Knighton

The activity coefficient of plutonium in liquid magnesium, over the temperature range 650° to 800°C, was obtained from measurements of the distribution of plutoninm between a 50 mole pct MgC12-30 mole pct NaCl-20 mole pct KC1 molten-salt mixture and liquid Zn-Mg alloys. For dilute solutions (0.08 at. pct Pu) the activity coefficient of plutonium was found to vary from 10.1 at 650°C to 12.2 at 800°C. The activity coefficients of plutonium in dilute liquid solutions of plutonium in uranium, silver, lanthanum. cerium, and calcium were estimated to be. The distribution data indicate a value of about 0.1 at 800°C for the activity coefficient of PuCl3 dissolved in the above ternary salt mixture. LIQUID magnesium and several liquid alloys of magnesium with metals such as zinc and cadmium have been shown to be useful solvents in pyrochemical processes for the recovery of uranium and plutonium from discharged nuclear fuels,' and for the separation of transuranium elements.' The present study was undertaken to determine the activity coefficient of plutonium in liquid Pu-Mg alloys in support of process-development work. The activity coefficient of plutonium in liquid magnesium was determined from experimental data on the distribution of plutonium between a liquid ternary MgC12-NaC1-KC1 salt mixture and various liquid Zn-Mg alloys. The distribution data were used to calculate the ratio of the activity coefficients of plutonium in liquid zinc and in liquid magnesium. The activity coefficient of plutonium in liquid magnesium was then computed from the known activity coefficient of plutonium in liquid zinc. It was not necessary to know the thermodynamic properties of the molten-salt system explicitly. The major features of the Pu-Mg system have been reported by Schonfeld.3 At the temperatures of interest in the present study, i.e., above about 600°C, the phase diagram indicates the existence of a wide liquid-miscibility gap, with the plutonium-rich liquid containing about 8 at. pct Mg and the magnesium-rich liquid containing about 10 at. pct Pu at the intersection with the solidus regions. Additional data on the compositions of the two equilibrium liquid phases obtained in this laboratory4 have defined the miscibility gap up to the consolute temperature (at about 1040°C). EXPERIMENTAL PROCEDURE AND RESULTS Materials. The 50 mole pct MgC12-30 mole pct NaC1-20 mole pct KC1 salt mixture was prepared by melting the required proportions of reagent-grade NaCl and KC1 with anhydrous MgC12. The molten salt was then purified by contacting it with liquid Cd-30 wt pct Mg alloy (at 450°C) to reduce oxidizing impurities, followed by filtration through a stainless-steel frit (pore size, 65 µ) to remove solid MgO formed during the reduction. The purity specifications of the zinc, magnesium, and plutonium were 99.999, 99.8, and 99.85 pct, respectively. Apparatus. The liquid salt and metal were contained in a tantalum crucible inside a graphite secondary vessel. The crucible assembly was located inside a resistance-heated stainless-steel furnace tube. The furnace tube was closed by means of a stainless-steel cover, which was attached by bolts, with a neoprene O-ring serving as a gas-tight seal. The top of the furnace tube was water-cooled to protect the O-ring. The furnace-tube cover was provided with a tantalum thermowell, a tantalum stirrer, and a port through which sampling tubes could be inserted and materials could be added to the melt without admitting air to the furnace tube. Vacuum and an argon atmosphere were available through a side-arm on the furnace tube. The furnace temperature was regulated by a proportional controller that was actuated by a chromel-alumel thermocouple between the furnace tube and the heating elements of the furnace. The melt temperature was measured by means of a chromel-alumel thermocouple in the tantalum thermowell. The accuracy of temperature measurement was ±3°C. The salt and metal phases were intermixed by a motor-driven tantalum paddle positioned at the liquid interface. The tantalum crucible was provided with four baffles to increase the turbulence. The sampling tubes consisted of 1/4-in.-OD tantalum tubing that terminated in a tantalum frit (Kawecki Chemical Co.; average pore size, 30 µ). Procedure. The zinc, magnesium, plutonium, and salt were charged to the tantalum crucible; then the system was evacuated and filled with argon. The melt was brought to the desired temperature, and agitated for 1 to 2 hr. After allowing the salt and metal to separate, both phases were sampled. Filtered samples were obtained by immersing the end of the sampling tube in the liquid and increasing the argon pressure sufficiently to force the liquid salt or metal through the frit into the tantalum tube. The sample was then partially withdrawn into the cooler portion of the furnace tube and permitted to solidify before being removed. The temperature sequence for sampling at each magnesium concentration was 800°, 700°, 600°, 650°, and 750°C. The composition of the liquid-metal phase was varied by incremental additions of magnesium in a series of experiments at low magnesium

Jan 1, 1967

By H. C. Stumpf, L. A. Willey, V. L. Fink

Very few studies of the aluminum-sodium system have been reported. Heycock and Neville1 were unable to detect any solubility of sodium in liquid aluminum. Mathewson2 prepared an equilibrium diagram consisting of two horizontal lines at the melting points of the two metals. He was unable to detect solubility at either end of the system. Scheuer3 first developed a method for the chemical determination of sodium in aluminum and then studied the solubility of sodium in liquid aluminum. His method involved heating aluminum with excess sodium under hydrogen until the two liquids were at equilibrium, chilling the melt, and analyzing the aluminum-rich layer. He reported the solubility to be 0.10 pct sodium at 700°C, 0.115 pct at 750°C, and 0.128 pct at 800°C. This paper on the aluminum-sodium system is the twenty-first in a series from the Aluminum Research Laboratories describing equilibrium relations in aluminum alloy systems. Materials The alloys for this investigation were prepared from electrolytically refined aluminum (99.99 pct) and sodium of reagent quality conforming to specifications of the American Chemical Society. Chemical analysis of the aluminum showed the fol- lowing impurities: 0.002 pct Si, 0.002 pct Fe, 0.002 pct Cu, <0.001 pct Mn, 0.002 pct Mg and 0.001 pct Na. The sodium content of all alloys was determined by either chemical or spectro-graphic standard procedures5 No. IIA and No. SI I respectively. Determination of Miscibilitv The boundary of the miscibility gap was determined by a modification of the method of Scheuer3 and of that used by Henry and Cordiano. As finally developed the method was as follows: A fused alumina crucible 25 mm id with 75 mm depth and 1.5 mm wall thickness was placed on the bottom of a container made from a 4-in. length of 1 1/2-in. iron pipe and pipe caps. ?&apos;he space around the sides of the crucible was filled with 40 mesh crystalline alun-dum. A charge of 60 g of aluminum and 10 to 15 g of sodium was placed in the crucible, the sodium first being trimmed and rinsed with iso-pentane to remove kerosene. The container was tightly capped, filled with argon (99.6 pct pure), and heated to the desired temperature (between 670 and 800°C). A positive pressure of argon (about 8 mm of mercury) was maintained through a small pipe to the upper cap. After soaking for from 2 to 5 hr, the container was quenched by directing a stream of water onto the base, so that solidification of the aluminum-rich layer was rapid and essentially unidirectional. Analyses were made on drillings taken from the bottom of the ingots after machining off the surface layers. Pre-

Jan 1, 1949

By Donald B. Hunter

The Ti-Be system up lo 10 wt pct Be with cortlmercialll&apos; pure titanium has been determined using metal-lographic techniques. Beryllium forms the p eutec-toid type of dinqarz with titanium; the eutectoid occurs at 0.5 xt pct Be azd 1500 F, while an eutectic is foritled at 1887°F containing between 5 and 7.5 rt pct Be. The solubility of beryllium in a titanium does not exceed 0.05 zvt pct and the maximum solubility of Beryllim in 0 titanium is 1 wt pet. PREVIOUS work on the Ti-Be phase diagram indicated that additions of beryllium to titanium resulted in a marked lowering of the melting point,&apos;&apos;&apos; and it was also observed that the solubility of beryllium in both a and p titanium was retricted.- With the limited data available, McQuillan and McQuillan constructed a partial hypothetical diagram of the Ti-Be system,= assuming that beryllium formed the 0 eutectoid type of system with titanium. Subsequently Bedford published a tentative diagram of the entire Ti-Be system: although he did not investigate alloys containing less than 10 wt pct Be. This diagram included several compounds described by other authorities.&apos;-l3 The following account describes work directed toward determining the form of the titanium-rich portion of the phase diagram up to 10 wt pct Be. MATERIALS AND METHODS Titanium sponge and a master alloy containing 25 wt pct Be were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 250-g compacts which were melted into buttons by arc melting under purified argon on a water-cooled copper hearth. Results of analyses for beryllium are shown in Table I but no determination of other elements was made at this stage. The alloys were hot-rolled at 1650°F to produce 0.1-in.-thick sheet. Alloys containing up to 1.5 pct Be were fabricated without trouble; samples containing 2 pct cracked initially upon hot rolling, but thereafter rolled satisfactorily to sheet. The 5, 7.5, and 10 pct were hot short and could not be rolled. Surface contamination was removed from samples by sandblasting and pickling in a 5 pct HF-35 pct HNOs solution. For metal log raphic examination, heat-treated specimens were mounted transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and electropolished at 20 v using a solution containing 600 ml of methanol, 60 ml of perchloric acid, 360 ml of butyl cellosolve, and 2 ml of Solvent "X". Difficulty was experienced in obtaining good electropolished surfaces with samples containing more than 1 pct Be, the degree of difficulty in-

Jan 1, 1967

By Jose A. Ruiz

INTRODUCTION For heterogeneous non-catalytic solid-gas reactions carried out in fluidized bed reactors, nominal bed temperature is an average value between gas and solid. For highly exothermic reactions, actual particle temperature can be up to hundred degrees above termocouple temperature, since heat dissipate at slower rate than heat generation during some steps of transformation. These micro instabilities at particle level can displace thermodynamic equilibrium from the desired phase to others. This effect is important when relatively narrow range of phase stability exists, like in sulphation roasting of sulphides, where bed discharge contains, in addition to the desired sulphate others metastable phases such as basic sulphate and ferrite. For example, for copper-iron sulphide concentration roasted below 680°C, no cupric ferrite is formed, as shown by Jakob et al., therefore the separate Kellogg&apos;s stability phase diagrams Cu-S-O represent the roasting (Fig.l). At temperature above this one, like 760°C for example, phase stability changes from CuSO4 to the basic sulphate Cu0•CuSO4. Solid state reaction between Cu0•CuSO4 and Fe203 also occurs to form cupric ferrite, Cu0•Fe2O3, therefore the Cu-Fe-S-O Kellogg&apos;s phase diagram of Fig. 1 (continuous line) represents this condition of roasting. Although both Cu0•CuSO4 and Cu0•Fe2O3 are metastable phases under normal operating conditions of sulphation roasting(1-10% SO2, 1-10% 02 and 680°C, points A and B,Fig. 1) sulphation of these species and particularly ferrite are slow and limited due to diffusional control. This explain why reactors discharge contains several phases: CuSO4, Cu0•CuSO4, CuO•Fe203 plus small amounts of CuS and FeS due to the baclonixed conditions of fluidized bed reactors. The presence of cuprous ferrite due to reducing conditions inside individual particles also occurs, but in very limited extent at the reaction interface, as it is demonstrated by the low soluble iron levels of calcines. On the other hand, the presence of cupric ferrites can be explained only due to the higher temperature achieved by particles, since below 680°C cupric ferrite formation does not take place. [ ] This phenomena also occurs for others non-ferrous metal sulphides concentrates roasted under sulphation conditions, such as 7n, Co and Ni. Therefore the prediction of discharge composition of fluidized beds is not possible based only on kinetics and mechanistics models alone or purely thermodynamical considerations, since all factors should be integrated to describe the overall phenomena. SINGLE PARTICLE TRANSFORMATION Assuming a first order reaction with respect to the gas and zero for solid, such as

Jan 1, 1984

By W. H. Hoffman

During the autumn of 1891, several heavy blasts (each throwing down some 3000 tons of ore) were made on what is known as the Theall side of these mines. Immediately after one of these blasts, the writer found that at least one-third of the ore was largely impregnated with pyrites, and besides this, fully 15 per cent. of the entire blast was composed of irregular lumps of magnetic pyrites. This was a revelation wholly unexpected, as previous examinations by many experts had failed to disclose any such quantity of sulphury ore. Over the center of the Theall tunnel there suddenly appeared a perfect keystone, as it were, of pyrites, 3 feet wide at the arch of the tunnel, 13 feet ride at the top, and 20 feet high. This keystone pinched out in February, 1892; but in that month large blocks of pyrites were more plentiful on or near the western wall, and these deposits extended the entire height of the workings, some 43 feet. The second blast in November, in the face and over, and on each side of the tunnel, was far more surprising. The whole cross-section it exposed was thickly interspersed with layers of magnetic pyrites, ranging in thickness from 10 to 24 inches, and quite irregular in form, while all of the ore carried much more than the usual amount of sulphur in the non-magnetic pyrite. One hundred and fifty-five tons from a portion of this breast (western side), showed the following composition upon sampling and analysis: Per cent. Metallic iron,...45.080 Phosphorus,..........304 Sulphur,...........23.510 And the balance of the blast showed: Per cent. Metallic iron,.....• 33.210 Phosphorus,...........349 Sulphur,.......... 6.680 vol. xxI.-33

Jan 1, 1893

By A. M. Skov, L. F. Elkins

First response to large-scale water flooding in the fractured very low permeability Spraberry sand has led to a new unique cyclic operation. Capacity water injection is used to restore reservoir pressure. This is followed by marly months production without water irzjection and the cycle repeated. Expansion of the oil, rock and water during pressure decline expels part of the fluids but capillary forces hold much of the injected water in the rock. At least with reservoir pressure restored and with partial water flood development, field performance has proved this cyclic operation is capable of producing oil from the nzatrix rock at least 50 per cent faster and with lower water percentage than is imbibition of water at stable reservoir pressure. INTRODUCTION The Spraberry Field of West Texas presents unusual problems for both primary production and water flooding. Extensive interconnected vertical fractures in the fractional-md sandstone permitted recovery of oil on 160-acre well spacing, but they made capillary end effects dominant. Primary recovery by solution gas drive is less than 10 per cent of oil in place. The concept of displacement of oil from the sand matrix by capillary irnbibition of water has led to field techniques which promise greatly increased oil recovery. Free exchange of laboratory research, reservoir information and results of field pilot tests among the various companies has been very important in development of this technology. Five units covering a total of 170,000 acres have been formed for water flooding, and 10 other areas covering an additional 175,500 acres are in various stages of unitization. Part of the Driver Unit reaching fillup first has demonstrated very unusual waterflood behavior and indicated numerous operating problems that will develop within and among the various units. SPRABERRY ROCK AND PRIMARY PERFORMANCE The Spraberry, discovered in February, 1949, is a 1,000-ft section of sandstones, shales and limestones with two main oil productive members: a 10-15 ft sand near the top and a 10-15 ft sand near the base. In part of the field some thinner intermediate sands are oil productive, and others are water bearing. All sands have permeabilities of 1 md or less and porosities of 8-15 per cent. Ordinary core analysis and electric and radiation logs are ineffective in differentiating between oil productive and nonprcductive sands. Sands capable of containing producible oil are best identified by mercury injection capillary pressure measurement and, in some cases, by core water saturation. About 3,500 wells have been drilled in the 500,000-acre trend. Vertical fractures were observed in practically all Spraberry cores. Continuity and interconnection of fractures were confirmed by pressure interference among wells during early development.&apos; Major fractures trend northeast-southwest as indicated by oriented cores and confirmed by five fluid injection tests, by analysis of the pressure transients observed during development,&apos;&apos;&apos; and by three interference tests in the Driver Unit Water Flood reported herein. Fracture spac- ing probably averages inches to a few feet. Spraberry wells typically produced 100-400 BOPD initially after hydrauLic fracture treatments. By 1962 oil production had declined to an average of 12 bbl/well/day, near the economic Limits of operation. Reservoir pressure had declined from 2,300 psi initially in the Upper Spraberry and 2,500 psi in the Lower Spraberry to 500-1,000 psi. Partial closing of the fractures with declining reservoir pressure is believed to be the cause of such low oil production rates at these relatively high reservoir pressures. Cumulative recovery of 208 million bbl of oil is 80 to 90 per cent of that recoverable by primary means. Performance of the entire reservoir is summarized in Fig. 1. IMBIBITION WATER FLOODING By 1952 reservoir performance indicated low primary recoveries. Most engineers, expecting serious channeling of injected fluids through the fractures, held little hope for secondary recovery. With its extensive background of research on the fundamentals of fluid flow within reservoir rocks, Atlantic&apos;s Research and Development Division on short notice in 1952 conceived that displacement of oil by capillary imbibition of water into the rock might significantly increase Spraberry recovery. Laboratory data reported by Brownscombe and Dyes scaled to probable reservoir conditions showed potential waterflood recovery equal to or greater than primary recovery with a 10-15 year flood life.= A pilot test using three 40-acre injection wells, one central producing well and 18 surrounding observation wells demonstrated technical feasibility of the process. Injection of 1.5 million bbl of water from November 1952 to August 1955 proved water entered the rock and displaced oil

By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)&apos; molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),&apos; which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.&apos; This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967

By Andrew A. Blair

It is now well known that certain pig-irons give a considerably smaller percentage of sulphur when determined by evolution-methods than when determined by oxidation-methods. The most striking examplcs of such irons are those made either wholly or in large part from New Jersey magnetites containing more or less titanium. It is never safe to use an evolution-method on such iron; for it is quite common that the sulphur result by evolution is only one-half or even one-third as great as that obtained by oxidation. For this reason, evolution-methods should be discarded, except in the analysis of pig-irons known to contain the sulphur in a state of combination from which it is evolved as sulphuretted hydrogen on treatment with hydrochloric acid. A good example of an iron containing, in the residue, sulphur insoluble in hydrochloric acid having come to our attention, it was determined to try to isolate a suspected insoluble sulphide. A large piece of high-silicon gray-forge iron was accordingly selected as the most promising material to work on. This piece was dissolved slowly, through several months, in dilute hydrochloric acid, aided by the electric current, yielding a soft graphitic residue. The object of dissolving a mass of iron, instead of drillings, was to prevent the crushing, by the drill, of any insoluble crystalline compound that might be present. The first step in the preparation was to break up the graphitic material and put it through bolting-cloth of 157 meshes to the linear inch. This was done by crushing the mass under the fingers on the bolting-cloth fastened over the top of a beaker, while a stream of water from a wash-bottle washed the finer portions through the cloth. The suspended matter was allowed to settle. It was then transferred to a platinum

Jan 1, 1902

By JOHN R. SUMAN

I WOULD like to spend a few minutes describing to you the present condition which exists in the oil industry and then point out some aspects of this deplorable situation in which I think petroleum engineers can be helpful. As you know, the oil business at this time is in a very critical condition, .due to the tremendous potential production in excess of current demand. This is a world-wide condition as well as a national problem, as it is estimated that the surplus production available for the market in foreign countries is of about the same proportion as that existing in the United States. Due to the inability within the United States to hold production within the bounds of demand prices have been slumping for the last four years and at this time have reached the point where the sales value of the average barrel of crude oil in the United States, is far below the cost, of production. In addition to the large amount of potential production available for the market in excess of demand we have in storage in the United States about six hundred fifty millions of barrels &apos;of oil. Unless something can be done to limit the amount of oil coming onto the market to a point well below the demand, which point will permit the reduction of stocks, it looks as though the &apos;oil business is facing demoralization.

Jan 1, 1931

By Richard Conkling

A SHALE layer, buried beneath two or three thousand feet of strata, in some instances, will upon folding become thicker in the synclines and thinner on top of the anticlines. This can be accounted for, in part, by the stretching on the crests of the fold and the compressing in the troughs; but this will by no, means account for all of it, as is shown in the example herein set forth. It is my firm belief that the rest of the thickness is due to flow. What causes the movement, however, does not concern us here, so long as there is movement, for this article purposes to show its effect upon the producing area of different sands. It is the author&apos;s hope, in this way, to drop a hint or two that may be valuable to the oil geologist, in making estimates of future productions and values of oil properties. An example will be given from property in the famous Cushing Pool in northeastern Oklahoma, where the author has had occasion to make a detailed study before recommending some property to his company, and has then been able to watch the results of this work. The author never mapped the surface structure in this pool, as this had been done by Frank Buttram when he was with the Oklahoma Geological Survey. We are using, therefore, a section of his map in this article for our surface contours. The main east clip comes farther east than this section shows.

Jan 10, 1916

By N. H. MacMillan, O. C. Dias

Recent work by Westwood et al. (reviewed in Refs. 1-6) has established that many rocks, minerals, ceramics, and glasses exhibit phenomenologically similar chemomechanical (Rebinder) effects when deformed in different liquid environments, apparently as the result of chemisorption-induced variations in their near-surface flow and flow-dependent fracture behavior. In particular, it appears that there exists an empirical, but apparently general, correlation between the near-surface flow stress of an inorganic nonmetal and its surface charge- namely, that such a solid is hardest at its zero point of charge (i.e., when its zeta potential [ ] = 0) and softens as [ ] increases, regardless of the sign of zeta. Moreover, because near-surface flow and fracture phenomena are two of the important determinants of the rates of machining and comminution processes, both Westwood et al. and others7 have been able to use this so-called "[ ]-correlation" to develop cutting fluids and grinding aids that in many instances have given rise to several fold increases in performance. In addition, Westwood et al. have demonstrated that both aqueous and organic environments can give rise to similar improvements in cutting rate for a given combination of tool and workpiece, provided that both impart the same surface charge to the work- piece (i.e., transfer the same number of electrons to or from its surface). This last finding implies that in any application it should always be possible to find some cutting fluid that is at once effective, cheap, nontoxic, and nonpolluting. Thus, reports of apparently similar environmental influences on the mechanical behavior of diamond,8 certain organic crystals and polymers,9-14 and coa1-15-21 suggest that it is pertinent to ask: (a) whether the [ ]-correlation (or any analogous relationship) extends to coal; and (b), if so, whether this relationship can be used to guide the development of superior aids for grinding coal. Accordingly, correlations have been sought between (1) the zeta potentials, (2) the hardnesses, and (3 and 4) the drilling and grinding characteristics of coals of different rank in different aqueous and organic environments. This paper reports the results of that search.

Jan 1, 1980

By O. J. Huber

HYDROGEN effects in titanium alloys have been the subject of extensive research in recent years. Lenning, Craighead, and Jaffee1 showed that hydrogen embrittles a titanium and, at the same time, elevates the temperature at which the transition from brittle to ductile failure occurs during impact testing. In later work: the same investigators concluded that several all-ß alloys tolerate large amounts of hydrogen without serious damage to mechanical properties, but two-phase alloys suffer varying degrees of embrittlement, depending upon the specific ß-stabilizing addition used and whether or not an a stabilizer is also present. The mechanism of hydrogen embrittlement has not been clearly established. Strain rate has been shown to be an important factor and, therefore, a strain-aging phenomenon is suspected to cause the effects that hydrogen has produced on mechanical properties.3-5 Ripling6 has pointed out that ductility damage varies inversely with strain rate in a-ß alloys and directly in a alloys. This effect in a alloys can be associated with transition-temperature behavior, but the embrittlemeat mechanism in two-phase alloys remains in question. During the course of research conducted for the U. S. Air Force, a dark-etching phase has been observed at the grain boundaries of certain two-phase titanium alloys after duplex (solution plus aging) heat treatments.5-7 An example of the dark-etching interface phase is shown in Fig. 1. Decrease in ductility accompanies the appearance of the minor phase but has not always been attributable solely to the presence of the phase. Although the dark-etching phase has been observed in alloys under a rather narrow range of heat-treatment conditions, it is of general interest since it is always associated with the presence of hydrogen. The known embrittling effect of hydrogen makes any facet of its behavior of particular importance. The intergranular phase has been observed in titanium-base alloys with relatively high amounts of the ß-stabilizing elements. Specific examples of such alloys include Ti-5 pct Mn-2.5 pct Cr, Ti-3.5 pct Cr-3.5 pct V, Ti-8 pct Mn, and Ti-3 pct Mn-1

Jan 1, 1958

By William A. Longacre

In a previous paper the author discussed the problem described by the title of this paper, outlining and reviewing the Gish-Rooney method, with comparison and brief analysis of the interpretation techniques of Roman2 and Tagg.3 Some aspects of the simple type of two-layer system were reviewed from various sources.4, 5, 6 The Two-layer Problem For the configuration shown in Fig. I, and for any electrode separation A, the SurfAce of earth p, DepthH i P2 Infinite depth Fig. i.—Two-Layer system. apparent resistivity is a function of the relative depth the overburden resistivity pl, and a factor K defined by the equation P2 + P1 where p, is the resistivity of the lower bed. Thus, by the known theory of electrical images, p = pi [1+ */(*-7)] where The Multilayer Problem As the number of isotropic, homogeneous, horizontal layers increases, the difficulties of interpretation multiply. The theory becomes much more involved, and in view of the state of our knowledge, the general problem is virtually impossible of exact solution. However, certain types of multilayer problems can be worked out in terms of two-layer theory. Humme1,7 Pirson,8 Tagg,3 Watson,9 and others have pointed out the possibility of building up approximations of multilayer resistivity curves with suitable combinations of two-layer curves. Many three-layer curves can be constructed in this way to a good degree of accuracy, and special types of four-layer curves can be approximated. It is very likely that as the number of layers increases, the method of combination will not give good approximations except in very special cases. In the analysis of actual field data, the author has found that many obviously multilayer curves can be solved partially with a good degree of accuracy, using the theory that thin adjacent beds may be considered as one layer or zone, and applying two-layer theory to the extremities of the field curve. Modified Tagg Method of Interpretation Tagg&apos;s second method, though superior to his first, necessitates a large number

Jan 1, 1946

By William A. Longacre

In a previous paper the author discussed the problem described by the title of this paper, outlining and reviewing the Gish-Rooney method, with comparison and brief analysis of the interpretation techniques of Roman2 and Tagg.3 Some aspects of the simple type of two-layer system were reviewed from various sources.4, 5, 6 The Two-layer Problem For the configuration shown in Fig. I, and for any electrode separation A, the SurfAce of earth p, DepthH i P2 Infinite depth Fig. i.—Two-Layer system. apparent resistivity is a function of the relative depth the overburden resistivity pl, and a factor K defined by the equation P2 + P1 where p, is the resistivity of the lower bed. Thus, by the known theory of electrical images, p = pi [1+ */(*-7)] where The Multilayer Problem As the number of isotropic, homogeneous, horizontal layers increases, the difficulties of interpretation multiply. The theory becomes much more involved, and in view of the state of our knowledge, the general problem is virtually impossible of exact solution. However, certain types of multilayer problems can be worked out in terms of two-layer theory. Humme1,7 Pirson,8 Tagg,3 Watson,9 and others have pointed out the possibility of building up approximations of multilayer resistivity curves with suitable combinations of two-layer curves. Many three-layer curves can be constructed in this way to a good degree of accuracy, and special types of four-layer curves can be approximated. It is very likely that as the number of layers increases, the method of combination will not give good approximations except in very special cases. In the analysis of actual field data, the author has found that many obviously multilayer curves can be solved partially with a good degree of accuracy, using the theory that thin adjacent beds may be considered as one layer or zone, and applying two-layer theory to the extremities of the field curve. Modified Tagg Method of Interpretation Tagg&apos;s second method, though superior to his first, necessitates a large number

Jan 1, 1946

Mr. Cottrell : I omitted to speak of the cost of installation. The precipitation-plant at the Balaklala smelter, up to the time of initial operation, including the construction of flues, installation of the apparatus, etc., cost $107,000, and subsequent modifications probably represented at least $15,000 more. Upon the information gained in this plant, the installation at the cement-mill, handling nearly twice as much gas, has been reduced in cost in a number of ways, but the overhead construction, carrying the precipitator at the top of the stacks, is naturally expensive, yet, even so, the total cost of construction will probably not greatly exceed $150,000. The mechanical details of the tubular form last shown have been worked out more recently than those of the plate form, and the tubular form promises to be still less expensive in construction, as you would naturally expect. The cost of operat-ing the plant varies somewhat with the character of the gases used. The amount of power consumed is not determined by the tonnage of the material collected, but by the volume of gas to be handled. It takes as much power to precipitate a thin cloud as a dense one. In the cement-plant they are getting a higher efficiency; i. e., a greater number of cubic feet treated per kilowatt than in the earlier plants. This is perhaps partly due to higher temperature of the gases, which here average about 450° C. The best figures on the cement-plant are between 3 kw. and 4 kw. Of

Jan 1, 1913

By D. G. Swarthout, J. W. Savage, R. W. Guard

The Nb-N constitution diagvam has been examined from 1100° to 1450°C at 1 atm N2 pressure. On the basis of- our work plus that of Brauer and coworkers the stable nitvide Phases are: a) a solid solutlion, basic niobium (bcc) with nitrogen contained interstitially; NbN,, x = <0.40; b) ß NhNx,x = 0.39 to 0.45; hexagonal (W2C type) (NbzN); a =3.058A,c = 4.961 + 0.001A c) y NbNx x = 0.75 to 0.80; tetragonal (distorted NaCl type) (Nb4N3); a = 4.386A,c = 4.332 + 0.001A; d) 6 NbN,, x = 0.88 to 0.91; cubic (NaCl type); a = 4.3885 + 0.0007A; e) E NbNx x = 0.92 to 1.00; hexagonal (Tip type); a = 2.958A, c = 11.272 * 0.0015A. In addition, a metastuble transition phase 6&apos; has been observed and occurs only during the transition 6 — E. 6&apos; NbN has these distinguishing parameters: NbNx,x = 0.96; hexagonal (anti-NiAs type); a = 2.94A, c = 5 .46A. The high-temperature phase fields in the system are governed by two reactions: a) 6 + Y + E, a entectoid reaction occurring at 1270" ± 20° C; b) o + N2 = E, a 2 012 1 reaction occurring at 1370" ± 20° C. As part of a study of the electronic low-temperature. properties of transition metal nitrides, a number of specimens of niobium nitride were prepared. Preliminary observations on these specimens showed several points of disagreement with data already in the literature. It was, therefore, decided to determine the constitution diagram for the Nb-N system between 1100" and 1450°C. The objective of this research was to define the temperature and composition regions of stability of the various phases and to explain the differences among previously proposed diagrams. Review of Previous Literature. The research on the Nb-N system to 1964 has been summarized by storms.&apos; Although he does not present a phase diagram, his review covers the research on the system thoroughly. One of the earliest works on NbN is that of Ascher-mann and coworkers2 who studied the superconductivity of the cubic 6 NbN. Subsequent work by Horn and ziegler,3 Cook, Zemansky, and Boorse,1 Rögener:5 Schroder6 and sellmaier7 has qualitatively confirmed the first results on superconductivity, although their methods of preparation differed considerably. The constitution diagrams proposed for the system by Brauer and Esselborn8 and Elliott9 are shown in Fig. l(a)and (b). The diagram in l(a) has been modified by more recent results in Brauer&apos;s laboratory (private communication). Although 6&apos; is shown on this diagram, Brauer has indicated that he now believes 6&apos; to be a metastable phase in the temperature range shown. The diagram of Elliott, Fig. l(b), is based primarily on the results of Elliott and Komjathy10 on ni-trided niobium strip or rod specimens examined by X-ray diffraction and metallography. It will be noted that these proposed diagrams are in conflict with respect to the temperature and composition ranges of

Jan 1, 1968

By Lyall, Zickrick

As a result of the studies on recrystallization and crystal growth made in this laboratory, certain theories have been developed. These are expressed briefly in a paper by Dean and Hudson.&apos; One of the principal points brought out in that paper is that in the deformation of a crystal, the energy supplied is distributed to the atoms of the lattice, probably by the forced formation of molecules. It is found that a Maxwellian distribution of the energy among these atoms will account for the grain growth at various temperatures. According to such a distribution the number of atoms with energy above a certain critical value, E, necessary for recrystallization at the absolute temperature T is given by n = Ne-E/kT where N is the total number of atoms. It is apparent that if this line of reasoning is correct, a metal which has been cold-worked and reheated to a temperature below that of complete annealing will have the atoms with the higher energy recrystallized, that is, reduced to normal energy and there will remain only atoms below a certain energy. If this metal is again cold-worked the peak in the number-energy distribution curve will, as compaied with its position after the first cold-working, be displaced toward the regions of lower energies, that is, the temperature of recrystallization will be higher. By a repetition of this process the position of this maximum and hence the recrystallization temperature of the metal could be raised considerably. In order to check this theory, experiments have been made on copper wire. The wire was drawn from 1/4-in. rod to 22 B & S gage and then sample lots were annealed at 400 and 220° C., respectively. The wire annealed at 400° C. gave an elongation of 34 per cent., whereas that annealed at 220° C. gave only 23 per cent. These wires were then drawn by identical practice to 34 B & S gage and the elongation determined after an anneal of 3 min. in an oil bath held at various temperatures. The figures obtained have been plotted in Fig. 1. It will be seen that the

Jan 1, 1927

By C. C. Nathan

Data are resented on the physical properties of five waxes obtained from fields in Texas and Louisiana in which "parafin" troubles are being experienced. The crude parafin was fractionated into three components, voluble in cold acetone, soluble in boiling acetone, and insoluble in boiling acetone. The acetone insoluble fraction was found to consist essentially of straight chain parafin hydrocarbons in the molecular weight range 525 to 700. Solubilities of the purified high molecular weight parafins were determined in a number of solvents. It was found that in hydrocarbon solvents, including crude oil, solubilities could be calculated satisfactorily by use of ideal solubility relations. In chlorinated, and oxygenated solvents, large deviations from ideal behavior were observed. These deviations could be partially correlated with the internal pressure of the solvent. INTRODUCTION A problem encountered in many producing oil fields is that of "paraffin" deposition. The problem refers to the deposition of material from the crude oil onto tubing, pumping rods, flow lines, or other material contacted by the crude. This problem has been recognized for nearly a hundred years, and numerous investigations have been reported on its causes and prevention or alleviation. One of the more comprehensive of such investigations was published by Reistle1 in 1932. A few of the salient findings of his report are briefly as follows: The term "paraffin" as used to describe this problem refers to the deposit of carbonaceous material which is not soluble or dispersible by the crude oil under the conditions where deposition occurs. The "paraffin" normally consists of high molecular weight paraffin hydrocarbons, both straight chain and branched, resins and asphaltic materials of undetermined nature, occluded oil and water, and possibly sand. In consistency, the deposit may vary from a soft, sticky material, to one which is hard and brittle. Deposits are usually black, although lighter colors are sometimes observed. Under the conditions of temperature, pressure, and crude oil composition occurring in the underground reservoir, the paraffin is in suspension or solution in the crude. As the oil flows to the surface, there is generally a reduction of temperature, pressure, and the amount of dissolved gases contained in the oil. Reduction of temperature and gas break-out were shown by Reistle to be factors causing reduced solubility of the paraffin in the crude. Thus, as the crude containing paraffin rises to the surface and flows to storage tanks at atmospheric temperature, the solubility of the paraffin may be exceeded. Deposition will begin at the point in the system where the temperature of the system falls below its cloud point, and continue as long as there is a further drop in the solution power of the crude for the paraffin. The severity of the deposition as well as the location of the bulk of the deposition, i.e., in subsurface or surface equipment, will depend on the amount of paraffin originally in the crude, the manner in which pressure and temperature of the crude

Jan 1, 1956

By F. H. Wilson, E. W. Palmer

G. L. Bailey (British Non-Ferrous Metals Research Association, London, England)—I was glad to see this further work on the structure and properties of the Cu-Ni-Fe alloys of low nickel content in which we have been so interested in the United Kingdom since before the war." The authors&apos; data on the variation in solubility of iron in both 5 and 10 pct Ni alloys with temperature is based on more detailed observations than we have made but is generally in line with our own work. The difficulty in these matters is in the identification of the structures obtained. The precipitation of the second phase which we presume to be the a&apos; solid solution, richer in nickel and iron, from the a solution with which it is in equilibrium occurs in such a fine state of division that its resolution by ordinary micro-graphic methods is impossible in the early stages. We have published some electron micrographs which illustrate the effects observed more clearly but we agree with the authors when they say that dark staining characteristics when the alloys are subjected to sea-water corrosion are more sensitive in detecting the presence of the a&apos; phase than is the microscope. After taking this point into consideration, however, I confess to some difficulty in understanding Fig. 4. I can only assume that the precipitates visible at such a low magnification as 150 diam in these relatively coarse forms are produced from iron-rich areas of the initial solid solution due to inadequate homogenization. If this is so I find it difficult to accept the authors&apos; contention that such local variations in iron concentration as are capable of giving the heavy precipitates shown in Fig. 4 do not in fact materially affect the solvus surfaces of their equilibrium diagrams. I share the authors&apos; enthusiasm about the resistance to corrosion of these alloys by seawater but I am not fully in agreement with them on the vexing question of the best iron content for these alloys. In Fig. 3 of ref. 8, we give many results showing that the resistance of these alloys to impingement attack in the Jet Test increases as the iron content rises to 2 pct. With higher iron contents pitting at shielded areas is likely to occur. Admittedly the addition of 0.75 pct Fe produces a large improvement in corrosion resistance compared with a pure 90/10 Cu-Ni alloy, but the further improvement on raising the iron to 2 pct is substantial. We recommend from 1.5 to 2 pct Fe as the desirable range from the point of view of corrosion resistance. While it is true that British practice generally uses a hard tube, the corrosion resistance of the 10 pct Ni alloys has in our work been little affected by the structural condition. Although the annealed alloys blacken in seawater, this effect seems to be superficial and not to be accompanied by any real decrease in

Jan 1, 1953

By T. S. Fuller

MUCH study has been given by engineers in general, and investigators in particular, to the concentration of stress which occurs under load in structural members having irregularities in section such as notches, shoulders, key ways, tool marks, etc. The result of the effect of both fresh and salt water corrosion upon the endurance properties of various metals and alloys has been ably determined and the general laws underlying these phenomena carefully pointed out by McAdam. From a practical standpoint, &apos;however, it is after all the endurance value of corroded, non-symmetrical sections which is most pertinent. In the experiments about to be described rotating cantilever specimens of nickel steel of the 3.5 per cent nickel &apos; 0.35 per cent carbon type have been used. These were machined from bars l 1/8. in. dia. and 9% in. long and were heat-treated by quenching in oil from 825 deg. C. followed by reheating to 650&apos; C. and oil quenching. The tensile and impact properties of this material so heat- treated follow:

Jan 1, 1931