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By W. Bonfield

A study has been made of the dislocation substructures produced in hot-pressed beryllium specimens strained to various levels in the range from 800 x 10-6 In. pev in. to fracture. A number of distinctive dislocation configurations were observed in this region which had not been noted at lower levels of strain. These included dislocation-dislocation interactions to form networks, dislocation "walls", subgrain boundaries and complex arrays, interactions between dislocations and large beryllium oxide particles, and the generation of dislocations from certain particles. The nature of these differences in substructure and their relation to the stress-strain characteristics of polycrystalline beryllium are discussed. In a previous study1 of the plasticity of commercial-purity, hot-pressed beryllium a transition was found in the deformation characteristics in the mi-crostrain region. The initial plastic deformation could be represented by a parabolic stress-strain equation, but above a critical stress there was a complete departure from this relation and a reduction in the strain-hardening rate. The dislocation configurations produced by various levels of micro-strain in this region were examined by transmission electron microscopy and a general correlation was established between the observed transition in deformation characteristics and the dislocation structure of the material. The two stages in the micro-strain region distinguished in these experiments were designated as Stage A' and Stage B'. Stage A' type deformation generally was noted up to a plastic strain of -80 x 10"6 in. per in. and Stage B' type from -80 x 10-6 to -800 x 10'6 in. per in. The discovery of two stages in the microstrain region naturally posed pertinent questions as to the existence of any further distinct stages in the subsequent plastic deformation. The purpose of this paper is to present a study of the dislocation configurations produced in similar beryllium specimens strained to various levels in the range from -800 x 10 in. per in. to fracture and to discuss the relation between substructure and the stress-strain characteristics. It is concluded that this region of strain can be considered as a distinct stage in the plastic deformation of polycrystalline beryllium. Tensile specimens of gage length 1 in. and cross section 0.18 by 0.06 in. were prepared from commercial-purity, hot-pressed QMV beryllium and then annealed at 1100°C for 2 hr. 2 followed by a careful chemical polishing procedure.3 The specimens were strained at a constant rate to various levels of strain in the range from -800 x 10-6 in. per in. to fracture (at 0.5 to 2 pct elongation), using the Tuckerman strain-gage technique1 to measure plastic and total strain. Thin foils were obtained from the strained and fractured specimens by chemical polishing3 and were examined using an RCA-EMU 3 electron microscope. Considerable care waS taken to avoid both accidental deformation during the preparation of the thin foils and excessive heating during their examination. Selected-area diffraction patterns were determined for each micrograph. Tilting experiments were also performed whenever appropriate to establish the dislocation zero-contrast position and hence determine the Burgers vector. This operation was sometimes not possible due to the rapid contamination of the foils which occurred in the electron microscope. RESULTS AND DISCUSSION To enable the distinctions between the dislocation arrays at high and low strain levels to be adequately made, the main characteristics of Stage A' and Stage B' deformation are briefly reviewed. 1) Stage A'. In the annealed starting condition there was a variable density (5 x 107 to 3 x 10' cm per cu cm) of isolated dislocations within a grain. The initial deformation in a tensile specimen was heterogeneous, with the dislocation density increasing in a few grains to 5 x 10g to 1.5 x 101° cm per cu cm. The deformation occurred exclusively on the basal plane by the movement of one or more 1/3 (1130) type dislocation systems. The dislocations were long and regular in form and nearly all the intersections exhibited a simple four-point node configuration. No interactions between glide dislocations and beryllium oxide particles were observed. 2) Stage B. In Stage B' there was a large increase in the number of grains exhibiting dislocation movement and also a change in the nature of the deformation, in which jogged dislocations and elongated loops became the characteristic feature. The splitting up of the elongated loops into smaller loops and the possibility of source action from the re-

Jan 1, 1965

By W. A. Riggs

In a single year the total transportation cost equals nearly 30 pct of the value of mineral commodities, the largest single cost from the deposit to consumer. The magnitude of this economic factor calls for more complete understanding of cost and operational problems between producer and carrier than now exists. Details are given of the costs of providing transportation as well as freight rates for selling transportation. In 1958, transportation of mineral commodities in the United States required 600 billion ton-miles to move 1 3/4 billion tons of products of mines comprising solid fuels, crude oil, industrial minerals and rocks, and ores. Possibly 17 pct was handled by more than one mode of transport, since combinations of several modes of transport may, at times, achieve better service/cost results than any single mode. Total transportation cost of nearly $5 billion equaled roughly 30 pct of the value of the mineral commodities, the largest single cost from the mineral deposit to the consumer. The tremendous magnitude of this transportation undertaking demands much more complete understanding than now exists between mineral producers and carriers about the economic and operational problems of each other. A substantial portion of the daily work of the writer is spent in trying to act as a combination interpreter and catalyst between potential shippers and carriers, hoping to direct both to points of mutual understanding and advantage. For the purpose of this paper, it is necessary to ask mining people to accept some terminology and to try to appreciate the mental approach of the freight rate making people of the carriers. This paper will consider costs of providing transportation as well as freight rates for selling transportation—although these are fields of limited certainty. There are no accurate statistical breakdowns for all modes of transport and types of carriers indicating commodities, volume of traffic, distances, costs, and rates. Much information is available for railroads, and some for the regulated portions of air, motor, pipeline, and water transportation. Unregulated carriers, handling about half of the transportation of products of mines, are not required to report, and very little is known of their activities. Figures used herein are national in scope, unless otherwise indicated, and have generally been derived from Interstate Commerce Commission reports and files. Tonnage figures have been reduced to net tons of 2000 lb. The very generalized comparison of average mileage freight rate levels for various modes of transport provided by Fig. 1 affords advantageous perspective for the entire field of transportation costs. Dashed guide lines show cents per ton-mile, and dotted guide lines show percentage of first class railroad freight rate. While costs of other than railroad transportation more nearly follow constant cents per ton-mile functions, costs of railroad transportation show characteristic taper, or decrease in cents per-ton mile with increasing length of haul. This fundamental difference in cost is due largely to the fact that railroads and pipelines provide their own fully taxed roadway facilities while highway, waterway, and air carriers use government-provided tax-free roadway at no cost other than fuel, license, and certain excise taxes. Thus railroad and pipeline transportation might be said to carry heavy threshold costs in addition to those transportation costs which are directly variable with ton miles of transportation produced. The original basis of railroad freight rate structures lies in the classification of all articles of commerce into railroad class ralings ranging from 7 to 40 pct of first class (100 pct) rate level, dependent on value, hazard, loading characteristics, service requirements, and whether carload or less than carload. Classification tables and mileage-based (but arbitrarily grouped), rate scales are published as tariffs subject to approval by regulatory bodies. Used together, these determine class rates in cents per 100 lb between points in the U. S. Where local commercial or operating conditions render it advantageous for carriers to depart from

Jan 1, 1961

By F. D. Rosi, C. H. Mathews

THE plastic properties of face-centered cubic metals below room temperature present a field of investigation which has not been extensively ex-plored. The work by Schmid and Boas1 has demonstrated the importance of temperature upon such properties as strain hardening and critical resolved shear stress. The work by Yamaguchi2 upon the shear stress as related to the number of slip bands accentuates the necessity for further experiments of a similar nature. The approach to a mechanical equation of state from the standpoint of thermal fluctuations and activation energies by Becker3 and more recently by Kauzmann4 further emphasizes the need for a quantitative and more comprehensive analysis of the dependence of fundamental plastic properties on temperature. The purpose of the present work was to investigate specifically: (1) The gross shape of the stress-strain curves at several temperatures, (2) the change in the critical shear stress as a function of temperature, and (3) the number and appearance of slip bands as a function of strain and temperature. Preparation of Specimens Single-crystal specimens of 99.996+ pct alumi-num, 1/2 in. in diam and 5 to 6 in. in length, were made by the Bridgman method of gradual solidification from the liquid state. The crystallographic orientation of the single crystals was determined from back-reflection, Laue X-ray photograms ac-cording to the method described by Greninger.6 In most specimens the Laue photograms showed double diffraction spots indicative of the lineage structure type of imperfection, discussed in great detail by Buerger.7 The angular spread of these spots was never observed to exceed 2". Most of the crystals were radiographed to insure against microporosity. In preparing the metal surface for optical microscopy, the following sequence of operations gave good results: The as-cast crystals were turned down in a lathe, 0.001 in. per cut, to obtain a 2.5 in. gauge length. The cold-worked layer resulting from this operation was removed chemically by etching with Tucker's reagent. Then the specimen was polished mechanically through 2/0 metallographic emery paper, after which it was etched again to remove the cold-worked layer resulting from the mechanical treatment. A 48-hr anneal at 580°C ±10°C followed so as to insure an essentially stress-free single crystal. After the annealing treatment, the specimen was electrolytically polished in a 2:l solution of methyl alcohol and concentrated nitric acid. With a current density of 10 amp per sq dm (decimeter) the time required to obtain a satisfactory surface varied from 10 to 12 min. The polish-ing was carried out for short periods of 2 min to avoid rapid deterioration of the solution as well as to enable the rotation of the specimen 180" for uniformity of polish. It was necessary to place the solution in a bath of dry ice in view of its explosive nature at room temperature. Etching of the electrolytically polished surface was accomplished by using the fuming etch-pit method recommended by Lacombe and Beaujard8 for high-purity aluminum. Method for Tensile Testing A modification of the loading equipment devised by Miller9 was used. In this apparatus, the specimen was suspended from a chain and gimbal arrangement (for axial loading) in a heavy steel framework connected at the bottom to a balanced 6:1 lever and bucket system. Loading of the specimen was accomplished by allowing sand to flow from a reservoir into the bucket suspended from the longer end of the lever-arm at a rate of approximately 3 lb per min. Strain measurements were made using the Baldwin SR-4, bonded, resistance-wire, strain gauge and an SR-4 portable strain indicator (type K), which permits a reading accuracy of 2 microinches per inch. For low-temperature study, the gauge was calibrated by measuring the elastic modulus of an annealed stainless steel rod, which is known to be independent of temperature."

Jan 1, 1951

By E. M. Porbansky

DURING the investigation of the electrical transport properties of copper, it became necessary to prepare large single crystals of the highest obtainable purity. In an effort to meet these demands, single crystals of copper have been grown by the conventional pulling technique—as has been used for the growth of germanium and silicon crystals.' Low-temperature resistance measurements made on these crystals show that, as far as their electrical properties are concerned, they are generally of significantly higher purity than the original high-purity material. The use of these pure single crystals with very high resistance ratios has made possible the acquisition of detailed information regarding the electron energy band structure of copper2-' and has stimulated widespread effort on Fermi surface studies of a number of other pure metals. It is the purpose of this note to describe our method of preparing very pure copper crystals by the Czochralski technique. Precautions were taken to prevent contamination of the melt from the crystal growing apparatus. A new fused silica growing chamber was used to prevent possible contamination from previous groqths of other materials such as germanium, silicon, and so forth. A new high-purity graphite crucible was used to contain the melt. This crucible was baked out in a hydrogen atmosphere at -1200°C for an hour, prior to its use in crystal growth. Commercial tank helium, containing uncontrolled traces of oxygen, was used as the protective atmosphere. A trace of oxygen in the atmosphere appears to be necessary for obtaining high-purity copper single crystals. A 3/8-in-diam polycrystalline copper rod of the same purity as the melt was used as a seed. The copper rod was allowed to come in contact with the melt while rotating at 57 rpm. When an equilibrium was observed between the melt and the seed (that is, the seed neither grew nor melted), the seed was pulled away from the melt at a rate of 0.5 mils per sec. As the seed was raised, the melt temperature was slowly increased, so that the grown material diminished in diameter with increasing length. When this portion of the grown crystal was -1 in. long and the diameter reduced to less than 1/8 in., the melt was slowly cooled and the crystal was allowed to increase to - 1-1/4 in. diam as it was grown. By reducing the diameter of the crystal in this manner, the number of crystals at the liquid-solid interface was decreased until only one crystal remained. Fig. 1 shows a typical pulled copper single crystal. The purity of the starting material and the crystals was determined by the resistance ratio method: where the ratio is taken as R273ok/R4.2ok. The starting material, obtained from American Smelting and Refining Co., was the purest copper available. Most of the pulled copper crystals had much higher resistance ratios than the starting material. The highest ratio obtained to data is 8000. Table I is an example of the data obtained from some of the copper crystals. Note that Crystal No. 126 had a lower resistance ratio than its starting material and this might be due to carbon in the melt. The melt of this crystal was heated 250" to 300°C above the melting point of copper. At this temperature it was observed that copper dissolved appreciable amounts of carbon. The possible presence of carbon at the interface between the liquid and the crystal will result in reducing conditions and negate the slight oxidizing condition required for high purity as discussed below. The possible explanations of the improvement in the copper purity compared to the starting material are: improvement in crystal perfection, segregation, and oxidation of impurities. Of these, the latter seems to be most probable. A study of the etch pits in the pulled crystals showed them to have between 107 and 108 pits per sq cm. The etch procedure used was developed by Love11 and Wernick.10 The resistivity of the purest copper crystal grown was 2 x 10-10 ohm-cm at 4.2oK; from the work of H. G. vanBuren,11 the resistivity due to the dislocations would be approximately 10-l3 ohm-cm, which indicates that. the dislocations in the copper crystals would contribute relatively little to the resistivity of the crystals at this purity level. Segregation does not seem likely as the reason for purification of the material, since the resistivity of the first-to-freeze and the last-to-freeze portions are approximately the same, as was observed on Crystal No. 124. On most of the crystals that were examined, the entire melt was grown into a single crystal. If the

Jan 1, 1964

By T. S. Spice, H. L. Lovell, R. W. Utley

With the increased demand for lightweight aggregate, such materials have been manufactured from slags, clays, slates and, to a minor extent, the refuse of coal preparation processes. The latter source is attractive due to current interest in eliminating air pollution and improving the unsightly appearance of refuse piles as well as potential economic advantages, if a satisfactory product can be manufactured. A study has been made relating the composition of coal refuse, expressed as washability data, and the properties of a resulting aggregate. Three different refuse samples (bituminous and anthracite) were separated at gravities ranging from 1.4 to 2.96. Their chemical composition was determined. Aggregates were prepared in the laboratory from these fractions before and after ashing, at temperatures between 1250' and 1350°C. The specific gravity, expansion and compressive strength of the products were measured. The response of the refuse to bloat is related to the chemical composition of the ash to yield a glass of desirable viscosity and to the presence of a material which will form a gas in the appropriate temperature range. Carbonaceous material within the particle is a negative factor since after the glassy phase forms, oxygen cannot enter the mass thus inhibiting bloating. Precombustion of the refuse is also detrimental since it removes substances of gas-forming capability. The fraction sinking at 2.60 yielded an aggregate which had the lowest specific gravity, greatest expansion and greatest compressive strength. The purpose of this study was to seek and evaluate possible relationships between the composition of coal refuse, as expressed by washability data and factors affecting the production of a lightweight aggregate from refuse by bloating. The study was related to an intense program in the Department of Mineral Preparation at the Pennsyl- vania State University to study the possible elimination of air pollution from coal refuse fires by producing a low-carbon secondary refuse. Another phase of this program is considering possible uses of such a secondary refuse. Thus one study was to determine if a lightweight aggregate could be produced from this new refuse material and what effect the nature of refuse beneficiation would have upon the characteristics of a commercial aggregate product. It was hoped that these studies would assist in the design of a process and in establishing the optimum specific gravities at which refuse separation could be made in respect to the production of a low grade fuel from the float product and a raw material for lightweight aggregate from the sink product. The combination of producing a saleable low grade fuel and a lightweight aggregate, while at the same time minimizing disposal costs and air pollution contributions would be attractive to the coal mining industry. MECHANISM OF BLOATING Austin, Nunes and Sullivan,1 Ehlers,3 Everhart, 4 Riley7 and others, have stated that bloating is an expansion process in which two essential conditions exist simultaneously. These are: the development of a glassy phase over a relatively wide temperature range (the viscosity of this glassy phase plays a major role in the retention of the evolved gases) and the evolution of gases (SO2, SO3, CO2 and O2) from mineral decomposition in sufficient quantities at appropriate temperatures to form a cellular structure in the mass. Unless these two "type" reactions take place at the same time or in overlapping ranges of time and temperature, cellulation will not occur. In this event, the gas will escape or the melt will be too fluid to retain it; or if retained, the cells may be too large or the walls too thin for good strength in the product. The stages that occur when clays and shales are heated in an oxidizing atmosphere may be summarized as follows: 1) Drying and removal of free water to 200°C. 2) Absorbed water dehydration period (200 to 480°C). 3) Chemically-combined water dehydration period (480 to 700°C).

Jan 1, 1965

By H. J. Ramey

A general solution is presented for the transient temperature distribution caused by radial movement of a cylindrical heat source through a homogeneous medium of infinite extent. This problem represents a highly simplified model of the movement of a combustion front during the thermal recovery of oil. Numerical solutions are presented for a heat source moving at a constant velocity, and a velocity inversely proportional to the radial location of the heat source. Numerical solutions are presented for both finite and infinite vertical thickness of the heat source, i.e., with and without vertical heat losses. The numerical solutions are used to estimate the fuel concentration needed to maintain a combustion front during the thermal recovery of oil. The sensible heat carried to the combustion front by the injected gas stream is discussed in regard to the fuel concentration. Numerical solutions for a heat source (combustion front) of finite vertical thickness indicate the field conditions that may be necessary to sustain the temperature of a combustion front above the ignition temperature of the fuel over considerable distances from an injection well. The results also have implications in regard to the quantity of heat required during ignition. The results of this computation apply to a highly idealized model of a thermal recovery process. But the results may be used as a guide in engineering consideration of the thermal recovery process. INTRODUCTIO N The thermal recovery of crude oil has received considerable attention since the publication by Kuhn and Kochl of laboratory and field tests of this method of oil recovery. Other publications2,3,4,5,6, since that time have dealt with various features of the thermal recovery of oil and have illustrated the extremely complex nature of this process. Vogel and Krueger7 described an electric analog computer designed to solve a moving heat source problem which was analogous to movement of a combustion front during the thermal recovery of oil. The heat source was maintained at constant temperature and was a cylindrical source of infinite height (no vertical heat loss) moving radially at either constant velocity, or at a velocity inversely proportional to the radial location of the heat source. Jenkins and Ramey2 presented analytical solutions to a similar heat conduction problem and pointed out the possible importance of vertical heat losses. The following presents a general solution to the transient heat conduction problem introduced by Jenkins and Ramey4 as well as numerical solutions for a wide range of conditions possibly similar to those that might exist during field operation of the analogous thermal recovery process. DESCRIPTION OF PROBLEM The problem considered in this paper is determination of transient temperature distribution caused by a cylindrical heat source of infinite or finite vertical height, moving radially through an isotropic medium of infinite extent. It is further assumed that the heat flux generated at the surface of the moving heat source may be a function of time such that the fuel concentration required may be constant, or permitted to vary, and that heat is generated at the surface of the heat source only. In regard to the thermal recovery of oil the assumption that heat is generated at the surface of the front is equivalent to assuming that the thickness of the combustion zone is infinitely small, or that the reaction rate between fuel and oxidant gas is infinite. The last assumption does not appear stringent. See laboratory information published by Martin, et al3 Under these assumptions the temperature distribution throughout an infinite medium caused by a heat source moving radially with an arbitrary velocity may be described by The heat generation function or heat flux at the surface of the source, +(t), is Note that the fuel concentration may be defined as a function of time. Eq. 1 is derived in the Appendix.

By Milton E. Wadsworth, W. Martin Fassell, William H. Dresher

A study of the rate of dissolution of molybdenite (MoS2) in alkaline solution was carried out under carefully controlled conditions. Effects of temperature, oxygen over-pressure, and KOH concentration were evaluated. Studies were made in the temperature range 100°C to 175°C and in the pressure range 0 to 700 psia of oxygen. Under these conditions molybdenite was found to leach according to a linear mechanism. Both oxygen over-pressure and KOH concentration were found to control the rate of leaching. The mechanism has been explained in terms of adsorption of oxygen at the molybdenite surface followed by configurational rearrangement of the adsorbed molecules. The hydroxyl ion dependency is believed to be diffusion-controlled. Laboratory batch studies have shown that molybdenite can be readily dissolved in alkaline solutions under moderate conditions of temperature and pressure. Commercial application of this process to the production of ferro-molybdenum and molybdenum chemicals is promising in view of the ease of dissolution of molybdenite and the relatively noncorrosive conditions involved in the process. HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.' The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.' National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 phalerite,4 galena,5 and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,8 who found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo+ + in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit's construction and operation have been discussed elsewhere,7 Only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-A1 alloys has been measured up to the solubility limit for formation of aluminum nitride using the Sieverts method. The activity coefficient of nitrogen decreases slightly with increasing aluminum content in the range of 0 to 4 wt pct Al. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from fhe elements dissolved in liquid iron has been determined to be: ?F" = -59,250 + 25.55 T in the range from 1600º to 1750ºC. The solubility of nitrogen in liquid iron alloys and the interaction of nitrogen with dissolved alloying elements in liquid iron have been the subject of a number of research investigations.' Most of this work, however, has been reported for concentrations well below those necessary for the formation of the alloy nitride phase. Data in the concentration region near the solubility limit of the alloy nitride, particularly for systems exhibiting stable nitrides, are important in evaluating the denitrifying power of various alloying elements. They are also useful in determining the stability of a given nitride if it is to be used as a refractory to contain liquid iron alloys. In view of the importance of aluminum as a deoxidizing agent in commercial steelmaking and the fact that its nitride, AIN, is a highly stable compound and has merited some consideration as an industrial refractory, the following investigation was undertaken. The use of the Sieverts technique provided a measurement of the equilibrium nitrogen solubility in liquid Fe-A1 alloys as a function of nitrogen gas pressure up to 3.85 wt pct A1 in the temperature range of 1600º to 1750°C. The values obtained by the Sieverts method were checked by means of a quenching method in which liquid iron was equilibrated with an A1N crucible under a known partial pressure of nitrogen gas, and the solubility of A1N in liquid iron determined by chemical analysis. EXPERIMENTAL PROCEDURE The theoretical considerations involved in determining the solubility product of a solid alloy nitride phase in liquid iron by measuring the point of departure of the nitrogen gas solubility from Sieverts law have been discussed by Rao and par lee.' The principal problem is to determine the variation of nitrogen solubility in an alloy as a function of the pressure of nitrogen gas over it with sufficient precision to establish the break point in the curve at the solubility limit of the alloy nitride phase. A fairly large number of data points are required to do this. A second problem is the determination of the composition of the precipitated solid nitride phase. This is necessary in order to define completely the thermodynamic relationships. The Sieverts apparatus used to make the nitrogen solubility measurements in this investigation is of essentially the same design as that described by Pehlke and E1liott.l The charge materials were Ferrovac-E high purity iron supplied by Crucible Steel Co. and 99.99+ pct pure aluminum. Recrystal-lized alumina crucibles were used, and were not attacked by the liquid alloys. The hot volume of the system which was measured for each melt ranged from 46 to 50 standard cu cm and was found to decrease linearly with decreasing pressure and with increasing temperature. The temperature coefficient of the hot volume at 1 atm pressure of argon gas was essentially constant for all experiments at a value of -6 X 10-3 cu cm per "C. The melt temperature was measured with a Leeds and Northrup disappearing filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature scale was calibrated against the observed melting point of pure iron taken as 1536°C. The emissivity of all melts was assumed to be that of pure iron, taken as 0.43. The charge weights ranged from 110 to 140 g and the range of aluminum contents covered was from 0 to 3.85 wt pct. Aluminum additions were made as 12 to 15 wt pct A1-Fe master alloys previously prepared in the system under purified argon. The compositions of the master alloys were checked by chemical analysis and found to be in agreement with the charge analyses. Vertical cross sections of the master-alloy ingots were used as charge material for the equilibrations in order to minimize the effect of any segregation which might have occurred during solidification of the master alloys. Determinations of the solubility product of

Jan 1, 1964

By G. W. Neighbor, M. S. Abrahams

The actice slip plane in InSb is found to be of the {111} type by using the method of two-tmce anulysis. Measurements of the rotation of the tensile axis with increasing plastic shear strain indicate that the tnacroscopic slip direction is a <110>. Recrystal-lization is first observed at a sheav strain of about 70 pct for a crystal deformed at a temperatzcre of 473° C and at a shear strain rate of 2.90 times 10- %ecc-I; the dislocation density corresponding to this value of the strain is 1 x 108 em-&apos;. At a shear strain of about 170 pct, the recrystallization process is complete. This appears to be the fimt time re-crystallization has heen observed in a semiconductor. V HE operation of the {Hi} glide plane in Ge was first noted by Gallagher.&apos; This finding was confirmed by Treuting who also extended the result to Si. Using X-ray techniques, Treuting3 demonstrated that the macroscopic slip direction in Ge was of the <110> type. The choice of the (111) <110> slip system in Ge is exected since in the diamond-type structure the {Ill7 plane is the plane of highest density and the <110> direction is the direction of closest packing.4 There is little reason to expect that the glide elements of InSb are different from those of Ge, since the zinc-blende structure characteristic of InSb is quite similar to the structure of Ge. With regard to InSb, Allen5 has indicated that the glide plane is the {111} type. There appears to be no quantitative determination of the glide direction, however. The present work was undertaken to establish both the glide plane and glide direction in InSb and also to see if recrystallization occurs at large shear strains. EXPERIMENTAL PROCEDURE Mechanical Deformation. The single crystals of InSb used in this investigation were deformed in uni-axial tension. The tensile axis of the specimens was [145] and the periphery was bounded by (111) and (321) planes as shown in Fig. 1. The metallographi-cally polished specimens were deformed in a dynamic atmosphere of He, using an Instron machine. The tensile tests were performed at temperatures in the range of 300°C to the melting point (525OC) and at shear strain-rates varying between 1.94 X 104 sec-&apos; to 1.94 x 103 sec-&apos;. Additional details concerning the preparation and deformation of the specimens have been presented previously.&apos; Analysis of the Glide Elements. The traces of the active slip plane in both (111) and (321) planes were analyzed according to the usual method of two-trace analysis." The macroscopic slip direction was determined by measuring the rotation of the tensile axis as a function of plastic strain,8 These measurements were made from Laue back-reflection X-ray photographs. The X-ray beam was perpendicular to the (111) plane. A given crystal was used for only one measurement of the rotation of the tensile axis after it had been strained to a predetermined value. Therefore, care was taken at all times to insure that the X-ray beam was parallel to the [Ill ] direction of all the samples. RESULTS AND DISCUSSION Glide Plane. After 3.4 pct plastic shear-strain, at a temperature of 369°C and a shear strain-rate of 1.94 x 104 sec-&apos;, the slip traces on the (111) and (3.21) planes appear as in Figs. 2(a) and 2(b), respectively. The results of an analysis of these glide markings demonstrate that the slip plane is (111). The operation of this plane is expected on the basis of the orientation of the specimen, since glide on this plane and in the [I011 direction will result in

Jan 1, 1962

By K. E. Brown, G. H. Fancher

An 8,000-ft experimental field well was utilized to conduct flowing pressure gradient tests under conditions of continuous, multiphase flow through 2 3/8-in. OD tubing. The well was equipped with 10 gas-lift valves and 10 Maihak electronic pressure recorders, as well as instruments to accurately measure the surface pressure, temperature, volume of injected gas and fluid production. These tests were conducted for flow rates ranging from 75 to 936 B/D at various gas-liquid ratios from 105 to 9,433 scf/bbl. An expanding-orifice gas-lift valve allowed each flow rate to be produced with a range of controlled gas-liquid ratios. From these data an accurate pressure traverse has been constructed for various flow rates and for various gas-liquid ratios. A comparison of these tests to Poettmann and Carpenter&apos;s correlation indicates that deviations occur for certain ranges of flow rates and gas-liquid ratios. Numerous curves are presented illustrating the comparison of this correlation with the field data. Poettmann and Carpenter&apos;s correlation deviates some for low flow rates and, in particular, for gas-liquid ratios in excess of 3,000 scf/bbl. These deviations me believed to be mainly due to the friction-factor correlation. However, Poettmann and Carpenter&apos;s correlation gives excellent agreement in those ranges of higher density. This was as expected and predicted by Poettmann. He pointed out that their method was not intended to be extended to those ranges of low densities whereby an extreme reversal in curvature occurs.l As a result of these experimental tests, correlations using Poettmann and Carpenter&apos;s method were established between the friction factors and mass flow rates which are applicable for all gas-liquid ratios and flow rates. Definite changing flow patterns do not allow any one correlation to be accurate for all ranges of flow. INTRODUCTION The ability to analytically predict the pressure at any point in a flow string is essential in determining optimum production string dimensions and in the design of gas-lift installations. This information is also invaluable in predicting bottom-hole pressures in flowing wells. Although this problem is not new to industry, it has by no means been solved completely for all types of flow conditions. Versluys,2 Uren, et al, 3 Gosline,4 May,5 and Moore, et al,6,7 were all early investigators of multiphase flow through vertical conduits. However, all of these investigations and proposed methods were very limited as to their range of application. Likewise, many are extremely complicated and therefore not very useful in the field. Only in the last decade have any significant methods been proposed which are generally applicable. The most widely accepted procedure in industry at the present time is a semi-empirical method developed from an energy balance, proposed by Poettmann and Carpenter8 in 1952. Their correlation is based on actual pressure measurements from field wells. Accurate predictions from this correlation are limited to high flow rates and low gas-liquid ratios. Although this method will be discussed in detail later, it should be pointed out that two important parameters, namely the gas-liquid ratio and the viscosity, were omitted in their correlation. The viscosity was justifiably omitted since their data was in the highly turbulent flow region for both phases, and most wells fall in this category. The gas-liquid ratio was incorporated to some extent in the gas-density term. In 1954, Gilbert9 presented numerous pressure gradient curves obtained from field data for various flow rates and gas-liquid ratios for the determination of optimum flow strings. However, no method is presented for predicting pressure gradients except by comparison to these curves. Baxendell, et al,10 proposed a method based on Poettmann and Carpenter&apos;s procedure

By G. T. Smith, R. C. Moyer

Cadmium, along with other impurities such as lead, gallium, germanium and indium, is characteristically found associated with zinc ores, the average ratio of zinc to cadmium being about 200 to 1. The increasing demand for cadmium has led most zinc producers to develop a means for its recovery. The separation and recovery of this byproduct constitutes an important development in the metallurgical field. Zinc sulphide concentrates, principally from domestic sources, are processed at Donora Zinc Works and they assay approximately 60 pct zinc, 30 pct sulphur, 0.37 pct cadmium, and 0.8 pct lead. Concentrates are roasted to convert zinc sulphide to zinc oxide. Sulphur evolved as sulphur dioxide is used to manufacture 60º Baume sulphuric acid by the lead chamber process. The roasted calcine is sintered to remove the remaining sulphur and volatile impurities. Fume from the sintering machines is collected by Cottrell pre-cipitators and sent to the Cadmium Department for cadmium removal. The sintered product, a crude zinc oxide, is then mixed with coke and salt and charged into horizontal retorts for reduction to zinc metal. Furnace residues are then passed through a Waelz kiln which recovers practically all of the remaining zinc as an oxide. This oxide is collected by Cottrell precipi-tators and returned to the sintering plant for further processing. The following discussion covers operating procedure, and equipment used in the Cadmium Department for the manufacture of cadmium and its byproducts. (See attached Flow Sheet, Fig 1.) The production of cadmium may be divided into several steps, each of which will be discussed separately. These steps are as follows: 1. Raw Materials—Sinter Plant Cottrell dust, acid sludge and sulphuric acid. 2. Sulphating—Separation of lead. 3. Purification—Separation of impurities other than zinc. 4. Precipitation—Separation of cadmium from zinc. 5. Briquetting—Preparation of sponge for charging to furnace. 6. Smelting—Distillation of cadmium metal. 7. Remelting—Casting into commercial shapes. 8. Recovery of Rare Metals—Separation of germanium, gallium and indium. Raw Materials The raw material, or Sinter Plant Cottrell dust, from which the cadmium is manufactured, is recovered by Cottrell units collecting fume from two Dwight-Lloyd sintering machines. An average analysis of this dust is 36 pct zinc, 1.5 pct sulphur, 17 pct lead, and 5.5 pct cadmium, with associated elements in smaller amounts. A lesser tonnage of material removed from the sintering machine fans, and called fan cleanings, is also treated for cadmium. It is lower grade material and analyzes approximately 41 pct zinc, 1.2 pct sulphur, 14 pct lead, and 4 pct cadmium. Cottrell dust and fan cleanings are delivered to the Cadmium Department by monorail crane in bell-bottomed dump buckets. Acid sludge and 60" Bauine sulphuric acid are received from the Acid Department. The acid sludge is a mixture of lead sulphate, sulphuric acid and zinc sulphate, and is recovered mainly from the floors of the acid chambers or storage tanks. The acid sludge is delivered to the Cadmium Plant in a lead lined bucket. The 60º Baume sulphuric acid is delivered through a lead pipe to a lead lined storage tank. Sulphating Four well ventilated lead lined sulphating tanks, 8 1/2 ft in diam by 12 ft deep, are used. These are steel tanks lined with 20 lb lead on the bottom and 16 lb lead on the ides, equipped with Hastelloy side agitators. 15 hp motors drive 24 in. propellers at 450 rpm. There are water connections to stuffing boxes to keep sludge from entering the bearings. The tanks are covered with removable wooden lids and are connected to marine plywood

Jan 1, 1950

By W. A. Backofen, D. H. Avery, W. F. Hosford

Sheets of the magnesium alloys AZ31B, HK31A, and ZE10A in several different tempers were tested in tension and determinations were made of the ratio of width-to-thickness strain. A marked increase in the ratio with tensile straining and a dependence upon alloy and test direction are rationalized in terms of a balance between the amounts of basal and prism-plane slip. All such variations are related, in turn, to the prevailing crystallographic texture. Fracture appearance is explained on the basis of anisotropy in plastic flow, and implications for developing texture -hardening effects in these alloys are discussed. ThE crystallographic texture or preferred orientation of a given material is determined by details of processing history. Such texture is known to influence many aspects of material behavior, in particular both the yielding and strain-hardening characteristics which are of special interest in the present work. Traditionally, the resulting plastic anisotropy has not been regarded as especially desirable. Earing in drawn sheet is perhaps the most common example of an unwanted effect of texture. However, it has also been recognized that suitable textures may be usefully employed to improve drawability,1,2 as a specific example, and generally to control yielding resistance under combined-stress loading.374 Texture would seem to be a detail of structure not yet exploited to nearly the fullest extent. A convenient basis for characterizing anisotropy in plastic behavior is the ratio of width-to-thickness strains obtained in a tension test;5&apos;6 the parameter is frequently labeled "R" and its value is revealing with respect to the nature of the prevailing texture. R gives a useful measure of a material&apos;s "thinning resistance". For an isotropic material, R = 1. With R > 1 the increased through-thickness strength in a sheet means greater resistance to yielding under biaxial tension, or "texture hardening";3&apos;4 if R < 1 the result may be a "texture softening" under the same loading conditions.4 Most R data relate to steel sheets for deep-drawing applications. Values for steel and other materials of cubic structures are not often much greater than 1 and nearly constant with strain in testing.1,2,7,8 To explore the implications of plastic anisotropy further, it was felt that experiments with much more strongly textured materials would be useful, and this led to the choice of magnesium alloys. The "ideal" sheet texture for magnesium contains the (0001) plane in the rolling plane, which ought to lead to R values approaching infinity. However, departures from the ideal texture, the possibility of slip in non-close-packed directions, and deformation by twinning would all be expected to introduce some range of R. Accordingly, studies on these materials were undertaken. EXPERIMENTAL Alloys in sheet form, Table I, were selected to obtain a variation in crystallographic texture, in the expectation that this would be reflected in differences in plastic anisotropy. Pole figures constructed by the Schulz surface-reflection technique9 were provided with the experimental materials by the Dow Metal Products Co. Profiles of pole density along great circles through the rolling (0 deg) and transverse (90 deg) directions were prepared from the pole figures and are collected in Figs. 1 and 2; considerable departure from the "ideal" (0001) alignment in the rolling plane is evident, with the largest angular spread in both directions being found in the ZEl0 alloy. Results of tensile tests on full-thickness specimens of 6-in. gage length by 1/2-in. width are given in Fig. 3 as engineering stress-strain curves* in rolling and transverse directions. All tests but one were made at a constant drive rate of 0.02 in. per min, and the final values of percent elongation at fracture, over the initial 6-in. gage length, are noted at the ends of the curves; one test on ZE10A-

Jan 1, 1965

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,&apos; and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson&apos; determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12&apos;13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By F. R. Cattoir, R. W. Kimball, C. T. Anderson

ONE of the principal impurities in all steels is sulphur. Sulphur-bearing, manganese-free steels exhibit hot shortness. Manganese is added to steel to improve the hot-working properties. If no sulphur were present in steel, it is probable that hot shortness would be nonexistent. This paper is the first of a series to be issued by this Laboratory reporting the measurements of hot forgeability tests and the physical properties of Fe-C alloys to which additions of various alloying elements have been made. The present paper describes the results- obtained by the addition of varying amounts of sulphur to Fe-C alloys. To obtain control over residual elements in the various charges melted in the arc furnace, it was considered advantageous to use sponge iron from one source as the melting stock rather than scrap metal having an unknown history. Small amounts of unwanted alloying elements might be introduced into the charge when scrap was used, thereby influencing the results of the various heats. A sponge iron having a high silica-lime ratio was used. Ore from Sunrise, Wyo., had been reduced to sponge iron and briquetted at the Bureau of Mines sponge-iron plant at Laramie, Wyo. The briquettes were 5 in. in diam and 2 to 3 in. in thickness, and weighed about 10 lb each. The chemical analysis of the sponge iron is as follows: C, 0.67 pct; Mn, 0.10; SiO2, 4.75; CaO, 1.4; P, 0.044; S, 0.72; MgO, 0.4; A12O3, 1.1; total Fe, 87.5; Fe metallic, 79.2; and reduction, 90.5 pct. Where a reducing agent was required, crushed graphite electrodes usually were used. The charcoal available contained 0.20 pct S. An analysis of the available coke showed it to contain 0.70 pct S. Where high sulphur heats were required, elemental sulphur additions were made to the ladle. Limestone of good quality was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2, 3.0; and P2O5, 0.014. Melting Procedure Sponge iron was melted to produce metal stock for the experimental alloys in a silica-lined, three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating. Fig. 1 shows this furnace installation. About 25 tons of sponge iron was melted in 75 heats, averaging 927 lb of sponge iron to the heat. An addition of carbon was required to complete the reduction of a portion of the iron oxide remaining in the sponge to prevent high losses of iron oxide in the slag and a low carbon content in the resulting metal. As reducing agents in preparing the melting stock, charcoal, coke, and a carbon product resulting from the thermal decomposition of natural gas were used. The quantity varied from 20 to 60 Ib per furnace charge, with an average of 38 lb. An average analysis of the metal obtained gave 0.52 pct C, about 0.01 pct Mn, 0.070 pct P, and 0.092 pct S. The average yield of metal was 647 lb with 241 1b of slag, the sponge-iron recovery being 70 pct. The metal obtained in melting the sponge iron was cast into pigs weighing about 20 lb each to facilitate recharging into the furnace for further refining. The pouring of the pigs is shown in Fig. 2. The average power consumption for the production of the 24 tons of metal obtained was 1704 kw-hr per ton.

Jan 1, 1954

By D. G. Westlake

The electrical resistance of a series of V-H alloys (0 to 3.5 at. pct H) has been measured over the temperature range G° to 360°. Interstitial impurities made contributions to the residual resistivity, but not the ideal resistivity. The contribution of hydrogen in solid solution is expressed by Ap = 1.12 microhm-cm per at. pct H; but the contribution of precipitated hydride was negligible. A portion of the so1vu.s for the V-H phase diagram is presented. The solubility limit is given by In N (at. pct H) = (5.828 i 0.009) - (2933 i 44)/RT. Comparison of critical temperatures joy hydride precipitation and published critical temperatures for hydrogen embrittlement suggests the two are related. ThiS study was initiated as part of an investigation of the mechanism by which small concentrations of hydrogen embrittle the hydride-forming metals at low temperatures. It has already been shown that, in the case of hcp zirconium, a reduction in ductility accompanies the strengthening resulting from precipitation of a finely dispersed hydride phase.&apos;&apos;&apos; Our attempts to detect a similar precipitation of a second phase at low temperatures in V-H alloys by transmission electron microscopy have been thwarted because we have been unable to prepare thin foils that are representative of the bulk material with respect to hydrogen concentrati~n.~&apos;~ The present investigation establishes the solvus of the V-H system at subambient temperatures. Subsequently, we hope to be able to determine whether the embrittlement temperature is related to the critical temperature for precipitation of the hydride in a given V-H alloy. veleckis5 has proposed a partial phase diagram for the V-H system based on extrapolations of the pressure-composition relations he measured at higher temperatures. Kofstad and wallace&apos; conducted a similar study of single-phase alloys but did not attempt to establish the phase diagram. Zanowick and wallace&apos; and ~aeland&apos; have studied a portion of the phase diagram by X-ray diffraction, but they investigated no alloys in the hydrogen concentration range 0 to 3 at. pct, the range of interest to us. EXPERIMENTAL PROCEDURE The vanadium was obtained from the Bureau of Mines, Boulder City, Nev., in the form of electrolytic crystals. The analyses supplied with them listed 230 ppm by weight metallic impurities, 20 ppm C, 100 ppm N, and 290 ppm 0. The crystals were electron-beam-melted into an ingot that was rolled to 0.64 mm. Strips, 60 mm long and 4.2 mm wide, were cut from the sheet, and both rolled surfaces were ground on wet 600-grit Sic paper to produce specimens 0.4 mm thick. They were wrapped in molybdenum foil, vacuum-encapsulated in quartz, and annealed 4 hr at 1273°K. The specimens were annealed in a dynamic vacuum of 2X lo-&apos; Torr for 30 min at 1073°K for dehydrogenation, and charged with the desired quantity of hydrogen by allowing reaction with hydrogen gas at 1073°K for 2 hr and cooling at 100°K per hr. Purified hydrogen was obtained by thermal decomposition of UH3. Sixteen specimens were studied: two contained no hydrogen and the others had hydrogen concentrations between 0.5 and 3.5 at. pct (hydrogen analyses were done by vacuum extraction at 1073°K). Electrical resistances were measured by the four-terminal-resistor method on an apparatus similar to the one described by Horak.~ The specimen holder was designed so that both current and potential leads made spring-loaded mechanical contact with the specimen. The potential leads were 30 mm apart, and the current leads were 55 mm apart. The current was 0.10000 amp. We used the following baths for the indicated temperature ranges: liquid nitrogen, 77°K; Freon 12, 120" to 230°K; Freon 11, 230" to 290°K; and ethanol, 290" to 340°K. Temperatures lower than 77°K were achieved by allowing the specimen to warm up after removal from liquid helium. Temperatures above 77°K were measured by a calibrated copper-constantan thermocouple (soldered to the specimen holder) and below 77°K by a calibrated carbon resistor. The temperature of the bath changed less than 0.l0K between duplicate measurements of the resistance. RESULTS AND DISCUSSION Typical plots of resistivity p vs temperature T are shown in Fig. 1. In the interest of clarity, only five curves are presented and the data points have been

Jan 1, 1968

By Gilbert L. Eggert

The effects of reactor irradiation on age hardening in a Cu-2 wt pct Be alloy have been investigated in two neutron-energy ranges. During some of the irradiations, specimens were exposed to high-energy fission neutrons which passed through a boron-10 shield; during other bombardments, the boron-10 was omitted and specimens were irradiated in a reactor thermal column, or the fuel configuration was modified to increase the thermal-neutron flux at a location in the core. Differences in length, X-ray diffraction angle, and hardness indicated that low-energy neutron irradiation made a small contribution to changes in the measured properties. The influence of defects generated by knock-om with less than the Brinkman critical energy or by prompt (n,y) recoil is suggested as the cause of this effect. EXPERIMENTS designed to test the effects of reactor irradiation on the properties of age-hardening alloys have to the present time employed fluxes un-differentiated according to neutron energy. Billing-ton and Siegell in 1950 were the first to perform such an experiment and to compare the results with those obtained by thermal aging. These authors concluded that precipitation in a Cu-2 wt pct Be alloy was not enhanced by the radiation. However, 4 years later, Murray and Taylor,2 working with specimens of the same Cu-2 wt pct Be alloy, reported that an increase in density, hardness, and resistivity which followed reactor irradiation resembled changes associated with thermal aging at about 100°C. (It should be noted that these authors reported that higher aging temperatures caused a decrease in resistivity.) cupp3 reported hardness results similar to those of Murray and Taylor. Koppenaal4 showed that irradiation-enhanced precipitation and irradiation defect hardening were not simply additive but that they acted separately in an irradiated alloy. Kernohan et a1.,5 working with Ni-Be, offered evidence that beryllium was removed from solid solution by reactor irradiation and suggested that the mechanism was one of increased diffusion through the use of vacancies in the structure. piercy6 also found that more precipitate particles were formed by fission-neutron irradiation of a Cu-Co alloy which contained a small amount of particles before irradiation. He proposed that the additional particles were caused by an appreciable amount of diffusion during the final cooling of displacement spikes. The retrogression of extant precipitate particles found by Murray and Taylor2 and Boltax7 as well as piercy6 indicated that nuclei were dissolved within a high-energy spike region and, upon resolidification of the perturbed volume, new nuclei precipitate and grow by enhanced diffusion. Bleiberg et al.&apos; and Konobeevski et al.&apos; explained phase changes obtained by irradiating fissionable alloys in terms of retrogression and re-precipitation in regions of high-energy spikes. Parsons and Balluffi10 used electron microscopy to verify that crystallization did indeed occur in displacement spikes which were formed in amorphous germanium by fast-neutron irradiation. The concept that low-energy neutron irradiation might cause structure-sensitive property changes in semiconductors by atomic recoil associated with the (n, y) reaction was first proposed by Schweinler" and walker." This thesis was tested by Cleland and crawford" and found to be valid. Coltman et al.14 exposed a variety of pure metals to thermal-neutron irradiation at cryogenic temperatures and attributed the resulting resistivity changes to the action of defects created by (n, y) recoil. The present work was undertaken to extend the concepts of Schweinler," walker," and Coltman et al.I4 to the case of an age-hardening alloy and to determine whether or not the action of defects produced by thermal-neutron irradiation would en-hance age hardening. EXPERIMENTAL PROCEDURE Omeea West Reactor Irradiations.* Thermal-

Jan 1, 1965

By J. A. Herbst, D. W. Fuerstenau

This paper examines the zero order production phenomenon in the context of the size discretized batch grinding model. A restrictive interrelationship between the selection and breakage parameters of the model, which is mathematically sufficient to ensure zero order behavior, is delineated. Based on this interrelationship, a scheme is developed for predicting the values of the selection and breakage parameters for all size fractions from a minimum of experimental data. To test this scheme, dolomite was ground in a laboratory batch ball mill. Successful simulation of the comminution behavior of this system was achieved using the batch grinding model with the parameter values obtained from the proposed scheme. Historically, a preponderance of comminution research has centered on attempts to relate breakage energy to the performance of comminution machines. Concomitantly, grinding data were interpreted almost exclusively in terms of inherently empirical energy-size reduction relationships1-3 or "laws of comminution"4- 6 which were based on highly oversimplified descriptions of the fracture process. In some instances, these relationships provide a crude basis for the correlation of experimental data, but, invariably, this approach is inadequate for meaningful process simulation. The control and optimum design of comminution circuits require a mathematical model capable of depicting the size reduction behavior of every size fraction for grinding conditions of technological importance. Energy-size relationships do not provide this detailed information. For example, an energy-size analysis for batch ball-milled dolomite has recently been completed in the authors&apos; laboratories.7 This analysis provided a satisfactory correlation between the hypothetical size modulus, which characterizes only the finer portion of the size distribution, and the input energy. However, this relation did not constitute an adequate description of the complete system. In general, one of two distinct viewpoints toward simulation has been adopted in recent comminution research. The first approach focuses on the fracture of single mineral specimens, with the essential aim of representing the over-all process in terms of the breakage characteristics of individual particles and the characteristics of the stress field which the particles experience within the particular size reduction device. As illustrated by Harris&apos;s review,&apos; the actual incorporation of single-specimen fracture information into a description of the behavior of a multiparticle comminution system has seldom been attempted. The only model to accomplish this incorporation was the one developed by Schönert.8 The Schonert model treats single-passage grinding machines in terms of a distribution of effective loads acting on a particle, a distribution of required particle breakage energies, and the breakage product distribution. However, the use of single-particle fracture behavior to derive models of the size reduction process is at present limited to machines in which the particle residence time is approximately equal to the time required to apply stress. As a result, Schönert&apos;s analysis cannot be used to advantage to simulate the complex environment which prevails within a tumbling mill. For multiple-passage systems a second approach to the description of comminution processes has been more fruitful. This approach entails the formulation of a mathematical model which is phenomenological in nature in that it lumps together the entire spectrum of stress-application events which prevail in a system under a given set of operating conditions. The appropriately defined average of these individual events is then considered to characterize the over-all breakage properties of the device. Thus, to analyze the performance of a tumbling mill, the manner in which the particles of a particular size (or size fraction) are stressed need not be distinguished. Instead, a single parameter is assumed to represent the resistance of that size to fracture, given the average grinding environment which exists in the mill. The isolation of such a parameter and a related set of quantities, which constitute the breakage product size distribution for the average event in this size fraction, allows the formulation of physically meaningful descriptive equations capable of yielding precise and detailed information for simulation.

Jan 1, 1969

By A. W. D. Hills, M. R. Moore

An apparatus has been developed in which metals can bc solidified under closely controlled unidirectional heat flow conditions. The metals are cooled by a multiple-air jet system, designed so that the heat transfer coefficient is uniformly distributed over the cooled surface. They are contained in a special furnace system of low thermal mass which enables unidirectional heat flow conditions to be rigorously maintained for certain specific cooling rates. This apparatus has been used to study the solidijication of pure lead and pure tin at zero superheat, solid metal thicknesses being determined by thermal analysis, and by dipstick readings. Detailed thermal balances have been drawn up on the experiments in order to determzne the cooling conditions that most rigorously correspond to unidirectional heat flow. Solid metal thicknesses, measured experimentally for these conditions, have beetz shown to agree closely with the theoretical wedictzons of different integml-profile methods. lt is concluded that any errors inherent in the integval-profile method are no greater than the errors inherent in experimental investigations of solidification. A knowledge of the influence of heat transfer rates on the solidification of metals is essential to the understanding and control of industrial casting processes. Since very few formal methods are available for solving the heat conduction equation under solidification conditions several authors have developed approximate techniques for doing so. One of the most promising is the integral-profile technique that has been used by Goodman,1 Hills,2,3 Tien4 and Hills and ~oore&apos; to predict solidification rates under certain specific heat transfer coniditions. In the first of this present series of papers6 Hills has further generalized the method and developed a universal integral-profile technique that can be used to predict solidification rates under a wide variety of unidirectional heat flow conditions. Since the method is approximate it is necessary to investigate the accuracy with which it predicts actual solidification rates. A review of the literature7 shows that solidification rates have seldom been measured under accurately known heat transfer conditions and it was therefore decided to develop experimental techniques that would enable this to be done. Results obtained would then be available as a check on the approximate solutions already developed, and in the development of further solutions that would be applicable under more complicated conditions. The initial work in this experimental program which is described here, is concerned with the solidification of pure metals at zero superheat under unidirectional heat flow conditions. Subsequent experiments have been concerned with the solidification of pure metals at appreciable superheats, under varying unidirectional heat flow conditions and under two dimensional heat flow conditions. In a series of experiments recently initiated, the solidification of binary alloys is also being investigated. The results of these subsequent experiments, together with relevant theory, will be described in later papers. The solidifying metal has been cooled in all the experiments, by a multiple air jet system designed so that the heat transfer coefficient to the cooled surface is constant and is uniformly distributed over the surface. This type of system has been chosen since only one parameter is needed to specify the heat transfer conditions and since these conditions are analogous to those met in certain continuous casting processes.&apos; Air cooling was chosen in preference to water cooling, however, since it offers a wider range of heat transfer conditions, and since it can be investigated by analogous mass transfer techniques. The first part of this paper discusses the existing integral-profile solutions that correspond to the heat transfer conditions used in the experiments, and describes the development and use of the experimental apparatus. In subsequent sections the heat transfer and solidification results are presented, and the various theoretical predictions are compared with them, and with one another.

Jan 1, 1970

By T. J. Whalen, M. Humenik

The liquid surface tension of copper-nickel ad copper-nickel-titanium-carbon alloys and the wettability of titanium caybyde by these alloys have been measuhed. It was found that the surface tensions of the binary copper-nickel alloys Lie on a smooth curve between the end members, copper and nickel. The addition of small amounts of titanium and carbon has nO effect on the surface tensions of copper-nickel alloys. Small additions of nickel to copper significantly reduce the contact angle of Ike alloy with titanium carbide. From a Gibbs treatment, nickel is shown to be adsorbed at the titanium carbide-alloy interface. X HE microstructure of two-phase materials has been shown to be influenced largely by the interfacial energies between the phases present.&apos; , In systems prepared by powder metallurgy techniques and densi-fied in the presence of liquid phase, a precise analysis of microstructure and interfacial energy relationships requires a knowledge of the solid-solid interface energies and liquid-solid interface energies. However, marly metal-nonmetal systems are characterized by the "sweating" of the liquid during sintering, and in these systems wettability is a principal consideration. The wetting in turn is dictated by the various interface energies of the system, as shown in Fig. 1 for a liquid drop formed on a solid substrate. The equation which expresses the vectorial balance of surface forces in the horizontal plane, at the point of contact, A, is given by: where ssv = solid-vapor interface energy sSL = solid-liquid interface energy sLV= liquid-vapor interface energy 6 = contact angle measured through the liquid phase. The angle and the surface tension, slv, can be measured accurately by the sessile drop method.3, The absolute value of the surface energy of the solid cannot be determined by this method, but with reasonable changes in the composition of the liquid only, the value of ssv can be considered constant. The changes in contact angle, then, can be attributed to changes in sSL and sLV and since sLV can be measured, the changes in sSL can be determined. Several studies have indicated that the surface and bulk properties of solid alloys can be correlated with electronic structure. The catalytic activity of copper-nickel alloys was reported to follow the dband vacancies in these alloys.5 Nickel has been considered to have 0.6 holes per atom in the d-band. The addition of copper to nickel is thought to bring about a filling of the d-band of nickel, since each copper atom contributes one electron. Thus, at an atomic concentration of 60 Cu-40 Ni (62 wt pct Cu-38 wt pct Ni) the d-band is believed to be full, and magnetic measurements support this view.6 If the electronic structure is influencing a property of the alloy, this property should show some sort of discontinuity as the composition changes from one side of the 60 Cu-40 Ni composition to the other. Since the catalytic activity can be considered as a surface property of the alloy, it is logical to assume that other surface properties, such as surface tension, may also be influenced by electronic structure. The suggestion has been made that there is a correlation between the solid titanium carbide-liquid Cu-Ni alloy interfacial energy and d-band filling.7 One purpose of this investigation was to determine if the changes taking place in the electronic structure with compositional changes in the solid copper-nickel alloys were reflected in the surface tension values of the liquid alloys. Such a change, if present, would lend support to the suggestion that one can refer to discrete energy bands in the liquid state. Other purposes of the present study were to investigate in detail the wettability in the system copper-nickel-titanium carbide, and to discuss the possible processes which take place during wetting in this system.

Jan 1, 1961

By S. S. Marsden, S. H. Raza

An experimental study of the flow of line-textured. aqueous foams through Pyrex tubes is described. The foams range in quality F (ratio of gas volume to total volume) from 0.70 to 0.96 and behave like pseudoplastic fluids. At lower flow rates they exhibit laminar flow ad have apparent viscosities which increase with quality, and which cover a range of 15 cp to 255 poise for tubes of 0.25- to 1.50-mm radius rj. At higher flow rates a plug-like type of flow is developed, the extent of which increases with both T and ri. When the same foams flow through either open or packed Pyrex tubes, remarkably high streaming potentials ?E are often generated. These can easily reach 50v if nonionic foaming agents are used, but are at least an order of magnitude less for ionic foaming agents. A linear relationship between ?E and the pressure differential ?p is observed; this usually extrapolates to positive values of ?p at ?E of zero. The slope of the line increases with both F and ri. An equation was derived to describe the streaming potential of non- Newtonian fluids in circular tubes and was used to correlate experimental results. The calculated < potentials are of the right order of magnitude. INTRODUCTION Foams are both unusual and inniguing in their physical properties, and have been the subject of many scientific studies. However, present knowledge of foams is still fragmentary, specific and often contradictory. Apparent viscosity of foam is the physical property of greatest interest to both rheo1ogists and engineers. sibreel reported that the apparent viscosity decreased with increasing shear rate in a manner similar to some non-Newtonian fluids. Penny and Blackman2 reported that fire-fighting foams had both a limiting shear stress and a tensile yield stress. There is little doubt that some foams at least behave like non-Newtonian fluids, and have apparent viscosities considerably higher than those of either constituent phase. The high apparent viscosity of foam with its concomittant effect on mobility ratio and sweep efficiency no doubt prompted several attempts by research groups to use foam as a displacing agent in porous media. Based on recent experience, most of these groups probably succeeded in completely blocking fluid flow in the porous media and then abandoned their efforts. Two groups apparently found the successful combination of experimental parameters at about the same time.3,7 Others have recently added to our knowledge of foam flow in porous media and its use as a displacing agent.8-13 An experimental problem encountered by Fried3 was a transient blockage of foam flow in porous media when distilled water was used to prepare the foam-producing solution. Fried surmised that this was due to an electrokinetic effect and he eliminated it by using electrolytes in preparing foaming solutions. He also measured the streaming potential of a number of foams in capillary tubes which he found to be appreciably higher than those obtained when the constituent liquid flowed under comparable conditions. This paper presents results of a more comprehensive study of the streaming potential generated by aqueous foam flowing in both open and packed Pyrex tubes. It also adds to knowledge of the rheology of these foams as deduced from their flow behavior in open tubes. APPARATUS AND PROCEDURE A diagram of the apparatus used is shown in Fig. 1. Details of its construction, testing and use are described elsewhere.14 Careful selection of materials, extreme cleanliness and rather elaborate electrical insulation and shielding were necessary to obtain reproducible results (±5 percent). Both streaming potential and streaming current were measured with an electrometer. The design of the foam generator developed for this work is novel (Fig. 2). It will produce uniform fine-textured foams at pressures sufficiently