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By V. Leroy, A. G. Guy

Serious disagreements are often found between experimentally determined intrinsic diffusion coefficients and those calculated employing the usual form of the vacancy theory. In the new theory it is proposed that the total intrinsic flux, Ji, of component i, is the sum of a part, f, due to the usual random exclzanges of component i with the vacancies, and a second part, Ji, due to exchanges with the uacancies composing the net vacancy flux. The present treatment, while less powerful than that of Manning, has the advantage of easy uisualization and of facilitating the application of the vacancy-flux effect to complex systems. IT is becoming increasingly evident that there are serious deficiencies in the version of the vacancy theory of diffusion that has been widely used for the past 20 years. One type of evidence is the frequent lack of agreement between intrinsic diffusion coefficients and tracer diffusion coefficients, even taking account of the thermodynamic factor. A second kind of evidence is the observation of a Kirkendall shift larger than theoretically possible, that is, larger than can be accounted for without assigning a negative value to one of the two intrinsic diffusion coefficient.'- The thermodynamic factor could conceivably make both coefficients negative, but not just one. It is clear that a cause of these anomalies, apart from any inadequacy of the usual vacancy theory, might lie in an oversimplified treatment of the data. Adequate experimental techniques, including the use of moderate pressure during the diffusion anneal, are now available to insure that porosity, lateral expansion, and so forth, can be kept negligibly small in most cases. The effect of differences in atomic volume can be of major importance, and it is essential that one of the available methods4 be used to account for this factor. In the present treatment this is accomplished by the consistent use of moles per cubic centimeter as the unit of concentration. Of the various possible inadequacies of the vacancy theory, attention will be given here only to effects of the net vacancy flux. annin' has previously considered this question, beginning with an analysis of atomic jumping of tracer atoms. When he added the effect of a concentration gradient, new terms arose that could be associated with the flow of vacancies. The present treatment uses quite a different approach. The usual vacancy flux, J,, is introduced explicitly, and a simple analysis predicts major changes in the intrinsic diffusion coefficients from this cause. The usual assumptions are made that only a vacancy mechanism is operative, that the formation of voids can be neglected, and that changes in the partial molal volumes, vl and v2, are negligible. The significant diffusion coefficients for the present topic are Dl and D,, the intrinsic coefficients, which enter in the equations, where the flux Ji, moles per sq cm per sec, is that crossing the Kirkendall interface. The concentration, ci, is in units of moles per cu cm, and the concentration gradient, aci/ax, is evaluated at the Kirkendall interface. It will be recalled' that the calculation of Dl and D2 involves the measurement of areas on the diffusion curve with respect to the positions of the Kirkendall and Matano interfaces. In the case of the anomalies mentioned earlier, the Kirkendall shift is too large to be accounted for by the diiferetzce in fluxes (J2 -J1), given by Eqs. [I] and [2]. The logical inference is that the flux of the solvent atoms, J1, is actually in the same direction as the flux of the solute atoms, Jz. In terms of Eq. [I] this requires that Dl have a negative value. However, it would be somewhat misleading to state that the solvent atoms are diffusing up their own concentration gradient. The explanation that will be advanced here pictures competing processes producing the net flux of solvent atoms: 1) diffusion of the solvent atoms down their own gradient by random exchanges with vacancies; and 2) diffusion of solvent atoms in the opposite direction by exchanges with the net vacancy flux. ACTION OF THE NET VACANCY FLUX Theories of vacancy diffusion can be formulated with varying degrees of refinement, and the present theory has purposely been kept as simple as appeared adequate to explain the phenomenon in question. In particular the following aspects have been neglected: 1) the gradient of vacancy concentration in comparison to the gradient of the atomic species; 2) departure of vacancy concentration from the local equilibrium value; 3) variation of the jump frequency, LO, with the specific surroundings of the atom-vacancy pair being considered; 4) correlation effects. These and other refinements can be considered once the essential mechanism has been established. The essential idea of the present analysis is to calculate the total intrinsic flux, Ji, of component i as the sum, JlJ?±j{ [3] where J; is attributable to the usual random atomic jumping, and J{ is a contribution arising from the net vacancy flux, J,. The latter quantity, of course,

Jan 1, 1967

By V. R. Garfias, R. V. Whetzel, J. W. Ristori

Since the entry of the United States into global war, virtually all data and information necessary for compiling figures on world petroleum consumption have become unavailable. This situation undoubtedly will continue until the world petroleum industry can return to a peacetime basis. During the past 10 years, the authors, by publishing annual estimates of .world consumption, have attempted to emphasize the importance of a yearly world-wide survey of petroleum supply and demand. It is beconling more and more evident that statistics for the United States alone can no longer give a comprehensive idea of the state of the petroleum industry, even within the United States itself. Therefore, when conditions in the industry again become normal, it is the hope of the authors that those bureaus equipped to do so will carry forward the study of petroleum supply and demand on a world-wide basis. Enough data and information are available, however, to attempt a rough estimate of world output of crude petroleum and petroleum substitutes for 1942, which to some extent may reflect the trend of world consumption. This estimate by countries, as compared with the output in 1941, is shown in Table I. The world production of crude petroleum and petroleum substitutes for 1942 is estimated at 2,208,000,000 bbl., or a decrease of 171,000,000 bbl. under 1941. Crude production is believed to have decreased by about 200,000,000 bbl., (about 9 per cent); while petroleum substitutes increased by 28,500,000 bbl., (nearly 20 per cent). The decline of crude output in the United States is estimated at 19,000,000 bb1.—less than 2 per cent; while that in foreign countries is estimated at 180,000,000 bbl., or more than 20 per cent. The marked decline abroad is due largely to losses in Venezuela and Colombia, where the lack of ocean transportation became the controlling factor, and in the East Indies and Burma, where military invasion brought about the destruction of the fields. The production of petroleum substitutes in 1942 apparently reached a new high figure of 7.5 per cent of the total world petroleum output. The important features of petroleum production outside of the United States are the changes that have taken place during the year in the supply of the Axis countries. In Japan the output for 1941 was estimated at 8,800,000 bbl., 5,500,000 of which were petroleum substitutes. It is believed that the output of synthetic oils during 1942 substantially increased, raising the total interior production of Japan to nearly 10,-ooo,ooo bbl. Also, during 1942 Japanese armed forces gained possession of oil fields having a normal peacetime output of about 78,000,000 bbl. per year. The production of these areas for 1942 is estimated at some 23,000,000 bbl., which indicates that Japan is now getting at least 33,000,000 bbl. a year, which exceeds by 8,000,000 bbl. Its

Jan 1, 1943

By J. W. Ristori, V. R. Garfias, R. V. Whetzel

Since the entry of the United States into global war, virtually all data and information necessary for compiling figures on world petroleum consumption have become unavailable. This situation undoubtedly will continue until the world petroleum industry can return to a peacetime basis. During the past 10 years, the authors, by publishing annual estimates of .world consumption, have attempted to emphasize the importance of a yearly world-wide survey of petroleum supply and demand. It is beconling more and more evident that statistics for the United States alone can no longer give a comprehensive idea of the state of the petroleum industry, even within the United States itself. Therefore, when conditions in the industry again become normal, it is the hope of the authors that those bureaus equipped to do so will carry forward the study of petroleum supply and demand on a world-wide basis. Enough data and information are available, however, to attempt a rough estimate of world output of crude petroleum and petroleum substitutes for 1942, which to some extent may reflect the trend of world consumption. This estimate by countries, as compared with the output in 1941, is shown in Table I. The world production of crude petroleum and petroleum substitutes for 1942 is estimated at 2,208,000,000 bbl., or a decrease of 171,000,000 bbl. under 1941. Crude production is believed to have decreased by about 200,000,000 bbl., (about 9 per cent); while petroleum substitutes increased by 28,500,000 bbl., (nearly 20 per cent). The decline of crude output in the United States is estimated at 19,000,000 bb1.—less than 2 per cent; while that in foreign countries is estimated at 180,000,000 bbl., or more than 20 per cent. The marked decline abroad is due largely to losses in Venezuela and Colombia, where the lack of ocean transportation became the controlling factor, and in the East Indies and Burma, where military invasion brought about the destruction of the fields. The production of petroleum substitutes in 1942 apparently reached a new high figure of 7.5 per cent of the total world petroleum output. The important features of petroleum production outside of the United States are the changes that have taken place during the year in the supply of the Axis countries. In Japan the output for 1941 was estimated at 8,800,000 bbl., 5,500,000 of which were petroleum substitutes. It is believed that the output of synthetic oils during 1942 substantially increased, raising the total interior production of Japan to nearly 10,-ooo,ooo bbl. Also, during 1942 Japanese armed forces gained possession of oil fields having a normal peacetime output of about 78,000,000 bbl. per year. The production of these areas for 1942 is estimated at some 23,000,000 bbl., which indicates that Japan is now getting at least 33,000,000 bbl. a year, which exceeds by 8,000,000 bbl. Its

Jan 1, 1943

By Walter Miller

Crude oil stocks were some 10,000,000 bbl higher on June I, 1947, than at any time during 1946 but the extremely heavy refinery runs the last half of 1947 cut crude inventories to approximately the 1946 closing level of 225,000,000 bbl. Many refiners were seriously short of crude oil during the year. This shortage was reflected in numerous advances in the posted price of crude, justified in part as an incentive for more production but more generally due to competitive bidding. Some purchasers of crude, endeavoring to keep their plants running, resorted to the payment, either directly or indirectly, of premiums above the posted price. Another common practice employed by some suppliers of crude oil was to demand refined products in exchange or trade for their raw material. The refined products picture has darkened in spite of record throughputs. Stocks of gasoline and light and heavy fuel oils were uncomfortably low at the beginning of the year and were in general still lower at the close. The rationing of some products, principally gasoline, to dealers and stations? initiated during the year, gained momentum as stocks continued to diminish. The emphasis placed by the manufacturers of oil-burning equipment on the convenience and economy of heating with oil, together with the tight situation in coal, has developed a tremendous demand for burning oils. Consumption of liquefied petroleum gas for domestic and household fuel had more than doubled in 1946 over 1943, and the demand seems to be limited only by the ability of the equipment builders to furnish necessary storage. transportation, and burning equipment. The supply situation is likely to become more acute in 1948. Demand for petroleum products is being pushed to new heights not only by the unprecedented domestic market but by a sudden and drastic upswing in estimates of military and governmental requirements. Additionally, oil exports are running far below the volume requested, amounting to less than forty percent in a recent quarter, and export licenses are reportedly being approved on the basis of urgent need *only. AX recent White House release sees little likelihood that estimated requirements of the sixteen nations participating in the proposed Marshall Plan can be met in full over its projected life—1948 to 1951. Present demand dictates maintenance of refinery operations at the highest possible level and the Bureau of Mines has forecast daily average crude runs in 1948 of 5,265,000 bbl. The Economics Advisory Committee of the Interstate Oil Compact Commission recently estimated the 1948 demand for petroleum products at nearly 6 pct above 1947. They further estimate daily average crude runs of 5,375,000 bbl in 1948, some 2 pct higher than forecast by the Bureau of Mines. Projected demand exceeds supply to the extent that Capitol Hill is reportedly investigating ways of enabling oil companies to act in concert without danger of antitrust prosecution, such as elimination of crosshauls, pooling of products, and lowering of octane.

Jan 1, 1948

By Walter Miller

Crude oil stocks were some 10,000,000 bbl higher on June I, 1947, than at any time during 1946 but the extremely heavy refinery runs the last half of 1947 cut crude inventories to approximately the 1946 closing level of 225,000,000 bbl. Many refiners were seriously short of crude oil during the year. This shortage was reflected in numerous advances in the posted price of crude, justified in part as an incentive for more production but more generally due to competitive bidding. Some purchasers of crude, endeavoring to keep their plants running, resorted to the payment, either directly or indirectly, of premiums above the posted price. Another common practice employed by some suppliers of crude oil was to demand refined products in exchange or trade for their raw material. The refined products picture has darkened in spite of record throughputs. Stocks of gasoline and light and heavy fuel oils were uncomfortably low at the beginning of the year and were in general still lower at the close. The rationing of some products, principally gasoline, to dealers and stations? initiated during the year, gained momentum as stocks continued to diminish. The emphasis placed by the manufacturers of oil-burning equipment on the convenience and economy of heating with oil, together with the tight situation in coal, has developed a tremendous demand for burning oils. Consumption of liquefied petroleum gas for domestic and household fuel had more than doubled in 1946 over 1943, and the demand seems to be limited only by the ability of the equipment builders to furnish necessary storage. transportation, and burning equipment. The supply situation is likely to become more acute in 1948. Demand for petroleum products is being pushed to new heights not only by the unprecedented domestic market but by a sudden and drastic upswing in estimates of military and governmental requirements. Additionally, oil exports are running far below the volume requested, amounting to less than forty percent in a recent quarter, and export licenses are reportedly being approved on the basis of urgent need *only. AX recent White House release sees little likelihood that estimated requirements of the sixteen nations participating in the proposed Marshall Plan can be met in full over its projected life—1948 to 1951. Present demand dictates maintenance of refinery operations at the highest possible level and the Bureau of Mines has forecast daily average crude runs in 1948 of 5,265,000 bbl. The Economics Advisory Committee of the Interstate Oil Compact Commission recently estimated the 1948 demand for petroleum products at nearly 6 pct above 1947. They further estimate daily average crude runs of 5,375,000 bbl in 1948, some 2 pct higher than forecast by the Bureau of Mines. Projected demand exceeds supply to the extent that Capitol Hill is reportedly investigating ways of enabling oil companies to act in concert without danger of antitrust prosecution, such as elimination of crosshauls, pooling of products, and lowering of octane.

Jan 1, 1948

By E. M. Porbansky

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

Jan 1, 1964

By Arthur L. Crawford

PLAGER gold is perhaps the most difficult of the common mineral deposits to evaluate. Not only are the erratic pay streaks a source of never-ending uncertainty, but the spotty distribution of the gold in iso¬lated nuggets is a perpetual source of error and disappointment to the sampler. Experienced engineers have long realized this difficulty and have been wary in predicting assay values except in the most general terms, and then only after extensive and usually expensive sampling. During the past year I have had the opportunity of checking a number of gold placers, and from the results obtained I believe that the microscope may be employed to advantage in placer sampling.

Jan 1, 1933

By Michael R. Cartwright

The Gold Acres outcrop was located by Lee Lakin in 1922, according to Mr. H. W. Treweek. There was no activity, however, until 1935, when prospect drifts and pits penetrated the deposit. It was then drilled by the Willow Creek Mining Company. Beginning in the late 1930s and continuing to the late 1940s more than 150 churn drill holes were drilled in the Gold Acres area. From this drilling came what is now known as the London Extension pit. Only oxidized ore amenable to cyanide vat leaching was mined during this time. Our records indicated that this period of mining removed some 1.4 Mt (1.5 million st) of ore at an average grade of 0.006 kg/ t (0.2 oz per st). Union Pacific and Newmont Mining Company worked in the area prior to acquisition by the Cortez Joint Venture. Union Pacific drilled a number of core holes in the area. The unoxidized nature of the ore, small tonnage, and low grade undoubtedly prevented mining at this time. From these indications of mineralization shown by previous companies, the Cortez Joint Venture developed and mined 2 Mt (2.4 million st) at 0.005 kg/t (0.15 oz per st) in the Gold Acres pit. This pit is located immediately southwest of the older London Extension pit. Cortez Gold Mines has continued to drill to the west and south of these pits along the downdip continuation of the former ore bodies. The downdip extension is unoxidized and more metallurgically difficult than the normal Carlin type ores, but, more than 2.4 Mt (2.7 million st) have been outlined. It depends now upon the gold price and milling costs to turn this mineralized area into an ore body. A possible lesson to be learned from this deposit is that continued mining success depends upon an ongoing adequately funded exploration-development-metallurgical research program. These three disciplines must always be present to locate the mineralization and to turn this mineralization into ore. [ ]

Jan 1, 1985

E. Hill, South Norwalk, Conn. (communication to the Secretary*) :—The phenomenon described by Dr. Ledoux, involving an apparently abnormal high temperature in the air-cylinders of compressors, has not been, so far as I know, discussed in technical literature. The common formula for the adiabatic compression of dry air does not account for heat suficient to flash ordinarily decent cylinder-oils, nor do the text-books include in their theoretical statements any quantitative consideration of the effect of leaks in the ideal machines which they contemplate. This lack I have endeavored to supply by preparing, in the form of a circular, for the use of the customers and correspondents of the Norwalk Iron-Works, a brief mathematical

Jan 1, 1904

AT the meeting of the Board of Directors on Jan. 28, 1927, the tentative budget of this Institute for next year was discussed, and in connection with the evident necessity for a larger income to meet increasing demands for service, the advisability of in- creasing the dues of members, was brought up. W. Spen- cer Hutchinson advocated an upward revision of the dues "believing it necessary that the Institute have a larger income, in order that it may carry on necessary work and render adequate service to its membership." Since this is a matter that directly affects every member, .President Taylor was directed to appoint a committee, which he did, consisting of George D. Barron, W. H. Bassett, and R. H. Sweetser, with T. T. Read as secre- tary, to bring in a tentative outline of the main factors in the problem for discussion at the annual meeting, on Feb. 15, and to prepare, after they have had the benefit of the discussion at that meeting, a report for the board. The amount of the annual dues is fixed by the con- stitution and can only be changed by proposing an amendment to the constitution. This amendment would have to be submitted to the members by letter ballot at the time of the election of officers for 1928, so that no change can be made in the dues for 1927 in any case. WHY THE INSTITUTE NEEDS MONEY At the annual meeting past-president Reynders, as chairman of the executive committee made the follow-ing report, which since it admirably sets forth the rea-sons why an increase in the dues has been suggested, is included here. "The report of the president has covered the situation so fully that little is left for me to say. However, a word in regard to the functions of the executive com-mittee may not be out of place.

Jan 3, 1927

By A. J. Brown

I herewith send to the Institute a sample of Pancake coal. It is rather early yet to make any estimate of the future value of the discovery; but it is certainly the most promising vein of coal yet discovered in the State of Nevada, and, I believe, the first true coal found west of the Rocky Mountains, or perhaps west of the Missouri River, unless some of the Utah coals belong to the coal measures of the Carboniferous age. The Pancake vein certainly belongs * Since the above paper was read before the Institute, some modifications in the description of the machine have been made in order that recent improvements may be embraced.—U. S. A.

By Z. Moser, W. Ptak

The experiments were carried out by the method of measuring the electromotive force of concentration cells having zinc as a reference electrode, the second electrode being the liquid alloy Zn-Sn-Cd-Pb. The electrolyte consisted of liquid chlorides and had zinc ions. The measurements were made for seventy -five alloys of different mole fractions within the temperature range of 714° to 877°K. The experimental results enabled the calculation of the activity of zinc in tested solutions. The activities of zinc were calculated by means of Krupkowski's formulas.3 In addition, the formulas for coefficients of activity of zinc, tin, cadmium. and lead as the function of composition and temperature were given. Activity of zinc was compared with the values obtained from experimental results, and good agreement has been observed. On this basis it can be stated that the theoretical formulas are suitable for determining the thermodynamic properties of liquid quaternary metal solutions. IN the metallurgical processes being carried out at present multicomponent liquid metal solutions take part. For the thermodynamic analysis of these processes it is necessary to know the thermodynamic properties of these solutions. Therefore, many experimental and theoretical papers deal with this problem. The theoretical papers are generally based on the assumption that the structure of liquid metals is similar to their structure in the solid state. In this manner the model of liquid solution, consequently described by means of statistical thermodynamics, has been accepted. This method is being lately developed, especially for solid solutions. Statistical thermodynamics was applied among others by Guggenheim 1 for describing the thermodynamic properties. Unfortunately, the formulas of statistical thermodynamics are often not suitable for the interpretation of experimental results. Attention should be drawn to the relations obtained by means of formulas of phenomenological thermodynamics which always have constants derived with the aid of experimental methods. In the case of the multi-component solutions which contain some additions of impurities besides the basic metal, wagner2 introduced interaction parameters. Equations for the relationship between the activity coefficients and composition were also given by Krupkowski." he application of these formulas requires a good knowledge of the thermodynamic properties of the corresponding binary systems. In these formulas, as in Wagner's, there appear constants which should be determined from ex- perimental data. Nowadays, different experimental methods are applied for evaluating the thermodynamic functions of solutions, for instance: vapor pressure measurements, calorimetric methods, and the measurements of electromotive force of concentration cells. In the present paper this last method for evaluating the thermodynamic properties of four-component systems, Zn-Sn-Cd-Pb, was applied. For instance in the case of Zn-Sn solutions Alabyshev and Landratov, 4 Fiorani and Valenti, 5 and ptak6 performed the investigations. The Zn-Pb system was worked out by Kleppa 7 and Cd-Pb and Cd-Sn by Elliot and chipman.' This method was also applied for determining the activity of zinc in ternary solutions. 1) EXPERIMENTAL METHOD The experimental arrangement with detailed description is given in Fig. 1. It consists of resistance furnaces, one serving for melting samples and the other containing the flat-bottomed, measuring quartz tube with the liquid electrolyte. Liquid metals and alloys are in glass supremax tubes, which have an opening in their lower part above the metal level. This opening allows the filling of the tubes by the electrolyte. In these tubes tungsten wires are placed which by means of suitable conductors are connected with a potentiometer. It is assumed that tungsten dissolves Fig. 1—Schematic diagram of the experimental arrangement for the investigation of the thermodynamic properties of liquid metal solutions: 1, resistance furnaces; 2, autotransfor-mers; 3, galvanometers; 4, regulator of temperature; 5, gas purifier with concentrated H2SOP; 6, U-tube with P2O5; 7, thermostats; 8, steel block for thermostating; 9, supremax tubes for alloys; 10, tungsten electrodes; 11, inlet and outlet of argon; 12, measuring quartz tube; 13, tube for melting samples; 14, tube for thermocouple; 15, cover of quartz tube; 16, rubber seal; 17, bottom cover; 18, outlet of electrodes to potentiometer; 19, outlet of thermocouples to potentiometer; 20, upper view of the quartz tube cover; 21, orifices for cover screws; 22, orifice for argon inlet; 23, orifice for thermocouple; 24, orifices for tubes containing liquid metals; 25, inlet for water-cooling system.

Jan 1, 1969

By P. H. Dudley

When we see the magnificent passenger-trains of from 8 to 12 coaches, drawn by locomotives weighing from 100 to 110 tons, at speeds of from 50 to 60 miles per hour between terminals, to make a schedule of 45 miles per hour, and freighttrains of from 50 to 75 cars of 60,000 pounds capacity, drawn by one locomotive, it is hard to realize that it lacks a few months of fifteen years since my pioneer 5-inch 80-pound rail for the United States was laid by the New York Central aid Hudson River Railroad Co., in July, 1884, on the Harlem line. Shorter passenger-trains, of from 4 to 5 coaches, are run much faster, notably the Empire State Express, the schedule of which for the 440 miles between New York and Buffalo requires 53.3 miles per hour, calling for a running-speed, for much of the time, of from 65 to 75 miles per hour, while higher speeds are very common. On other railroads laid with my 5 1/8-inch 80-pound rail, speeds of from 60 to 75 miles per hour obtain in daily practice. On many of the important railroads east of the Mississippi high speeds of from 60 to 70 miles per hour are part of the daily service. So many instances of speeds of 90, and even 100, miles per hour have been recorded that they must be considered as likely to occur on important lines, and provision must be made for them in the track. Solid mail-trains of from 6 to 8 cars are run from New York to Chicago, 1000 miles, in twenty-four hours; and, commeneing with the present year, shorter trains are running from Chicago to San Francisco, 2000 miles, in three and one-half days. In the freight-service equally important progress has been

Jan 1, 1900

By Johnston, T. L.

BISMUTH is found as native metal associated with tin, copper, cobalt, silver, gold, or other metals and in a variety of ores. The more important ones are: bismuthinite (bismuth glance), Bi2S3; bismite (bismuth ochre), Bi2O3.3H2O; and bismutite (bismuth carbonate), Bi2O3CO3?H2O. Of lesser importance are the arsenate, telluride, and vanadate. The sulfide is the most common; the others are often oxidation products from this mineral. Bismuth minerals have been found in various places in the United States, principally in Colorado and Utah, but no ores are mined solely for bismuth. In the Granite mining district of Beaver County, Utah, a stratum of limestone about 6 ft. thick has been almost completely replaced by contact minerals in which bismuthinite associated with pyrite and molybdenite was found intergrown with silicate minerals. In the early days a few small lots of ore assaying 7 to 10 per cent bismuth were shipped from this district. Native bismuth has been found in the Clifton and Tintic districts of Utah. Bismuth is produced as a byproduct in the refining of lead, copper, gold and silver ores, it being recovered from the anode mud from the Betts process. Deposits of bismuth minerals exist in Argentina, Aus¬tralia, China, Japan, Germany, Spain, Peru, Bolivia, and Canada, but Bolivia is the principal, producer and could easily supply all of the present world's demand.

Jan 1, 1933

By C. S. Roberts

THE advent of a sensitive X-ray method of analysis recently has allowed the determination of retained austenite in amounts as low as 0.3 pct.' As a result this phase has been found in quenched low carbon steels where its presence has not been generally suspected. In the course of a study of the tempering process,' retained austenite determinations were made by the X-ray method on a series of high purity Fe-C alloys and plain carbon steels. The chemical analyses of these materials and details of the hardening procedure are given in Table I. Results were obtained after quenching to 72°F (22°C) and — 321 °F (—196°C). Austenitizing temperatures were between 100" and 150°F above A, or Acm. All proeutec-toid cementite or ferrite was in solution. The combination of the results with those of Averbach, Castleman, and Cohen,' and earlier results of Esser

Jan 1, 1954

By Claus G. Goetzel

Pressing of powdered metal parts is best done in the direction of the shortest extension of the piece, to avoid too great a loss of pressing force through internal iriction. As long as curved surfaces, re-cessej, or offsets occur only parallel to this shortest axis of pressure, no special difficulties arise: the cross sections, perpendicular to the pressure, do not vary, nor does the shape of the parts change during compression except for a gradually reduced thickness (Fig. IA). The problem becomes more dificult, however, when the curved surfaces or recesses are perpendicular to the shortest axis of the part (Fig. IB) Two processes for molding uniformly dense parts with complicated shapes from powdered metals are described in detail in this paper. Both can be employed successfully by those trained in the art. The first refers to curved parts; the second is especially adapted to parts having one or more recesses or steps. Both methods, as set forth here, are applied under the condition that presents the more difficult problem. For clarity, before description of the two practical methods, the variable factors in molding powdered metal parts will be reviewed, then an idealized procedure will be considered briefly. Variable Factors in Molding Powdered Metal Parts Compression Ratio Compression ratio is defined as the proportion of the final relative density of the compact to the apparent density of the powder. For iron powder of an apparent density of 3.0, for example, a compression ratio of 2 1/2:1 would be required to produce a compressed compact of 7.5 density; whereas for another iron powder having an apparent density of only 1.5, a compression ratio of 5:1 would be required to produce the same density. The lower the powder's apparent density, the greater must be the compression ratio for pressing compacts of high density.

Jan 1, 1946

By Claus G. Goetzel

Pressing of powdered metal parts is best done in the direction of the shortest extension of the piece, to avoid too great a loss of pressing force through internal iriction. As long as curved surfaces, re-cessej, or offsets occur only parallel to this shortest axis of pressure, no special difficulties arise: the cross sections, perpendicular to the pressure, do not vary, nor does the shape of the parts change during compression except for a gradually reduced thickness (Fig. IA). The problem becomes more dificult, however, when the curved surfaces or recesses are perpendicular to the shortest axis of the part (Fig. IB) Two processes for molding uniformly dense parts with complicated shapes from powdered metals are described in detail in this paper. Both can be employed successfully by those trained in the art. The first refers to curved parts; the second is especially adapted to parts having one or more recesses or steps. Both methods, as set forth here, are applied under the condition that presents the more difficult problem. For clarity, before description of the two practical methods, the variable factors in molding powdered metal parts will be reviewed, then an idealized procedure will be considered briefly. Variable Factors in Molding Powdered Metal Parts Compression Ratio Compression ratio is defined as the proportion of the final relative density of the compact to the apparent density of the powder. For iron powder of an apparent density of 3.0, for example, a compression ratio of 2 1/2:1 would be required to produce a compressed compact of 7.5 density; whereas for another iron powder having an apparent density of only 1.5, a compression ratio of 5:1 would be required to produce the same density. The lower the powder's apparent density, the greater must be the compression ratio for pressing compacts of high density.

Jan 1, 1946

By James Boyd

As our society grows in complexity, it becomes more urgently incumbent upon scientists and engineers to bring their experience to bear on the solution, not only of technical problems, but also on socio-economic difficulties. It is to this field that I have directed a large part of my energies. Raw Materials Basic to the Economic Process There are certain premises, frequently overlooked, which bear emphasis. As economics concerns the production, distribution, and consumption of goods, so our whole society is based on raw materials. Without the basic extractive industries of agriculture and mining, there would be no economic problems with which to deal. This principle has been expressed as: "All productivity is based on three factors: (1) natural resources, whose form, place, and condition are changed by the expenditure of (2) human energy (both muscular and mental), with the aid of (3) tools."*

Jan 3, 1967

By C. R. Whitney, G. N. Maniar, D. R. Muzyka

Previous results have shown that Pyromet 860, an Fe-Ni-base heat-resistant alloy, is stable at temperatures as high as 1500°F for aging times as long as 100 hr. This Paper describes the results of long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Times as long as 37,660 hr were employed. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffraction, and microprobe techniques. phase, containing cobalt, nickel, and molybdenum, was detected after extended exposures from 1200" to 1400°F and careful study was performed to describe the kinetics of its formation in this alloy. µ phase formation apparently has little effect on the elevated-tem-perature properties of Pyromet 860. For times as long as 500 hr at 1300°F and below, with µ phase present, m significant effects on ambient temperature properties were noted. For longer times at 1300°F and after 1400°F exposure, the effects of u phase on ambient temperature tensile strength properties are not clear due to y' effects and grain boundary reactions. Electron-vacancy, N,, numbers were calculated using different methods described in literature and correlated with the present findings. In the selection of alloys for use in gas turbine applications, structural stability ranks as a primary criterion. High-temperature strength and cost are also of major concern. With these factors in mind, Pyromet 860 alloy, an Fe-Ni-base superalloy was designed. This alloy combines the cost advantages of Fe-Ni-base alloys such as A-286, 901, and V-57 with improved strength and structural stability'1,2 and no tendency to form the embrittling cellular 77 phase. A previous study3 reported on the stability of Pyro-met 860 at temperatures from 1375" to 157 5°F and times up to 100 hr. That study showed that the y' precipitates increased in size and separation and decreased in number with an increase in time or aging temperature. No deleterious phases were found to occur. In the present work, samples from four production heats were subjected to long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Various heat treatments were used on the starting samples and tests were run up to 37,660 hr. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffrac- tion, and microprobe techniques. Electron vacancy numbers, Nv , calculations were made by TRW.4 Experimental results are correlated with the Nv data used to predict occurrence of intermetallic phases such as a phase. EXPERIMENTAL PROCEDURE Mechanical Tests. Material for the present study came from four production size heats of Pyromet 860 alloy, weighing from about 3000 to about 10,000 lb. All of these heats were made by vacuum induction melting plus consumable electrode vacuum remelting. The nominal analysis for this alloy is compared with the actual analysis of the four heats in Table I. Sections of these heats were forged to 9/16-in. round bar,3/4-in. square bar, 3-in. round bar, 4-in. square bar, and a gas turbine blade forging about 16 in, long, about 6 in. wide, and weighing about 20 lb. In general, all forging of this alloy is done from a 2050°F furnace temperature. Longitudinal test blanks were cut from the centers of the smaller bars, from mid-radius positions for the 3- and 4-in. bars, and from the air foil of the gas turbine blade and heat-treated according to the procedures outlined in Table 11. Heat treatment A is the "standard treatment" recommended for this alloy for best all-around strength and ductility. Heat treatment B is a modification of treatment A for improved tensile strength at moderate temperatures. The treatment coded C was designed for treating large sections according to a procedure previously described.' Heat treatment D was developed to yield optimum stress relaxation characteristics at 1050°F for a steam turbine bolting application. After heat treatment, the test blanks were machined either to plain bar creep specimens with a gage diameter of 0.252 in., to combination smooth-notched stress-rupture bars with a plain bar diameter of 0.178 in. and a concentration factor of Kt 3.8' at the notched section, or to notch-only specimens. All specimens conformed to ASTM requirements. Metallography. Most of the creep-rupture tests were continued to failure. A few bars were fractured as smooth or notch tensiles after creep-rupture exposures. After fracturing, ordinary metallographic sections were made primarily in gage areas adjacent to fractures to represent a "high-stress" region and through specimen threads to represent a "low-stress" region. All metallographic sections were made in a longitudinal direction with respect to the test specimen axes. For optical microscopy, the samples were etched in glyceregia (15 ml HC1, 5 ml HNO,, 10 ml glycerol). For XRD analysis, the phases were extracted electrolytically in two media: 20 pct &Po4 in H20 for selective extraction of y' and 10 pct HC1 in methanol for carbides and other phases.

Jan 1, 1970

By R. A. Graham, R. W. Rohde, J. R. Holland

In a shock wave compression study of a martensitic Fe-30 pct Ni alloy, Graham, Anderson, and Holland' found a region of unusual compressibility extending from a few kilobars up to about 20 kbars. This region was characterized by a continuously decreasing shock wave velocity with increasing stress. In this note, we report the results of a study initiated to determine the source of this unusual compressibility. In earlier shock-loading experiments on martensitic Fe-30 pct Ni, Loree et a1.' determined that a phase change occurred at about 80 kbars. Subsequently, Bowden and elly found that samples of a similar material shock-loaded at about 100 kbars experienced a martensite-to-austenite transition. Their crystal-lographic analysis showed the transition was a direct reversal of the established martensite system to the austenite phase. The shock loading in the present experiments was accomplished by precisely controlled plane impact between two discs of the sample material. This configuration created a state of uniaxial strain in the two the front of a projectile which was accelerated to various velocities. Planarity between the impacting discs was controlled to 5 x 10-4 rad, and impact velocities were measured to 0.5 pct. From a knowledge of the Hugoniot relationships of the material and the impact velocity, the shock-wave stress can be calculated. Samples were shocked at 18, 50, 70, and 100 kbars. The specimen discs shocked at 18 and 50 kbars were instrumented with quartz gages to observe the stress time profile. A more detailed description of the experiment has been given previously.4 The shock-loaded specimens were recovered intact by decelerating them in a catcher filled with soft wood. Discs of Fe-30 pct Ni nominally 12.7 mm thick and 64 mm in diam were cut from bar stock. Chemical analysis of the material provided the following composition in weight percents: 29.5 Ni, 0.50 Mn, 0.21 Si, and 0.10 C, with traces of Cr, Cu, Mo, Al, and Co. The discs were austenitized at 650° C for 2 hr at a pressure of less than l0-' torr, and furnace-cooled. Martensite was then produced by quenching the discs at -196" and holding 168 hr. The initial martensitic structure formed is shown in Fig. l(a). Typical microstructures of samples shock-loaded at 18 and 100 kbars are shown in Figs. l(b) and l(c). The banded structure with the austenite regions running parallel to the shock propagation direction was characteristic of samples shock-loaded at all stresses. No such banding was found in samples that were not shock-loaded. Comparison of Figs. l(b) and l(c) shows that, although under the optical microscope the two microstructures are quite similar, the martensite plates of the specimen shocked at 100 kbars etched in a distinctly different manner. This unique etching behavior of martensite in samples shock-loaded above the 80 kbar transition point has also been observed by Leslie el al.' These investigators determined from X-ray and electron microscope studies that fcc martensite, similar in appearance to normal bcc martensite, had been formed under shock loading. A quantitative determination of the amount of austenite present after shock loading was made by X-ray techniques. Both the methods of Lindren' and Miller' were utilized. The results are shown in Table I. The error limits are those experimentally observed from two independent analyses of each sample and represent the precision of the experiment. The absolute error, which should be similar for each sample, is believed to be about 10 pct. It is seen that as the shock stress increases the amount of austenite present also increases. On the basis of the X-ray and microscopic observations, we conclude that shock loading below the 80 kbar ersal will initiate a martensitic reversal: the amount of reversal that occurs increases with in-

Jan 1, 1969