Search Documents

By John D. Gill

THIS paper assumes the incontrovertible nature of the statement that the validity of competition in the nonnatural resource industries is established firmly on the rate and extent of the economic development of the United States. It then demonstrates the nonexistence of any condition within the petroleum industry that would invalidate the principle of competition as applied to it. It points to the benefits that competition has effected in the oil industry and the reasons why the practice of the competitive principle should continue to keep the industry virile and progressive in meeting the requirements of future generations for the kind of products natural to it. Finally, it pleads for a clearer view of the affairs of the oil industry by seeing them against a background of the whole economy. INTRODUCTION Even a few years ago there would have been only an academic reason for presenting before this Institute a paper on the validity of competition in the oil industry or any other natural resource industry; today there is no more practical subject for this body to consider. In social importance it transcends attempted solutions of perplexing technical problems; and even the numerous legal and economic problems that grow out of administration of state regulatory measures appear to be of secondary importance because they would cease to exist if competition were abolished. The aspiration of certain elements of the Federal Government to acquire control of the oil industry has long been suspected The vital need for petroleum in the national defense ... confirms my belief in the urgent need of Federal legislation to safeguard our petroleum supply through prevention of waste and by establishment and maintenance of sound economic conditions in the oil industry... . But also it may be dismissed with this mere mention of it because it predicates government control and the abandonment or broad reduction of competition on a war emergency. Clearly, the fight for a nation's life may justify a government's control over men and resources that would be abhorrent and economically enervating under conditions of national security. More pertinent to the present matter, because it appears expressive neither of a personal ambition nor of an emergency condition but rather of the long-range view of a certain school of conservationists, is the pronouncement of no less an authority than the Attorney General of the United States, who has been repeatedly quoted by the press as saying that the American Petroleum Industry constituted a case "where the principle of conservation of an exhaustible and irreplaceable resource should replace the principle of competitive exploitation." The significance of this statement in the light of the commonly accepted meanings of the " principle of conservation" and of the "principle of competitive ex-

Jan 1, 1941

By L. J. Demer, W. W. Walker

AMONG several variables of the indentation hardness test is the effect of loading time on the measured hardness of a material. The most generally recommended duration of loading is 10sec.1-3 Although this short loading duration is undoubtedly satisfactory for harder metals, it is questionable that it is sufficient for very soft metals,4 or for certain plastics.5 The effect of duration of loading on the measured hardness of ionic crystals is largely unknown, although Onitsche and Mitsches found that the indentor (under a very low load) had not yet reached equilibrium after 60 sec in a variety of ionic crystals. To extend further the data of Onitsche and Mitsche, a systematic study was made of the effect of duration of loading for longer periods, up to 50,000 sec, on the 136 deg Dph of synthetic lithium fluoride. For comparison, less extensive tests were made on synthetic magnesium oxide and copper single crystals. The general procedure used was to indent a cleaved and polished (100) face of a lithium fluoride crystal using a Leitz Durimet microhardness tester. In certain cases, the indentor was so oriented as to align the diagonals of the 136 deg diamond pyramid indentation parallel to a (100) edge. In other cases the diagonal of the indentation was aligned at 45 deg to a (100) edge of the crystal. After indenting, the surface tested was etched in the acid etchant recommended by Gilman and Johnston.' This revealed the position of dislocation lines which intersected the surface tested. At these points of emergence were formed the usual sharp, pyramidal etch pits as shown in Fig. 1. The specific procedure used in studying duration of loading was as follows. The surface of the crystal was indented, and the load was left on the indentor for a predetermined time. This duration of loading was varied systematically from 1 to 50,000 sec. After the desired amount of time had elapsed, the indentor was removed from the crystal and the size of the resulting indentation was determined using a micrometer eyepiece. The surface was then etched to reveal the dislocation etch pit pattern around the indentation. Procedures used for lithium fluoride, magnesium oxide, and copper were similar. Preliminary studies revealed that, although an indentation was enlarged by increasing loading time, no corresponding changes occurred in the surface etch pit pattern. Since no evidence of dislocation movement was observed on the surface, it was assumed that the plastic deformation indicated by the indentor sinking into the surface was a result of dislocation movement inside the crystal. This movement was studied bf making a series of surface indentations in a crystal corresponding to various lengths of time, cleaving the crystal vertically through the indentations, etching the freshly

Jan 1, 1964

By Sidney A. Swensrud

The 24-in. crude-oil line. and- the 20-in. petroleum-products line, built as a war emergency by the United States Government and running from points in Texas to the New York-New Jersey-Philadelphia area, were constructed only because of the inability during the war to continue nor-inal ocean tanker movements from the Gulf Coast to the East Coast. The postwar disposition of these lines may be considered as one of the important problems of the postwar readjustments in the oil industry, if not the most important one. In the first place there appear to be many complications in keeping the lines in crude-oil or petroleum-products service. This conclusion was reached also in a study by T. E. Swigart, President of Shell Pipeline Corporation.' Since the lines are too largc for any one company to utilize, and since it appears likely that a surplus rather than a deficiency of tankers will exist after the war, most companies probably will feel that they can achieve lower costs and more satisfactoiy results from the resumption of tanker movements to the East Coast rather than by endeavoring to take over or utilize the capacity in the large pipe lines under some tariff-rate structure. As for using the lines for making deliveries to the middle west or central eastern areas, it would appear that when the war is over and normal transportation arrangements can be resumed, there will be no need of any extra capacity for such deliveries. Therefore, the War Emergency lines could be utilized for this purpose only if privately owned pipe lines and other transportation facilities were to be displaced. Against this rather unprepossessing prospect for use in petroleum or product service is the fact that at or near the source of the lines lie the greatest developed gas reserves in the world, for much of which there is at present no satisfactory market outlet; and at the other end of the lines lies one of the greatest concentrations of population in the world, which is not now served by natural gas. These who have been fortunate enough to use natural gas can have little doubt of its desirability as a domestic fuel. An analysis of the market potentialities and comparison with other areas where natural gas is being distributed, and where it has displaced manufactured gas, makes it seem clear beyond question that the full capacity of both of the large-diameter lines could be fully utilized in this service, and this without creating any undue drain upon the gas reserves of the nation. On the basis of an estimated capacity of roo to 120 billion cubic feet per year, the gas that might be marketed through these lines would amount to only 3 to 4 per cent of the total con-

Jan 1, 1944

By Walter Showak

The published phase diagrams for the copper-zirconium system1,2 indicate that the solid solubility of zirconium in copper is not accurately known. Studies made on relatively impure alloys by Pogodin, Shumova, and Kugucheva3 yielded a maximum solubility value of 1 wt pct Zr at the eutectic temperature. Allibone and sykes5 reported that an as-cast 0.2 wt pct Zr alloy is single phase at room temperature. Limited results obtained by Raub and Enge14 indicated that zirconium solubility in copper is less than 0.13 wt pct Zr at 940°C. Tn 1960, on the basis of a microstructural examination of several copper-rich Cu-Zr alloys, saarivirta6 placed the maximum solubility of zirconium in copper at 0.15 wt pct at the eutectic temperature, 980°C. The present note describes results obtained during a re-investigation of the Cu-Zr system for the purpose of accurately establishing the solidus and solvus curves and the eutectic temperature in copper-rich alloys. High-purity copper (99.99 pet) and zirconium (99.64 pet) consolidated reactor grade sponge were used to prepare several alloys, containing up to 2 wt pct Zr, by induction melting in graphite crucibles in vacuum and chill casting into a split steel mold. The melting procedure consisted of first melting the copper charge and then adding the bulk zirconium wrapped in pure copper foil. Chemical analyses were made of both the cold-rolled alloy ingots after homogenization at 925°C for 450 hr in evacuated quartz capsules and of small specimens which had been used in the phase diagram studies. 'The carbon content of each alloy was also determined and was found to be less than 0.001 wt pct in every case. Metallographic and electrical resistivity measurements were used as the primary methods for this investigation, although some thermal analysis studies were also performed. Heat treatments of all the alloys were carried out with the specimens wrapped in molybdenum or alloy foil (of the same composition as the specimen) and sealed in quartz tubes either in vacuum or under a purified helium atmosphere. Following high-temperature anneals for long periods of time, slight depletion of zirconium from the specimen surface was observed. Therefore, careful preparation of samples for microscopic examination and chemical analysis of the samples themselves was necessary to check the composition of samples used in determining phase boundaries. Points on the solvus curve were determined on quenched specimens by both isothermal reaction after solution heat treatment at 950°C for 8 hr and by isothermal annealing of alloy specimens at successively higher temperatures for times ranging from 24 to 500 hr. Liquation studies for positioning of the solidus and eutectic temperatures were performed by holding a pre-

Jan 1, 1962

By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

The Inspiration ore body was discovered in 1904, but a 50 -ton mill which was installed to treat the disseminated copper ore promptly failed. The original Inspiration Company then gave way to another, backed by W. B. Thompson, which found 40 million tons of ore. Control then passed to Anaconda and Dr. Louis Ricketts took charge as consulting engineer. He abandoned the mill which had been partially built (to the horror of the stockholders, according to Ira Joralemon) and spent a year and a million dollars experimenting with flotation. The first large copper flotation plant was then built and recovered 50% more copper than had previous gravity mills. It, of course, was highly successful and became the forerunner of modern flotation plants. Inspiration is distinctive as the first fully integrated copper operation in the United States. Three open pits supply sulfide ore to the concentrator and mixed oxide and sulfide ore to a vat leaching and electrowinning operation with leached ore also being sent to the concentrator. In addition, dump leaching supplies pregnant solution for scrap iron precipitation. Inspiration has recently constructed an electric furnace smelter and also operates a continuous casting and rod plant. The new primary 54 in. by 74 in. crusher was completed in May of 1972 and replaced an older unit which was in the way of the open pit development. It is of an unusual circular silo design, which permits dumping 0 from two positions at 90 from each other. One dumping position is in line with the spider, while the other one is at right angles to it. A box girder splitter bar hung from the dump pocket slopes downward from the second dump point, across the spider cap, and rests on the pocket bottom. This splitter was not installed to protect the spider but was to aid in distributing wet ore being dumped from that position to both sides of the spider. Any large amount of wet ore delivered to one side of the spider would pack in the crusher cavity. The round front wall of the 18 ft (5.5 m) deep pocket is unlined except for light steel protection at the top, while the straight back wall is lined with vertically positioned railroad rails. Water for dust suppression is sprayed into the pocket through a cluster of 3/8 in. (9.5 mm) nozzles at the back of the pocket. About 5 gpm (19 lpm) of water are mixed with 90 psi (620 kPa) air upstream of the nozzles to produce a fog which is effective in dust control. The 54 in. Allis -Chalmers gyratory is placed mostly within one quadrant of the circular enclosure to permit placement of the apron feeder on the lowest level in the proper position to transfer crushed ore to the

Jan 1, 1978

Copper ores from small mines in the area south of Tucson, where the Twin Buttes mine is located, were first operated in the 1880's. Today this area is one of the great copper mining centers of the world. In 1963, Anaconda Company acquired the property from Banner Mining Company and in recent years joined with AMAX in a 50/50 partnership to work the Twin Buttes property. From the beginning, Anaconda had relied on conveyors to remove overburden, oxide material for eventual leaching, and ore from the open pit. In the large st preproduction stripping program in mining history, Anaconda in a four-year period (1965 to 1969) removed 266 million tons of overburden of an average depth of 500 ft (152 m) lying over the ore body. The alluvium overburden was stripped by scrapers carrying 70 to 80 tons and push-loaded by two D9 tractors operating in tandem. The scrapers delivered their loads to bins which fed a 60 in. (1.52 m) conveyor having a capacity of 8500 tph. The 25% slope belt conveyor, which was 2100 ft (640 m) long, transported the material to the brow of the pit, where it was transferred to an 8300 ft (2530 m) surface belt to a 1000 ton loadout bin. At this point, the overburden was trucked to the sites of the tailings ponds, where it was used for dam construction. During 1976, the one billionth ton of overburden was removed from the Twin Buttes mine. The Twin Buttes quartz monzonite porphyry contains only scattered mineralization of which chalcopyrite is the most abundant mineral, associated with chalcocite, covellite, minor bornite, and several oxide minerals. Oxidation has progressed to variable depths of up to several hundred feet below the base of the alluvium. Because of the depth of the sulfide and oxide ores and hard rock waste, two in-pit crushers and conveyor systems were also installed for their transport out of the pit; and in 1976 a third crusher and conveyor system was installed lower in the pit for waste rock only. The two initial crushing and conveying systems were designed to handle any of three functions: crushing waste to be disposed of by a rail-mounted stacker -conveyor, crushing oxide ore for conveyor and then truck transport to stockpiles for future leaching, and primary crushing of sulfide ore for conveyor transport to the two 30 in. by 70 in. (0.76 by 1.78 m) secondary crushers and the two 7 ft (2. 13 m) standards and four 7 ft shortheads in the third and fourth stage crushing plant. A third standard crusher has been in- stalled recently. Mining is done by 15 yd (11.5 cum) shovels which load 100- and 150-ton

Jan 1, 1978

By R. G. Hall

The method of crushing rock by throwing with violence against a resisting surface does not differ in principle from the method of dropping it from a height upon a specially arranged surface. The former is applied in various mills now in use, especially those for reduction of the softer rocks and minerals. The latter is the principle of the Hadsel mill. Probably not new, but Hadsel's method of approach is at least novel, and applicable to hard as well as softer rocks. An elevating wheel raises the rock and drops it from a height upon a hard metal plate or series of plates. The first commercial mill consisted of two units, one on each overhung end of a horizontal shaft, driven by a gear train from a 100-hp. motor. A description of this machine, then in operation at a mine at Georgetown, Calif., was printed in the Engineering and Mining Journal (April, 1932) and need not be repeated here. That machine took mine run ores of a size up to 12 in. and successfully produced a pulp of approximately minus 60 mesh, suitable for flotation. The mills were each 24 ft. in diameter and 3 ft. in width of face. The elevating buckets were formed of steel plates, extending inward from the periphery, inclined to the tangent at 75". This plate was 3 ft., the width of the wheel, and 2 ft. deep. One side of the wheel towards the carrying shaft was closed, the other was open except for the rim plate enclosing the ends of the buckets and extending inward about 5 ft. on the radius. About a 90" arc was immersed in a concrete tank, which acted as a classifier. The breaking plates, seven in number, were carried cantilever through the open side of the wheel. The lowest plate was placed just above the water level. The illustrations (Figs. 1 and 2) make plain the general arrangements. The plant set-up was somewhat crude but worked well enough to demonstrate the weak points of the mill. In this operation it was early apparent that, considering all the factors from delivery of the mine run ore to the final pulp for flotation or cyanida-tion, the Hadsel mill offered possibilities of great simplicity of plant and savings in power. Continuous operation developed mechanical weaknesses, some of which were readily discernible in details of design, some became more apparent as operations progressed.

Jan 1, 1935

By D. B. Robinson, C. A. Macrygeorgos, G. W. Govier

Experimental data have been obtained on the volurrletric behavior of ternary mixtures of methane, hydrogen sulfide and carbon dioxide at temperalures of 40°, 100" and 160°F up to pressures of 3,000 psia. The results indicate that the compressibility factors for this system do not agree with compressibility factors for sweet natural gases at the same pseudo-reduced conditions. The deviation increases as the temperature and methane content decrease. Discrepancies of up to 35 per cent were observed. A careful analysis has been made of the existing pUrblished data on compressibility factors for binary systems containing light hydrocnrbons and hydrogen sulfide or carbon dioxide. It has been found that the deviation of actual from predicted compressibility factors for methane-acid gas mixtures is a function of the methane content and the pseudo-critical properties,.v of the mixture. The ratio between actual compressibility factors for methane-acid gas mixtures and compressibility factors for sweet natrlral gases at the same pseudo-reduced conditions has been currelated over a range of pP,, from 0 to at least 7 arid a range of pT, from about 1.15 to at 1east 2 0 with an error not exceeding 3 per cent and over most of the range within I per cent. The validity of the correlation for mixtures containing appreciable hearvier hydrocorbons has not been fully established, but it is shown to be preferable than the use of a corretation based only on hydrocarbons. INTRODUCTION Although a relatively accurate method for predicting compressibility factors of pure materials is provided by charts based on reduced properties and the assumption that the compressibility factor is a unique function of T P and z the determination of the correct values of compressibility factors for gas mixtures is somewhat difficult. Two general methods of dealing with gaseous mixtures have been proposed. The first assumes a direct or modified additivity of certain properties of the mixture in terms of the properties of the individual components. Examples of this method are based on the familiar laws of Dalton and Amagat. The second method averages the constants of an equation of state applicable to the pure components. Both of these methods are of limited value in engineering calculations because the first usually provides reliable answers only over narrow ranges of pressure and temperature and the second is cumbersome to handle. In petroleum engineering practice accurate estimations of the volumetric behavior of natural gases arc frequently required. To fulfill this need, several generalized compressibility charts have been developed.' ' Of these, the one prepared by Standing, el al is widely used at present. In the construction of charts of this type a third method for dealing with mixtures has been followed. It is based on correlation of pseudo-critical properties as outlined by Kay and calculated from the critical properties of the individual components in a mixture. Although these charts provide relatively accurate information on the compressibility of dry or wet sweet natural gases, they are less reliable when used for gases containing high concentrations of hydrogen sulfide or carbon dioxide or both. Thus, an experimental program, although time consuming, is the best means now available for the determination of the volumetric behavior of sour or acid gas mixtures. An increased interest in the behavior of these gas mixtures, particularly in connection with some of the fields in Western Canada where the acid gas concentration of the reservoirs may be as high as 55 per cent and where hydrogen sulfide alone may be as high as 36 per cent, provided the incentive for this study. It was the purpose of the investigation to determine the volumetric behavior of selected mixtures of methane, hydrogen sulfide and carbon dioxide over a range of temperature from 40" to 160°F and at pressures up to 3,000 psi. EXPERIMENTAL METHOD The apparatus used in this investigation was basically the same as that described by Lorenzo.'" The amount of each pure component used in preparing the gas mixtures was measured over mercury in a glass-windowed pressure vessel. The pure components were then transferred individually in the desired amounts to a second glass-windowed pressure vessel where the volumetric behavior of the mixture was determined. Volume was varied by mercury injection or withdrawal. The capacity of the cell was about 125 cc. Temperatures in the cells were measured with copper-constantan thermocouples and a Leeds Northrup semi-

By C. H. Li, R. J. Stokes

This paper compares the fracture behavior of tungsten rods in three conditions: recrystallized. recovered, and wrought. Notched specimens suhjected to a 50 in.-lb impact load showed ductile-brittle transitions at 700, 4.90°, and 440°C, respectinely. The recrystallized material had an equiaxed pain structure and jracbred by simple cleavage from a grain boundary source at all temperatures up to 700°C. The wrought and recovered material had an elongated fibrous structure and at low temperatures fractured by cleavage originating from the notch. As the transition temperature was approached cleavage was preceeded by more and more intergvanular splitting which deflected the crack front into planes parallel to the tensile axis. The enhanced toughness of wrought and recovered tungsten was attributed both to its inability to initiate cleavage because no pain boundaries were suitably oriented perpendicular to the tensile stress and to its inability to maintain cleavage because of intergranular splitting ahead of the crack. It has been appreciated for a long time in a qualitative manner that the room-temperature brittleness of fully recrystallized tungsten may be alleviated by working the material at relatively low temperatures.' More recently this difference in mechanical behavior between wrought and recrystallized tungsten has been examined quantitatively by measurement of the tensile properties as a function of temperature. In these experiments brittleness has been expressed in terms of ductility or reduction in cross-sectional area upon tensile fracture or in terms of the bend radius before fracture under bending.' This work has shown the existence of a fairly sharp transition from brittle to ductile behavior with an increase in temperature. The ductile-brittle transition temperature for recrystallized material is approximately 200°C higher than for wrought material. An increase in strain rate, small additions of impurity,' or an increase in grain size4 shift the respective transition temperatures to higher values, but the difference between them remains approximately the same at 200°C. A number of explanations for this embrittlement by recrystallization have been given. It has been blamed either on the concentration of impurity at the grain boundaries, the increase in grain size, or the change in texture which occurs upon recrystallization. The present paper examines the effect of different heat treatments on the notch-impact behavior of commercial powder-metallurgy tungsten rods. The change in the ductile-brittle transition temperature for this method of loading and the fracture mode has been related to the different mi-crostructures produced by heat treatment. EXPERIMENTAL PROCEDURE Commercial swaged powder-metallurgy tungsten rods 1-3/8 in. in length and 1/8 in. in diameter were machined to introduce a sharp V notch 0.030 in. deep. To change the microstructure from that of the as-received wrought material some of the specimens were subjected to an anneal in nitrogen either at 1300° or 1400°C for 8 hr or at 1600° or 2000°C for 1/2 hr. The notched rods were then placed in a miniature Charpy-type impact machine and struck at their midpoint (opposite the notch) with a hammer designed to deliver 50 in.-lbs of energy. The strain rate at the base of the notch was estimated to be approximately 100 sec-1 at the instant of impact. The specimens were heated in situ to the desired impact temperature. The microstructures produced by the various anneals were studied by both X-ray diffraction and metallographic techniques. Fig. 1 reproduces the microstructures observed metallographically following a 10-sec electroetch in a 10 pct KOH solution. Fig. l(a) shows the elongated fibrous grain structure of the as-received material. Following the anneal at 1300" or 1400°C the grain structure was still elongated as shown in Fig. l(b) but the etch pits delineated dense polygonized dislocation arrays within many of the grains. Occasionally a relatively dislocation-free recrystallized grain was found growing into the matrix. The anneals at 1600° and 2000°C resulted in complete recrystallization and some grain growth. The grains produced at 1600°C were still slightly elongated as shown in Fig. l(c) whereas the anneal at 2000°C produced equiaxed grains. The changes in grain size produced the expected changes in the X-ray back-reflection patterns; there was no indication either in the as-received material or the annealed material of any preferred orientation. RESULTS a) Impact Behavior. Fig. 2 reproduces the ductile-brittle transition curves measured in the manner described in the previous section. It can be seen that under these testing conditions the as-received

Jan 1, 1964

By W. A. Oates, J. A. Lambert, P. T. GaIIagher

Monte Carlo methods have been used to compute the arrangements of interstitial atoms dissolved in tetrahedral sites in bcc lattices. It is assumed that the presence of an interstitial atom "blocks " a certain number of neighboring sites and prevents their occupancy. Sites "blocked" by more than one filled site are allowed for. The computed values of. the mean occupation number (defined as the ratio of the total number of sites blocked to the number of solute atoms are used to calculate the configurational entropies of the solutions. These entropies are compared with those resulting from previous theoretical studies of this problem and also with available experin~ental data for the p Zr-H, Nb-H, V-H, and Ta-H systems. Evidence is also given that the "blocking" explanation of low limiting compositions in these systems, rather than this being due to initial limitations on the number of sites available, is probably correct. THE ideal partial configurational entropy of mixing of an interstitial solute in a metal is given by: where p is the number of interstitial sites per metal atom and Xi is the atomic fraction of the interstitial. For the bcc lattice. which we shall be concerned with in this paper, the interstitial positions are shown in Fig. 1. It can be seen that for the tetrahedral sites, p=6. whereas for the octahedral sites, p = 3. Different emphasis has been placed on the relative importance of energy and entropy effects in determining deviations from ideality in interstitial solid solutions. In some cases the same system, e.g., Fe-C, has been described by the contradictory regular and athermal solution models indicating that the enthalpy and entropy functions, derived from equilibrium data, are frequently not accu.rate enough to differentiate between these treatments. However, for certain metal-hydrogen solutions the equilibrium data is available over sufficiently wide ranges of temperature and composition to permit a reasonably accurate determination of the compositional variation of the heats and entropies. Hoch&apos; has attempted to interpret the results of interstitial solid solutions in terms of a regular solution model. In the case of the Ta-H system where 13 = 6, this model entails fitting the experimental relative partial entropies of solution, asH, to the equation: where ASgs is the relative partial excess entropy of solution of hydrogen. Hoch found that the results of Mallett and Koeh1 could be fitted to this equation with an approximately constant value of AF up to XH = 0.25. However, it is apparent from the solubility isotherms in this system which become asymptotic to the composition TaH that, since (Xh /6 - ~Xh ) becomes infinite only at TaH6, it is necessary that AS<&apos; tends to infinity at TaH. In other words, the low saturation composition of TaH, instead of the anticipated TaH,, eliminates the possibility of applying regular solution theory to such systems. Rather large negative excess configurational entropies must exist at higher hydrogen concentrations in order to explain the lower saturation values. To account for these low limiting compositions and excess entropies two distinctly different approaches have been followed. Rees and many others1-l2 have assumed that not all interstitial sites are crystallographically equivalent with respect to the interstitial addition; that is, in Eq. [I] p is less than the value anticipated from geometrical considerations. To describe, say, a bcc metal-hydrogen system with a limiting composition of MH by this approach one would consider that p = 1 in the first instance instead of p = 6.&apos;j3 In some cases, nonintegral values of B have been taken in order to improve the fit with the experimental data over limited ranges of composition. The other approach which has been used to explain the low saturation compositions is to assume that, although all sites are available for occupancy, strong repulsive interactions exist between the neighboring interstitial atoms, and hence occupancy of any site excludes or blocks a certain number of neighboring sites from being occupied. Earliest treatments of this concept considered the exclusion of an integral number, of nearest-neighbor sites from being occupied at all concentrations. In this case, the partial configurational entropy is given by: These early treatments failed to allow for the overlap of the blocked sites which will arise at all but the very lowest concentrations. More recently attempts have been made to calculate the effect of this decrease in the number of blocked sites on the configurational entropy. Using the quasichemical treatment of interstitial solid solutions as given by Lacher and assuming that an infinite repulsive interaction energy existed between the solute atoms. atom obtained an approximate configurational entropy applicable to the blocking with overlap case:

Jan 1, 1970

By Forrest V. Williams

The dislocatiorl and stacking-fault structuve of epitaxial GaAs1-,PX lms been examined by chemical etching. The layers were groun in the (100) direction and etch Pils were developed on (111} planes which nad been lapped and polished on the epiLaxia1 layevs. Tile effecL of the jollolcing cariables on the quality of the epilaxial layers has been examined: doping leuel, grouth rate, and composition. High stacking-faullL densilies weve found in the GuAsi_xpx layers. These are not observed in heavily dolled epitaxial layers tzar in layers with low phosphorus compositions. The dislocatiorz density in GuAsi-x px was highest at the sub-stvate- epilaxia1 layer interface. Composilion changes introduced dislocations in the epitaxial layers. ManY semiconductor p-n junction lasers of Group TIT-Group V compounds and their alloys have been reported in the past several years. Laser action at visible wavelengths in GaAsl-x,Px was first reported by Holonyak and Bevacqua. GaAs, a direct transition semiconductor which lases, and Gap, an indirect transition semiconductor which does not lase, form a continuous series of solid solutions.2 Laser junctions can be fabricated in GaAsl-xPx crystals with phosphorus compositions up to about 40 mol pct. In addition to the production of coherent radiation in these crystals, the efficient recombination radiation of p-n junctions in this material has equally important potential in the development of low-power semiconductor lamps. To achieve a high conversion efficiency of electrical to optical energy in p-n junctions in this material, the relation of physical properties of the crystal to luminescence efficiency must be better understood. Although the electrical, optical, and device properties of GaAsl -xPx junction lasers are understandably of considerable interest, the work to date indicates that the more serious problems are the chemical and metallurgical difficulties encountered in the growth of this material.3 In addition to the problems of chemical purity, crystal imperfections, such as dislocations and stacking faults, can be expected to affect both the efficiency of the radiative recombination process and the perfection of the p-n junction.3 The last requirement, i.c., that of the perfection of the p-n junction, is a particularly troublesome one in the fabrication of laser diodes. To obtain good laser diodes, the p-n junction must be flat, which permits the radiation to be reflected from the resonant cavity boundaries. Junction planarity is extremely sensitive to the crystal perfection of the semiconductor material. Also, it is known that at high dislocation densities (-105 per sq cm) it has not been possible to build laser junctions in GaAsl-xPx . Few studies have been reported on the crystal defect structure of GaAsl-,P,. The first serious study seems to be that of Wolfe, Nuese, and Holonyak,3 who examined the dislocation structure of monocrystalline bulk (nonepitaxial) material grown by halogen vapor transport. In this paper are reported some observations on the dislocation and stacking-fault structure of GaAsl_,P, crystals grown by a vapor transport process on substrates of GaAs. EXPERIMENTAL Crystal Growth. The GaAsl-xPx crystals were grown in an open-tube flow system, using two sets of reagents. GaAs, Pr(red), and HC1 were employed in one method. The transport reaction is =950JC GaAs+HC1 = GaCl +1/4As4 +1/2H2 and the deposition reaction is 2GaAs1-xPx +GaCl3 Composition control is obtained by the flow rate of the HC1 and the vapor pressure of the P4, which is maintained in a separately controlled furnace. The second method has been described by Ruehr-wein4 and utilizes gallium, AsH3, PH3, and HC1. The same transport and deposition reactions as above are involved. Composition control is obtained solely by the flow rates of the three gases involved. All of the crystals were grown on chemically polished GaAs substrates oriented on the (100) plane. The thicknesses of the epitaxial layers were typically 100 to 300p. Revealing of Dislocations. Dislocations were re-vealed on both the( 111 ) and { l l l }b faces by chemical etching. The specimen to be examined was mounted at 54.7 deg, lapped on glass with 3-p alumina, polished on cloth with 3-p diamond paste, and, to remove work damage, chemically polished at room temperature for

Jan 1, 1968

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20&apos;- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes&apos;5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1&apos;8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.&apos; Esin and his coworkers5&apos;10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,&apos;~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,&apos;~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "&apos;~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970

By Joe O. Ledbetter

INTRODUCTION Health physics as a profession really got a significant start during the Manhattan Project of World War 11. The Health Physics Society has recently published its 25th anniversary issue of the journal (June 1980). There was concern over radiation exposures during and after uranium production, especially about radium and its daughter products [Jackson 19401 and, as evidenced by the frequency of articles in the literature, there still is. The reason for this concern was expressed by Harley as "Workers engaged in the mining and pro- cessing of radium-bearing materials are exposed to dusts of the parent, to radon, and to the radon daughter products. In- haled radioactive particulates may be retained in the lung or redistributed to other organs of the body. Relatively minute de- posits of radioactive substances, particularly alpha emitters, have been clearly shown to be the etiological factor in a variety of injuries to industrial and re- search workers. " [Harley 1953] Emphasis in measurements has been placed on radium in water and radon in air, since these are the principal mobilized phases; however, it should be kept in mind that radium-containing particles do become suspended in air as aerosols and radon absorbs in liquids. Much of the uranium mining and production is being carried out aboveground. The principal difference between underground and surface (pit or leach) mining of uranium is the reversal in the relative importance of roles for the types of radiation dose. For aboveground the major radiation exposure is external gamma ray, whereas for underground it is internal alpha; for aboveground, the whole body penetrating is of greater importance than the lung alpha dose. AS a result of the politics involved and the law- suits for any and all diseases as being occupationally- caused, today , more than ever before, the successful performance of the activities connected with uranium production--before-, during-, and after-the-fact-- must include the provision of first class radiation protection. Such protection can be achieved by good measurements, thorough risk evaluations, and adequate controls. Meeting the ALARA (As Low As Reasonably Achievable) philosophy necessarily entails the determination of what is reasonable exposure. The necessary and sufficient elements of radiation safety under the ALARA dictum require a hard look at the dose versus effects data. There are times when the health physicist needs to make decisions of judgement rather than compliance with a well-defined regulation value. In order to facilitate such decisions, the real world must be separated from opinions that are merely artifacts of statistical variation and from the unprovable "what ifs" that are slanted to question the morality of any non-Luddite. UNITS VOCABULARY FOR DOSIMETRY There have been many radiation quantifying and dosimetric units introduced in the past. Fortunately, most of them did not catch on enough to become required knowledge for reading the health physics literature. The unit definitions necessary for our purposes here are the following: -curie (Ci)--unit of radioactivity equal to 3.7 x 10 10 disintegrations per second Webster&apos;s 19711 or the quantity of radionuclide that undergoes 3.7 x 10 nuclear transformations per second. Environmental levels of radioactivity are usually measured in picocuries (10-l2 Ci) per cubic meter for air and in picocuries per liter (pCi/~) for water and sometimes for air. .roentgen (R)--exposure dose of x or gamma rays that gives 1 esu of charge (either sign) to 1 cc of dry air @ STP. The roentgen is equivalent to an energy absorption of 86.7 ergs/g of air [Gloyna and Ledbetter 19691. .rad--radiation absorbed dose of 100 ergs per gram of absorber. The SI unit for absorbed radiation dose is the Gray; 1 Gy = 100 rads. orem--radiation absorbed dose of 1 rad times the quality factor (QF) for that radiation. The QF is 1 for x rays, gamma rays, beta rays, and posi- trons. For heavy ionizing particulate radiation, QF is a function of the amount of energy trans- ferred per unit length of travel, i.e. , the linear energy transfer (LET); the values of QF:LET in keV/um are as follows: 1:<3.5; 1-2:3.5-7; 2-5:7-23; 5-10:23-53; and 10-20:53-175 [Morgan and Turner 19 671 . For radiobiology, relative biological effectiveness (RBE) is recommended for use instead of the quality factor above that is for radiation protection: the RBE is the ratio of the dose of 200 kVp x rays to the dose of radia- tion in question (both in rads) to cause the same

Jan 1, 1980

By L. D. Jaffe, F. W. Cotter, E. Cordon

The hardenability of titanium-base alloys was studied by metallographic examination and hardness survey of Jominy specimens end-quenched from the B range. Analyses of the data led to the equation log J = -0.57 + 0.25 @ct Fe + pct Mn + pct Mo) + 0.19 @ct Cr) +0.16 @ct V) + 0.03 @ct Zr). Here J is the distance, in sixteenths of an inch, from the quenched end of a Jominy hardenability specimen in the position of peak hardness, for material quenched from the B range. This equation fitted the experimental data with a standard deviation of approximately 0.29. The effects of the elements Al, Sn, W, Cu, Ni, B, C, N, 0, and H, and of pain size, were not statistically significant or not practically significant. A check against hardenability measurements in the literature showed agreement within the stated standard deviation. The equation should be useful in estimating hardenability of new or modified titanium alloys. HARDENABILITY in a titanium-base alloy is the ability of the alloy to retain the B structure on quenching. An alloy with high hardenability will retain the /3 structure even when cooled relatively slowly from a temperature at which B or P plus a is stable. A low hardenability material will retain P only if quenched extremely rapidly from the range of p or 0-plus-a stability, or will not retain it at all, at room temperature. High hardenability is desirable in titanium alloys to be heat-treated to high-strength levels. Its value is by no means limited to large section sizes. With high hardenability, a material can be solution-treated and cooled at a variety of rates, either to give high strength directly or, more generally, to give a soft ductile condition from which high strength can be obtained by subsequent aging. With low hardenability, high strength can be obtained, if at all, only by very rapid quenching, and there will generally be little increase in hardness on subsequent aging; an alloy of this type is limited in its applicability. On the other hand, alloys of very low hardenability have some advantages in weldability; essentially, they are always in the annealed condition, after welding as well as before. For commercial alloys, hardenability data are usually available, in the form either of property data after cooling from the solution temperature at various rates, with or without subsequent aging, or of results of a standard hardenability test, such as that originally developed for steels by Jominy and Boegehold.&apos; When modifications of an available alloy are considered, or preparation of new alloy compositions, it would be Very convenient to be able to estimate the hardenability of the new material without having to make and test it. A method of estimating hardenability of titanium alloys from their composition was suggested by one of the authors some time ago, on a preliminary basis, utilizing scattered data found in the literature.&apos; It seemed worthwhile to carry out a systematic experimental study of the effect of composition upon hardenability. EXPERIMENTAL PROCEDURE Approximately fifty heats of various compositions, weighing 8 to 10 Ib apiece, were melted in a small inert-gas tungsten-arc furnace with water-cooled copper walls. The starting material was 110 Brine11 titanium sponge, with high-purity metals added for alloying. Each heat was bottom-poured under vacuum through a molybdenum burnout strip into a cold graphite mold, to form an ingot approximately 4-1/2 by 3-1/2 by 3 in.* From each ingot were cut *The material was melted and cast by Pitman-Dunn Laboratory, Frankford Arsenal, to whom the authors must express their thanks. two pieces 4-1/2 by 1-1/2 by 1-1/2 in. These were forged, at temperatures adjusted to the composition, into 1-1/4-in. rounds, from which standard 1-in.-diam hardenability specimens3 were machined. A number of small samples were also prepared from forged materials of each heat, annealed, quenched from various temperatures, and examined metallographically. The P-transus temperature was determined by observation of the degree of resolution of primary a in these pieces. samples for chemical analyses were also taken from the forgings. One hardenability specimen of each heat was solution-treated for 1 hr approximately 50°F above the measured transus temperature, and the other for 1 hr approximately 250°F above the transus. (An additional hour was allowed for the specimens to reach furnace temperature.) These are not necessarily the temperatures that would be selected for

Jan 1, 1964

By H. W. Meyer, H. N. Lander, F. D. Delve

A method of calculating the changes in blast-furnace performance brought about by burden and/or blast modifications is presented. Essentially the method consists of three simultaneous equutions derived from materials and heat balances. These equations can be used not only to evaluate quantitatively the effect of changes in process operating variables on furnace performance, but also to provide a useful means of evaluating changes in process variables which cannot be measured directly. It has been customary for a number of years to use simple heat and materials balances as a basis for assessing blast-furnace practice. A good example of the method used to set up these balances is that proposed by Joseph and Neustatter.1 This approach to process assessment has limited utility, however, in that it cannot be used to predict the furnace coke rate or production under new operating conditions. Using an approach based on multiple correlation of blast-furnace variables, R V. Flint2 has developed an equation which may be used to predict the change in coke rate that will result from some changes in operating conditions with a reasonable degree of accuracy. Although this equation has useful applications in production planning, it cannot be used to study the relationships between the operating variables and the fundamental thermochemi-cal characteristics of the process. In attempting to analyze the blast-furnace process quantitatively, the idea of dividing the furnace into zones3 may at first appear attractive. In our present state of knowledge, however, it is not possible to define with any accuracy the physical limits of such zones in relationship to their temperatures or to the reactions which may occur in them. Although its application is restricted, the zonal approach to blast-furnace analysis is useful in some instances. For example, the change in the calculated flame temperature in the "combustion zone" caused by injecting steam constitutes information which is helpful in understanding why the addition of steam to the blast is best accompanied by an increase in blast temperature. The zonal approach cannot, at the present time, be used to establish the relationships between process variables and process performance if the whole process rather than part of it is to be considered. One of the earliest approaches to the problem of relating blast-furnace operating variables to pro- duction and coke rate was that developed by Marshall.4 Essentially Marshall&apos;s work showed that it was possible to estimate the performance of a furnace by solving three simultaneous equations which consisted of rudimentary carbon and heat balances plus a further equation relating the production, wind rate, and the carbon burned at the tuyeres. Although these equations did not include all of the chemical and thermal variables of the process, their derivation and application seems to be the earliest attempt which achieved any success in relating prior furnace operating data to the calculation of furnace performance under different blast conditions. Work carried out in Germany has been directed mainly towards prediction of coke rates using material and thermal balances rather than statistical methods. wesemann5 used prior furnace operating data as part of the basis for predicting the change in coke rate accompanying a change in burden composition. This author employed a method of successive approximations to estimate the secondary changes in slag volume and stone rate brought about by the change in coke rate. The most recent analysis, which seems to have been developed concurrently with the thermochemical model presented in this paper, has been described by Georgen.6 This author has succeeded in improving on Wesemann&apos;s approach by expressing the total changes in the slag volume and stone rate in terms of the change in coke rate itself. This is accomplished in a manner similar to that used in the thermochemical model described in this paper. Although Georgen makes use of a calculated furnace heat loss, he does not relate the heat loss per unit of hot metal to the production rate as is done in the present work. Georgen&apos;s approach may be used to calculate the changes in materials requirements accompanying changes in furnace operation; it cannot be used to assess the resulting changes in production. The fact that blast-furnace behavior can be interpreted by consideration of the heat requirements of the process was demonstrated by Dancy, Sadler, and Lander.7 In the analysis of blast-furnace operation with oxygen and steam injection these authors showed that it was possible to account for the changes in production and coke rate

Jan 1, 1962

By E. C. W. Perryman

The wide grooves formed at the grain boundaries when high purity aluminum is attacked by hydrochloric acid or sodium hydroxide have been attributed by earlier workers to the high energy of the grain boundary material. The effect has been investigated for high-purity AI-Fe alloys with up to 0.055 pct Fe as a function of iron content and heat treatment. It is shown that the explanation given above is untenable, but that the results can be explained on the assumption that iron segregates to the grain boundary in solid solution. IN 1934, Rohrmann¹ showed that aluminum of 99.95 pct purity suffered intercrystalline corrosion when immersed in 10 to 20 pct hydrochloric acid, and that the susceptibility to intercrystalline corrosion depended upon the heat treatment given. The greatest susceptibility was found for specimens quenched from a high temperature (600°C) and the lowest susceptibility for specimens cooled slowly from that temperature. Lacombe and Yannaquis2 have shown that super-pure aluminum (99.9986 pct) annealed at 600°C suffers intercrystalline attack in 10 pct hydrochloric acid and that this attack is intensified by anodic dissolution in the same solution at a current density of 10 milliamperes per sq dm. No difference in extent of intercrystalline attack was found between the 99.993 and 99.986 pct Al, which led the authors to suggest that impurities played only a secondary role in the mechanism of intercrystalline corrosion. It was found, however, that the attack at the grain boundaries depended upon the relative orientation of the grains, large differences in orientation favoring rapid attack. Boundaries where the two neighboring grains were similarly orientated showed high resistance to attack as did boundaries between grains which were in twin relationship. These observations led Lacombe and Yannaquis to suggest that the intercrystalline attack was due to lattice discontinuities present at grain boundaries. Assuming that the grain boundary is a layer three to five atoms thick and has a crystal structure which is a compromise between the two neighboring grains it is clear that the discontinuities will increase with increasing difference in orientation between the neighboring grains and hence the increasing tendency to intercrystalline attack. Roald and Streicher³ investigated the effect of heat treatment of aluminum alloys ranging in purity from 99.2 to 99.998 pct on the corrosion resistance in 20 pct hydrochloric acid and 0.30N sodium hydroxide. They found that in hydrochloric acid the intercrystalline attack appeared to be determined by the type and quantity of impurities present and by the relative orientation of the grains. No difference in the susceptibility to intercrystalline attack was observed between specimens quenched and those furnace cooled, from 575°C. In 0.30N sodium hydroxide some materials exhibited intercrystalline attack, this taking the form of V-notches. Rohrmann¹ offered no explanation for the greater susceptibility to corrosion of material quenched from 600°C. It seems possible that this difference is connected in some way with a different distribution of impurity elements in the quenched and slowly cooled specimens. The fact that Roald and Streicher8 observed no difference between quenched and slowly cooled specimens may possibly be due to differences in either rate of cooling or silicon content or possibly both. Both these would be expected to have an effect on the distribution of impurity elements. Although the rate of cooling used by Rohrmann was slightly more rapid than that used by Roald and Streicher the position cannot be clarified because Rohrmann does not give the silicon content and Roald and Streicher give the silicon contents of only a few of their alloys. That Lacombe and Yannaquis2 found no difference in corrosion behavior attributable to impurities between the two materials they used may be because both were of high purity compared with the aluminum used by Rohrmann.¹ Although they found no difference in the corrosion behavior of their two materials it is possible that the results obtained by Lacombe and Yannaquis may, nevertheless, have been influenced by impurity distribution, since, on the transition lattice theory of grain boundary structure, it would be expected that sparingly soluble impurities would tend to segregate to boundaries where the orientation difference is such that there is a greater density of atomic sites of suitable size to contain them. It was considered worth while, therefore, to examine the corrosion properties of a series of materials of differing impurity content with the objects of confirming the experimental observations made

Jan 1, 1954

By D. Atkinson, C. Bodsworth, I. M. Davidson

A geometric model of interstitial solid solutions, which has been used previously as a basis for the prediction of carbon activities in Fe-C austenite, is shown to serve also for the calculation of nitrogen activities in Fe-N austenite. The model has been developed to enable predictions to be made of the activities of an interstitial element in the presence of two host atom species. The activities calculated via the model are shown to be in satisfactory agreement with the measured values in the austenite phase for carbon in Fe-C-Co, Fe-C-Cr, Fe-C-Ni, Fe-C-~n, Fe-C-Si, and Fe-C-V alloys and for nitrogen in Fe-N-Ni alloys. The effect of the second substitu-tional solute on the logarithm of the activity of the interstitial element is expressed as the product of a constant mad the atomic concentration of that solute. The constants so derived we related to the thermo-dynamic interaction coefficients which describe the effect on the activity coefficient of carbon of an added solute element. In recent years the thermodynamic activities of carbon and nitrogen in the single-phase austenite field have been determined for iron binary alloys and for several iron-base ternary alloys. In order to extend the use of these measurements, it is desirable to be able to predict with reasonable accuracy the activities of the interstitials at compositions and temperatures other than those which have been measured experimentally. In all the systems studied to date, the interstitial elements do not conform to ideal behavior. Hence, the available data cannot be extrapolated or interpolated using the simple thermodynamic concepts of solutions. Several models have, therefore, been formulated for the purpose of predicting the activity of an interstitial element in the presence of one species of host atom. These models can be divided into the geometric1"5 and energetic6-&apos; types. The former group is based on the assumption that at low concentrations the activity of the interstitial species is determined by a composition-dependent configurational entropy term and an excess free-energy term which is temperature-dependent but independent of composition. The purpose of this paper is to show that the treatment, based on a geometric model, can be extended to enable predictions to be made of interstitial activities in the presence of two substitutional host atom species. THE CONFIGURATIONAL ENTROPY OF MIXING ICaufman5 has shown that the configurational entropy, S,, for a binary solution comprising of a host atom species, A, and an interstitial species, I, can be expressed as: where NI is the atom fraction of the interstitial species, R is the gas constant, and (2 - 1) is the number of interstitial sites excluded from occupancy by the strain field around each added interstitial atom. The number of interstitial sites per host atom, p, is unityg for the fcc austenite solutions considered here. The configurational entropy of mixing for a ternary solution comprising two substitutional atom species, A and B, and one interstitial species, I, can be derived similarly. Let the number of atoms per mole of each of these species in the solution be represented by «a, ng, and nI. From geometric considerations, it is improbable that the addition of a few atom percent of a second host atom species will change the type of sites (i.e., octahedral) in which the interstitial atom can be accommodated in the austenite lattice. At higher concentrations (determined largely by the relative atomic radii of the atomic species present and any tendency to nonrandom occupancy of the host lattice sites) other types of interstitial sites may become energetically favorable. Restricting consideration to compositions below this limit, for 1 = 1 the number of suitable interstitial sites is given by (n + nB). However, if each interstitial atom excludes from occupancy (Z - 1) additional sites, the total number of sites available for occupation is reduced to (n + ng)/Z. The number of vacant interstitial sites is given by: The total number of recognizable permutations of the atoms must include the recognizable, different configurations of the A and B atoms on the host lattice. Assuming that these arrangements are purely random, and are not affected by the presence of the interstitial species, the total number of recognizable permutations in the ternary alloy is given by: The configurational entropy is obtained by expanding, using Stirling&apos;s approximation, and collecting like items, as:

Jan 1, 1969

By J. Alfred Berger, O. M. Katz

Selected samples of hydrided Zr-Hf alloys were rapidly quenched to voom temperature and exrtrnined metallographically, by X-ray diffraction, and through micro hardness studies to confirm high-temperutuve data Confirming experiments sllowed that there were five phases in this Lernary system: 1) hextrgonal with lattice parameters similar to that of the initia1 Zr-Hf alloy but slightly enlarged due to dissolved hydrogen; 2) fee with properties of a brittle, intermediate, hydride compound; 3) fct with c/a crvoltnd 1.07 and which appeared as a neetilelike precipitale; 4) hexagonal, designated ?, with c/a ratio of 2.37; and 5) orthorhombic, designated X, with a = 4.67, b = 4.49, and c = 5.093 and whose tnicro-st?ruct~ival nppetrl-nnce depcncled o/i, heat lvecrt~r~ent. The tetragonrrl phase never crppeal-erl witkorct the cubic hydricle. Abpecrrtrnce of 0 and A also tlependet on the hafnium content of the zirconium. A previous paper&apos; on the Zr-Hf-H system described the thermochemical data obtained with a high-vacuum, high-sensitivity mirrogravimetric apparatus. This data presented a fairly complete picture of the phase relationships at elevated temperatures. However, it could not establish the actual crystal structures, lattice parameters, or metallographic disposition of the hydride phases. The present complementary study utilizes X-ray powder patterns along with light and electron microscopy to characterize completely the five hydrided phases found in Zr-Hf-H alloys quenched to room temperature. Crystallographic features of the zr-Hf,2,4 zr-H,5-7 and Hf-H8 systems have been summarized in Table I. Designations of a, ß, and ? were retained in the Zr-Hf-H system for the phase regions through which the pressure-composition isotherms always sloped. However, it was not firmly agreed that these were single-phase regions.&apos; In fact, the region designated y always contained a cubic as well as a tetragonal phase after quenching to -196°C. MATERIALS Preparation of the high-purity Zr-Hf alloys has been described.&apos; The four zirconium alloys which were hydrided contained 37 wt pct Hf (23 at. pct), 51 wt pct Hf (37 at. pct), 73 wt pct Hf (58 at. pct), and 91 wt pct Hf (82 at. pct), respectively. These were designated B-2, B-4, B-6, and B-8. Photomicrographs of the initial alloys showed the material to be quite clean as would be expected from the precautions exercised in producing them. However, there were a number of annealing twins but no other subgrain structure. In addition to the four original alloys, fifteen hydrided samples were observed at room temperature. Hydrogen compositions are given at the top of Tables I1 to V. APPARATUS The phases present at elevated temperatures were studied by quenching hydrided samples to room temperature by two different methods, both under vacuum: 1) fast cooling of the sample tubes of the microgravimetric apparatus1&apos;9 with flowing air and 2) rapid quenching into liquid nitrogen. The cooling rate for 1) was 750° to 250°C in 30 sec. Since the microbalance chamber was not designed to permit very rapid cooling of a hydride sample, all liquid-nitrogen quenching was done in an auxiliary experiment. The auxiliary quenching apparatus consisted of a small-bore, high-temperature furnace, a sealed SiO2 tube containing the sample, and a dewar quenching flask filled with liquid nitrogen. The hydrided sample, previously quenched in the microgravimetric reaction chamber, was placed in a platinum boat in a vacuum-degassed SiO2 tube. A zirconium wire getter and degassed SiO2 rod, to reduce the internal volume, were also in the tube. After sealing the tube under vacuum the zirconium getter was heated to absorb the last traces of gas. Only the sample was heated at the reaction temperature for the desired length of time, and then the tube dropped through the opposite end of the furnace into the dewar. A quenching rate of 200" to 400° C per sec was estimated. Analyses of samples after the auxiliary experiment also showed practically no increase in oxygen or nitrogen content from heating in the SiO2 tube. All of the samples were examined at room temperature by the X-ray powder method. The majority of the powder patterns were obtained with double nickel-filtered CuKa radiation after 8- and 16-hr exposures in an 11.48-cm-diam camera. Cobalt and chromium radiation were also used to spread out the high d value end of the Pattern. Such patterns readily identified the minor phases. NO oxide or nitride lines were found. Where sharp back-reflection lines existed it was possible to reduce the

Jan 1, 1965

By A. U. Seybolt

The solubility limit of oxygen in columbium has been determined in the range between 775&apos; and 1100°C by means of lattice parameter measurements and microscopic examination. The solubility is a function of temperature and varies, in the range given above, from 0.25 to 1.0 pct O, respectively. BECAUSE of the marked deleterious effect of oxygen upon the mechanical properties of some of the transition metals, it is desirable to know something about the solubility of oxygen in these metals. The brittleness caused by oxygen in solution is particularly marked in the case of the group VA elements, vanadium, columbium, and tantalum. The solubility of oxygen in vanadium has already been reported in an earlier paper,&apos; and Wasilewski2 has given a value (0.9 wt pct) for the solid solubility of oxygen in tantalum at 1050°C. Brauer3 in 1941 investigated the Cb-0 system up to Cb2O5, but made no real effort to investigate the extent of oxygen solubility in the metal. He made the observation, however, that this solubility must be less than 4.76 atom pct (0.86 wt pct) oxygen. This estimate was made from X-ray diffraction results on the alloys CbO, CbO, and CbO; all alloys consisted of the terminal (Cb) solid solution plus CbO, but the last alloy containing 4.76 atom pct 0 showed only three very weak CbO lines. It is surprising that Brauer, by examining only three alloys, arrived at an estimate of the solubility which agrees very well with the results to be reported herein. Experimental Procedure A columbium strip obtained from Fansteel Metallurgical Products was cut into strips, 0.020x1/2x2 in. Two holes, about 3/16 in. in diameter, were made near the ends of the strips in order to hold them against a flat steel block for mounting in a General Electric X-ray spectrometer for lattice parameter measurements. The same holes were used to hang the specimens inside a fused silica vacuum furnace tube which was part of a Sieverts&apos; gas absorption apparatus. The apparatus and method of adding oxygen gas has been previously described.1 According to the supplier, the columbium obtained had the analysis given in Table I. After degreasing the samples, approximately 0.001 in. was etched from each side of the samples in order to remove possible surface impurities from the last rolling operation. For this purpose the following cold acid pickle was found satisfactory: 8 parts HNO3, 2 parts H2O2 and 1 part HF. Various Cb-O compositions were obtained up to 0.75 wt pct O by the gas absorption and diffusion technique. After the sample had absorbed all the oxygen gas added at 1000°C, an additional 24 hr was allowed for homogenization. This treatment appeared to be adequate, as shown by the linearity of the lattice parameter-composition plot. More concentrated alloys were prepared by arc melting mixtures of Cb and Cb2O5 since it was very time-consuming to make Cb-0 alloys in the neighborhood of 1 pct O, or over, by the diffusion method. When the flat strip specimens were used, they were ready for the X-ray spectrometer after cooling from the Sieverts&apos; apparatus. The cooling rate obtained by merely allowing the hot fused silica furnace tube to radiate to the atmosphere (when the furnace was lowered) was sufficiently fast to keep the dissolved oxygen in solution. Arc-melted alloys were reduced to —200 mesh powder in a diamond mortar, wrapped in tantalum foil, sealed off in evacuated fused silica tubes, and then heat treated as indicated in Table 11. The fused silica tubes were quickly immersed in cold water without breaking the tubes after the heat treatments. The tantalum foil prevented reaction between the fused silica and the sample; there was no reaction between the powdered samples and the foil at 1000°C, but some trouble was experienced at 1100°C. At this temperature level a reaction between the sample and the foil was sometimes observed, which resulted in erroneous parameter values. Experimental Results Hardness Tests: Since most of the X-ray samples were in the form of flat strip, it was convenient to obtain Vickers hardness numbers as a function of oxygen content. Compared to the V-O case,&apos; oxygen hardens columbium much more slowly, presumably because of the larger octahedral volume in colum-bium (about 12.0 compared to 9.3Å3 in vanadium), hence, requiring less lattice strain for solution. The plot of VHN vs wt pct O is shown in Fig. 1.

Jan 1, 1955