Search Documents

By D. E. Peacock, B. Harris

The mechanical behavior of a niobium (columbium)TUNG alloy containing 20 wt pet Ta. 15 wt pet W, and 5 wt pct Mo has been studied in the temperature range 77° to 423°K. All specitrzens tested, apart from those into which oxygen was introduced deliberately, were fully recrystallized at 1500°C, had an average grain diameter of approximately 0.03 mm, and a combined carbon, ox-vgen. nitrogen, and hydrogen content of not not more than 250 ppm The meckatnical behavior of this alloy was found to be similar in seine respects to that of unalloyed bcc transilion metals. Both yield and flow stresses were sensililae to changes in deformation rate and both increased rapidly as the temperature was lowered below 150°C. A detailed examination revealed, however, that most of the temperature dependencc of the yield stress could be accounted for by the temperature dependence of the elaslic, modulus, whish is not true of the unualloyed metals. In lension at moderate strain rates, the trunsition fvom ducfile to hvittle behavior occurred just belour room teunperature bur incveasing the oxygen content from 190 to 200 pptn raised the transition temperature to about 4000K. TUNGSTEN and molybdenum have been found to be very effective high-temperature solid-solution strengtheners of niobium, but the amounts of these elements that can be added are limited if the alloy is to retain useful room-temperature ductility. It has been shown, however, that partial replacement of niobium with tantalum lowers the ductile-to-brittle transition temperature of such alloys and allows larger additions of molybdenum and tungsten to be made. Some of the high-temperature properties of niobium alloys containing these elements have been reported by Bartlett et al.,' and the work presented here describes the low-temperature behavior of one of these, a solid-solution alloy containing, by weight, 20 pct Ta, 15 pct W, and 5 pct Mo. The elastic modulus, the temperature and strain-rate dependence of the yield and ultimate tensile stresses, and strain-hardening effects are discussed and compared with those of unalloyed niobium. EXPERIMENTAL MATERIAL AND PROCEDURE The material used in this investigation was produced from a 6-in.-diameter, double arc-melted ingot. This was can-extruded at about 1150°C to a 3-in.-diameter billet, and after annealing for 1 hr at 1345°C the billet was heated to 1315OC and part rolled and part forged to 0.5-in.-thick plate. The resulting material exhibited a cold-worked structure

Jan 1, 1965

By AIME AIME

IV. THE BOUNDARY BETWEEN STEEL AND IRON. It would be well to decide on a definite carbon-content to serve as a boundary line between ingot-iron and ingot-steel, between puddled-iron and puddled-steel, and between any other varieties of wrought-iron and weld-steel. Two plans have been considered. One is to draw this line at 0.32 per cent. of carbon or its equivalent in other elements, for the reason that this carbon-content appears to correspond to the critical point, 0, in the diagrams of Roberts-Austen and Rooze-boom.8 This has the merit of corresponding to a definite physical boundary. The other plan is to draw the boundary at 0.20 per cent. of carbon, because this is a convenient place to separate the important classes " soft steel " and " half-hard steel," so that if this point was adopted "ingot-iron " would be synonymous with "soft steel," and " ingot-steel " would be the equivalent of the two classes, " half-hard steel " and " hard steel."

Mar 1, 1908

By Laurence Hicks

CONSIDERATION of the past work on the subject of the diffusion of chromium into iron suggested that additional information might be given by the use of X-ray spectroscopy in following the concentration changes through the diffusion zone. Grübe and Fleischbein1 packed rods of electrolytic iron in a mixture of alumina and chromium. These specimens were heated in an atmos-phere of purified hydrogen for varying lengths of time. After treatment the specimens were examined metallographically and showed the usual structure, consisting of a border of radially oriented columnar grains ending in a sharp boundary line. Reference is made to the fact that etching with certain reagents will attack only the material inside the border of columnar growth and also to the fact that polishing seems to develop a ridge at the position of the boundary between the etched and unetched areas. By chemical analysis of thin layers turned off on a precision lathe, the authors were able to obtain depth-concentration curves. These curves, reproduced in Fig. 1, show that 'in most cases a pronounced change of slope occurs, corresponding to the position of the boundary of the columnar grains. In a later paper Grübe extends his work to other systems which show the same characteristics.2 He concludes that the reason for the break in the curve is that a hindrance of diffusion occurs at the place where the regularly oriented grains of the diffusion zone meet the random grains of the interior portion, on the assumption that the diffusion velocity in one direction in a grain may be greater than in another direction, and that the grains in the diffusion zone orient themselves so as to give the maximum diffusion rate. Kelley3 points out that Grübe has failed to note that the boundary line does not consistently cross all grains and

Jan 1, 1933

By AIME AIME

THE papers on geophysics were roughly divided into two groups*, those presented Monday morning being of a more technical and theoretical nature, whereas the afternoon session was principally taken up with discussions of a predominantly geological flavor. Thus it was made possible for those of a mathematical turn of mind to indulge their penchant for formula and differentials before lunch, leaving the field comparatively free, after lunch, for the geologists to learn of practical applications. The advantage of this classification is evident, and it is to be hoped that in some future meetings it will be possible to hold joint sessions of the geophysicists and mining geologists, to consider the overlap of the two fields.

Jan 1, 1931

By J. W. Rutter, K. T. Aust

In previous studies of grain boundary migration in zone-refined lead, the authors used bicrystal specimens consisting of a striated crystal which was grown from the melt, and an adjacent striation-free crystal, introduced by artificial nucleation and growth.1 While this method permits the study of the motion of individual grain boundaries, it does not provide control of the relative orientations of the grains. The present note will describe a technique for controlling the orientations of the two crystals in this type of specimen. The technique consists essentially of placing a striated crystal and a striation-free crystal of controlled orientations end-to-end in a graphite trough, then melting a short zone at the junction of the two crystals and allowing it to freeze to form the desired grain boundary. The apparatus used to carry out this process is illustrated in Fig. 1. It consists of a trough milled from high-purity graphite,with grooves in the underside for the placement of thermocouples. The graphite piece fans out on one end at the level of the bottom of the trough; the sides of the trough are completed in this region by the attachment of a mating plate with a slot cut at any desired angle to permit reorientation of the crystal placed at this end of the assembly. The joint between the crystals is made at or near the point where the slotted plate joins the rest of the trough. The thermocouple slots are deepened in this region so that the thermocouples are separated from the melt by only 1/32 in. of graphite. An induction heater, with suitable temperature control, is used to obtain the molten zone. The two single crystals used are first chemically polished in a solution consisting of eight parts glacial acetic acid and two parts 30 pct hydrogen peroxide. They are then placed in the trough with the ends to be joined at the position of the thermocouples. Next, cooling is applied to the two crystals by means of air

Jan 1, 1962

By Dubois Eastman

BEHIND the contrasting liquid-fuel technologies of Germany and the United States lie the basic differences of scarcity and abundance. The chemists and engineers of each nation have developed processes that accommodate available raw materials. In the United States, processing is based on an abundant supply of petroleum, which is refined into a variety of fuels and lubricants. Germany has little indigenous petroleum but has a readily available supply of coal that can be converted into liquid fuels and lubricants. As a result, in Germany several basic processes have been developed for the conversion of coal into synthesis gas (carbon monoxide and hydrogen). In turn, this gas is processed into products. As a normal function of its researches into petroleum processing, the petroleum industry in the United States has made careful studies of various conversion and synthesis techniques. A number of oil companies are carrying out independent development programs with the aim of synthesizing hydro- carbon products that can be marketed at a price that will compete with the price of refined petroleum products. American oil companies hope to perfect synthesis processes that will directly benefit the consumer. A good example of progress in these terms is the synthesis plant at Brownsville, Texas, which is based on the conversion of natural gas to synthetic fuels and other valuable products. When this plant is operated at near capacity, it is expected that the products will be able to compete favorably for the consumer dollar. The complete gasification of coal is a technique well rooted in history. As a controlled process on a small scale, it goes back centuries. As a practical technique on a commercial scale, it dates back to 1839, when "producer gas" appeared in Germany for limited industrial use. By 1873, "water gas," or "city gas" as it is sometimes called, was being manufactured commercially in the United States for use in heaters and stoves. The water-gas process was the cornerstone for modern synthesis. To older methods that were concerned only with carbon and oxygen reactions, it added hydrogen by means of steam. Thus far the goal of conversion was to produce gas for heating, lighting, industrial use, and cooking. The long step forward to synthesis was made in 1927, when Germany started to make gasoline from coal by means of the revolutionary Bergius hydrogenation process. A year earIier, Franz Fischer and Hans Tropsch had announced their process, which finally reached the

Jan 1, 1953

By Frank Alfred Fahrenwald

Discussion of the paper of FRANK ALFRED FAHRENWALD, presented at the New York meeting, February, 1916, and printed in Bulletin No. 109, January, 1916, pp. 103 to 149. F. A. FAHRENWALD, Cleveland, Ohio (communication to the Secretary*).-Since the publication of my paper in the January Bulletin, (which was largely a metallographic treatise), I have been questioned regarding two points referred to therein. One of these is that which deals with the application I have made, p. 119, of the equation for melting pressures which correspond with different working temperatures. The other refers to the statement, p. 137, that "Prolonged heating at relatively low temperatures gave fewer and larger crystals and crystals of different sizes, while a flashing at higher temperatures gave a very fine and uniform crystalline structure, which was much' to be preferred." Especial emphasis was not placed upon either of these two factors, for each seemed perfectly logical and obvious. As they do not seem to be self-explanatory, I will supplement with those portions of my notes which were purposely omitted from the manuscript submitted for publication. A few practical illustrations may serve as evidence in support of the first of these, but it must be understood that in this work the "amorphous theory" is considered as being sound, and that it is assumed that metals allow of distortion, without fracture, by virtue of the formation of slip surfaces, accompanied by the transformation of crystalline material to the, amorphous phase. Effect of Pressure.-In all forging, rolling, and drawing operations, it is known that specimens of small cross-section may be worked at a lower temperature than can be used for the same material in much greater mass and sectional area. In -the larger pieces the maximum pressure is brought to bear upon the material near the surface, so that the interior is not subjected to great pressure, but to, a stress more nearly tensile, or shearing, so only the surface is subjected to the critical melting pressure. In the case of wires which draw hollow, the center is subjected to practically a tensile stress which breaks it, while the surface skin draws perfectly, due to the enormous "flowing" pressure exerted upon it by the surface of the draw-plate.

Jan 5, 1916

By Ernst F. Eurich

Alexander Parkes patented in England in 1851-52-53 a process for desilvering lead by means of zinc, making use of the greater affinity of silver for zinc than for lead, discovered by Karsten in 1842. The efforts in England to develop it commercially were not particularly successful, nor was the attempted introduction into the United States. This last was not surprising, as it was about the beginning of our Civil War, and at that period there was very little lead-bullion produced in the United States and there was no field for the process here. There was at that time on Staten Island an establishment that pattisonized lead, probably from Rossie, N. Y., and Chester, Pa., and possibly some Spanish lead, but the production of lead-bullion in the Far West had not yet begun. In 1864, Edward Balbach, of Newark, N. J., patented in this country a process for desilvering lead by means of zinc, and in 1867 Edward Balbach, Jr., patented a " movable black-lead retort with a neck, placed in a furnace," for the purpose of distilling the alloy of zinc, lead, and the precious metals. A brief comparison of the Parkes and the Balbach processes is interesting. The Parkes process as practiced in England consisted in stirring into silver-bearing lead, melted in a kettle, from 1 to 2 per cent. of zinc, cooling, skimming the alloy of lead, zinc, and silver that rose to the surface, liquating it in an iron retort, distilling the residual rich alloy in fire-clay retorts, thus regaining the zinc, and refining the desilvered lead at a low heat in a shallow cast-iron pan that formed the hearth of a reverbera-tory furnace. If the lead was too impure, it was first softened

Jan 1, 1913

By M. E. Wadsworth, J. R. Lewis, J. M. Quets

Samples of snythetic magnetite were reduced in hydrogen at various partial pressures and temperatures. The reaction mas found to be surface controlled and directly proportional to hydrogen partial pressure over the temperature range studied (400° to 1000°C). A transition in the mechanism occurred at approxirnately 590°C. This has been attributed to a change in the slow step of the reduction reaction resulting from the presence of stable wüstite at higher temperatures. Below 590°C the heat of activation for the reduction was found to be 14,700 cal per mole and it was 3,200 cal per mole above 590°C. THE reduction of the oxides of iron has been a subject of study and interest for many years. Edstrom1 has reviewed the work up to 1953 and his findings provide much basic information concerning details of the reduction of hematite (Fe2O3 ) and magnetite (Fe3O4) with both H2 and CO. He concluded that below 600°C the reduction of both hematite and magnetite was essentially identical, since the rate was controlled by a surface reaction at a magnetite gas interface and the iron formed was very porous. The decrease in the reduction rate for both hematite and magnetite immediately above 600°C was attributed to the formation of a stable wüstite phase across which diffusion was very slow. The wide difference in reduction kinetics for hematite and magnetite above 600°C was explained in terms of the character of the wüstite formed. The rate of magnetite reduction increased slowly with temperature beyond the minimum immediately above 600°C and rates equivalent to those observed at 550°C were not obtained until the temperature was increased beyond 850oC. Edstrom and Bitsianes2 studied the solid-state reduction of magnetite, the reaction of which can be written (4x-3)Fe + Fe3O4—4 FexO [1] where x is between 0.83 and 0.95. The rate was found to be controlled by the kinetics of transport of iron ions through the wüstite phase. Bogdandy and Riecke3 studied the kinetics of reduction of small grains of iron oxide in hydrogen and qualitatively attributed the slow step in the reduction process to the diffusion of hydrogen and water vapor through pores. McKewan4 has analysed the data of Joseph,5 Stalhane and Malmburg,6 and Lewis7 and has demonstrated that the kinetics of reduction of both hematite and magnetite are controlled by surface reactions and also that the variation in surface area during reduction must be accounted for. McKewan was able to correlate the reduction data by the equation rodo[1-(1-R)1/3] = Kt [2] where ro is the initial particle radius, do is the density of the iron oxide, R is the fraction reduced at time t, and K is a rate constant. The applicability of Eq. [2] for temperatures above 600°C where a stable wüstite phase is present, indicates the slow step in the over-all kinetics does not result from diffusion unless diffusion occurs laterally along the oxide metal interface or through a wüstite layer of constant thickness. Diffusional control through a layer of wüstite is unlikely, however, in view of the pressure effects demonstrated by Tenenbaum and Joseph,' Diepschlag,9 McKewan,10 and the results of the present study. McKewan has demonstrated a linear rate dependence on the hydrogen partial pressure over the temperature range 400" to 1050°C for the reduction of hematite.

Jan 1, 1961

By A. S. Eve

IN the spring of 1930, the question was raised as to the possibility of estimating the depth to which the pyrrhotite-nickel deposit at the Falconbridge mine extended in the earth. This body is 7500 ft. long, it dips at 80° to the north, and it is fairly straight with slight sinuosities. Dr. F. W. Lee suggested that it might be possible to solve the problem by measuring the vertical magnetic intensity, with a good magnetometer, both near the surface of the earth and also at a level a 'few feet higher in the air. The writer regarded this suggestion with some scepticism, but it was decided to put the scheme to a prac¬ tical test. In July, 1930, Dr. Lee, Dr. Keys and I ' the writer, with Mr. Joyce and Mr. Belloc as assist¬ ants, made a firm, light wooden platform (Fig. 1) E measuring 4 by 4 ft. on the top, which was 10 ft. above ground. This platform could be moved easily a few yards by four men, and carried across I country in a wagon or by motor truck. Some iron nails were used in its construction, but we were not able to detect their influence on the - Askania magnetometer. Nevertheless, in future work, the use of iron should be completely avoided. Readings were taken along a traverse at right L angles to the orebody, at several stations, both on FIG. 1.-VERTICAL the ground and on the platform. The excess read- ASKANIA MAGNETOM¬ ETER ings, over the dike, as compared with those about 10 ETER ON A FT. HIGH. PLATFORM 800 ft. away, are shown in Table 1. The largest reading, 6.8, is open to suspicion and should be rejected. The depth of the top of the orebody is known by electrical survey, and by actual drilling, to be about 112 to 123 ft., and the covering is sandy glacial drift. Similar readings were taken over a long straight magnetic diabase dike. These also are shown in Table 1. The magnetic vertical intensity is consistently less at the higher level, which is l0 ft. above the lower level.

Jan 1, 1931

By R. W. Raymond

to same extent, the assumptions tinderlying Dr. Ilu?ley's con alusions. These amrrmptions are: that 'the loss of metal per million tons of trafffc, depends, first upon the circrtnistances under which the rail is worn; secondly, upon the proportions of its various constituents, ancl that the anlorlnt of loss is afEect~d by eacb constitnent in a cer tain ratio, so that if the circunlstances were the same for all tlie mils, the wear per nliilion tons might he upproxi91ately expre~sed by an equation of the form I + Cc + Pp + SR + Mm = R, io wtlioh I is an unknown valne, dependi~.rg on the quantity of iron (and other ingre dients not determined) in the rail, and assumed to be constant for all the rails ; c, p, s, and m are the experimentally determined quan tities of carhon, phosphorus, sulphur, and manganese, as tabulater1 in YIates VT and VII of Dr. Dudley's paper; and R is the experirnen tdlly dcterlnincd wear per million tons; while C, P, S, and M are onknown wfficients. In other words, it is assunled that the differ ence in wear is proportional to a difference in c, p, s, or m, and that the effects of a change in the amonnt of either are independent of the amount of the rest-—within the experinlental limit5 of the problem. It is also assr~med that sulphar, copper, and other ingredients, not determined, are qually present in all the rails, or at least {lo not affect the wear, since I is taken as constant. Dr. Dudley tacitly assumes the coefficient6 C, P, S, and M to be positive; and assigns certain valries to them, by means of which he redom t.he equation to the form I + Pa: = R, x being equal to cc + Es +Mm i Pp, or tjje uanjbe,. of so-called phosphorus units in the rail. But we do not have R directly given under constant circumstances. The varying weights (per engine, car, or train) and the varying epds, we must neglect for lack of data, and assume that in these rwpects the rails examined have been treated srlbstantially alike. But there remain the varying conditions as to track, which mnst he elirninsted. Dr. Dudley gives six clrlsses, four of which contain 8 rails each, and two 16 rails each. Beginning with the 6~st (tangent grade), take the mean of the figures expressing wear for that clam; and continaing tliis process through the other five, we obtain six expressions in quantity of loss 'by wear, which we assome tc, represent, in their differences, the varying conditions of the trarli, with respect to grade and direction. We now take the mean of these moans (giving double weight to the gmiip containing 16 ohwrvafieras). This general rnean is the 10 of metal per million tons of trafio for a rail of avorage constitution under mean ciroumstances.

Jan 1, 1881

By Frederick Rhines

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), ? in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activa-tion heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. Much of the argument concerning the properties of metals that deter-mine D and Q has been drawn from data in which variations of the quan-tities with concentration are unknown, for these data- have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concen-trations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By O. W. Ellis

The writer has dealt with the effect of various methods of melting copper upon the gas content of the metal.' The copper referred to in his earlier paper was melted in the foundry both in the oil furnace and the electric furnace. As the metal did not measure up to conductivity standard, the term "casting copper" was applied to the material in the title of the paper. It was thought that some information in regard to the gases in a sample of overpoled copper might also be of interest, and through the courtesy of C. R. Stevens, superintendent of the copper mill of the West-inghouse Elec. & Mfg. Co., such a sample was obtained. The metal was chill-cast in the form of an ingot about 7 in. long, 2 1/2 in. deep (from the base to the raised surface of the ingot) and from 1 3/8 to 1 7/8 in. wide. A photograph of part of the ingot is shown in Fig. 1. The effect of over-poling on the surface of the metal is here quite clearly shown.

Jan 1, 1929

By O. W. Ellis

The writer has dealt with the effect of various methods of melting copper upon the gas content of the metal.' The copper referred to in his earlier paper was melted in the foundry both in the oil furnace and the electric furnace. As the metal did not measure up to conductivity standard, the term "casting copper" was applied to the material in the title of the paper. It was thought that some information in regard to the gases in a sample of overpoled copper might also be of interest, and through the courtesy of C. R. Stevens, superintendent of the copper mill of the West-inghouse Elec. & Mfg. Co., such a sample was obtained. The metal was chill-cast in the form of an ingot about 7 in. long, 2 1/2 in. deep (from the base to the raised surface of the ingot) and from 1 3/8 to 1 7/8 in. wide. A photograph of part of the ingot is shown in Fig. 1. The effect of over-poling on the surface of the metal is here quite clearly shown.

Jan 1, 1929

By A. J. Ardell

SASS and cohenl (S-C) have recently reported some transmission electron microscope observations of an interesting effect which they call "veining". They observed veining in thin foils of solution-treated and (in certain cases) aged samples of a Ni-10.3 at. pct Ti-0.6 at. pct A1 alloy (assumed equal to 10.9 at. pct Ti). S-C suggest that veining in solution-treated samples is due to the selective electrolytic etching of titanium-rich regions in alloys which are otherwise homogeneous. They associate the veins with the discrete titanium-rich regions detected in a magnetic study of aging in this system by Ben Israel and Fine,' and they also suggest that the initial strengthening of aged Ni-Ti alloys is due to these titanium-rich regions, rather than the formation of the coherent precipitate (Ni3Ti, L12 crystal structure).

Jan 1, 1970

By A. C. Fieldner, F. H. Gibson, W. A. Selvig

A foRmer paper1 described in detail various methods of calculating coal analyses to obtain the composition and calorific value of the pure coal substance—that is, of the coal free from its mineral matter. The paper included a table showing calorific values of pure coal, as calculated from float-and-sink portions, by means of the Parr formula for "unit coal" and by the customary moisture-free and ash-free formula. A modification of the Parr formula was proposed, based on the assumption that one-half the sulfur present in Coal occurs as pyritic sulfur and one-half as organic sulfur. In the published discussion of the paper Cady gave a table of results on a large number of Illinois coals as obtained by the Parr formula and the proposed modification thereof. The results obtained by Cady indicate that the Parr formula applies better to Illinois coals than does the modified formula proposed by Fieldner and Selvig. The present paper gives results obtained by applying the modified Parr formula to the analyses of the float-and-sink portions of the coals shown in the former paper, and results obtained by applying the Parr formula, the modified Parr formula, and the simple moisture-free and ash-free formula to various coals of the United States ranging in sulfur content from less than 1 per cent to more than 4 per cent sulfur. A graphic method of estimating the calorific value of pure coal and determining the relation of the coal ash to the mineral matter of coal, as proposed by Stansfield and Sutherland,2 was applied to a number of coals, and the results are given herein. Testing Formulas with Float-and-sink Separations The former paper by Fieldner and Selvig gave heat values of pure coal of the float-and-sink portions of 21 coals, as calculated by the Parr formula

Jan 1, 1932

By d&apos, C. Antonio, S. H. Reichman

In the course of our studies of the annealing behavior of vapor-deposited silver films we have determined the electrical resistivity as a function of annealing temperature for films in the thickness range of 630 to 3240A. Fig. 1 shows the resistivity of the silver films vs film thickness in as-deposited and annealed conditions. The films were prepared by depositing 99.999 pct pure silver from molybdenum boats onto Vycor substrates. Deposition was conducted at a residual pressure of 5 x 10"6 Torr at rates of 20 to 408, sec-'. Thicknesses were determined using a multiple-beam interferometer. During annealing, resistance was measured using the four-probe method. Measurements were made every 5°C during two consecutive anneals to 300°C under a continuous vacuum of 2 x X6 Torr. The heating and cooling rates during annealing were approximately l° and 2°C min-', respectively. Typical resistivity vs temperature curves are shown in Figs. 2 through 4. There is an inflection point evident at 120°C on Fig. 2, the first anneal of a 3240A film. This inflection point was found on all films above approximately 1!00A on both first and second anneals. Below 1400A the inflection occurred at approximately 180°C. Figs; 3 and 4 show the first and second anneals of a 1370A film. The inflection point occurs at 180°C on the first anneal and approximately 120°C on the second. Our interpretation of this phenomenon is based on oxygen liberation from the film surface. It is well-documented that the presence of oxygen on silver surfaces causes a reversible increase in resistivity.1"3 The liberation of this oxygen, for example during vacuum annealing, would therefore cause a decrease in resistivity as observed on Figs. 2, 3, and 4 as a change in slope. This is accounted for by the decomposition of Ag20 on the film surface. The free energy of AgzO becomes positive between 125" and 225°C.4 The thickness dependence of the inflection points can be explained as an orientation effect. The films used in this study were preferentially oriented with their (111) planes parallel to the Substrate.''~ In addition it has been sten that the thinner films, below approximately 1500A, possess a decided "hill and valley"

Jan 1, 1969

By Robert B. McCormick

WORLD WAR II has developed a use for the nonmetal mineral quartz crystal that was unknown in World War I. During the interim period of peace, experimental work in the radio field with the piezoelectric properties of quartz crystal resulted in the almost universal adoption of quartz-crystal radio oscillator plates to control frequency in radio broadcasting, police, commercial and amateur communications equipment. Telephone resonators and filters made from quartz crystal also were developed, which vastly improved the frequency control of long distance telephone circuits. EXPANSION OF THE INDUSTRY The sudden war demands of the armed services for radio equipment using quartz crystal for frequency control led to an unprecedented expansion of the manufacturing industry. It is estimated that the 1940 peacetime volume amounted to approximately $1,500,000, while today a vast new quartz-crystal industry supplies more than $150,000,000 worth of quartz oscillator plates to the Army and Navy each year. This demand has caused an enormous expansion not only of American manufacturing facilities but also of Brazilian mining output, virtually our only source of raw quartz crystal. Actual figures of imports and consumption cannot be cited, for security reasons, but certain comparisons have been made, which indicate the transformation of quartz crystal from a minor to a major nonmetal. Lends has shown that the value of quartz-crystal exports from Brazil is now about equal to that of phosphate rock produced domestically in 1941 and actually exceeds the combined value of crude feldspar, gypsum and fluorspar production in the United States in the same year. This great expansion under wartime pressure was not accomplished without some anxious moments, but all the demands of industry have been met and the Government has been able also to accumulate a substantial stock pile of material against future contingencies. INSPECTION AND GRADING OF QUARTZ CRYSTAL The swift growth of the quartz-oscillator industry necessitated the simultaneous evolution of methods and criteria for inspecting and grading quartz crystal. It has been found that, generally speaking, it is economically feasible to cut only crystals that are at least 30 per cent by volume free from major defects such as optical and electrical twinning, cracks and fractures. Blue needles, bubbles, "chuva" and other minor imperfections can be tolerated in the usable portion unless present in great excess. The present marketing system in use in both Brazil and the United States, as far as quality is concerned, depends solely on the "usability" of a crystal, which is defined in the Brazilian-American agreement2

Jan 1, 1945

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By J. W. Wolfe

The Benedict-Webb-Rmbin equation of state was used in digital computer programs to make rapid determinations of natural gas equilibrium phase compositions. Mixture components were the nine hydrocarbons, methane through heptane. Comparative tests were made with data from field separators, plant exchangers and literature sources. For most tests made, the B-W-R equations predrcted component K-vallles, mixture enthalpies and phase aensities within tile accuracy of available correlations for rune-component mixtures: significant deviations were noted when mixtures contained components heavier than heptune. INTRODUCTION Rapid, accurate methods for calculating the properties of hydrocarbon mixtures are needed for predicting the behavior of natural gas processes. For example, because of the common use of two-phase separation methods in gas proccssing, calculations must be made for the density and composition of equilibrium vapor and liquid phases. In addition, predictions must often be made for the temperature and pressure changes associated with the flow of single- and two-phase natural gas fluids through heat exchangers, chokes and turbines. The complex nature of non-ideal mixtures makes rigorous calculations for these natural gas properties difficult and time-consuming. Natural gas properties have conventionally been determined with generalized data correlations. These correlations, such as the K-values presented in the NGAA Equilibrium Ratio Data Book, are usually based on some average property of the mixture and have proven to give satisfactory estimates for the properties of most oil and gas systems. Digital computers, however, have not only increased the utility of these correlations, but also have made practical the use of equations of state for calculating the properties of natural gases. Potentially, if basic pure component data are available, all the desired thermodynamic properties of mixtures can be derived from a single equation of state describing the mixture. Currently. the best equation of state for describing the behavior of pure, light hydrocarbons over single-and two-phase regions, both below and above critical pressure, is that of Benedict. Webb and Rubin.' The equation contains eight constants which are determined by empirically fitting the equation to pure-component PVT data. Benedict and his co-workers presented the clevelopment of their equation as early as 1940.2 The B-W-R equation is a modification of the Beattie-Bridgeman equation of state and gives better PVT predictions than the Beattie equation at densities above the critical density. Benedict et al. made the equation applicable to mixtures by relating the mixture constants to composition and the constants for pure compounds. These authors, in a serics of articles in 1951,' showed the accuracy of the B-W-R equation when applied to light hydrocarbons and their simple mixtures, and demonstrated the equation's utility for making vapor-liquid equilibria calculations. Since its inception, the B-W-R equation has been the subject of many papers. Numerous additions and modifications have been proposed,'-',"'-':' the purpose of most being to improve the equation's ability to predict PVT properties of specific mixture systems. In 1959, Opfell, Pings and Sage summarized much of the work on the B-W-R equation in their book on equations of state." Since natural gases are primarily mixtures of light hydrocarbons, the B-W-R equation is a natural choice for an equation of state to compute both phase equilibria and thermodynamic properties of natural gases. Consequent-

Jan 1, 1967