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By O. F. Walker, W. C. Hahn, V. A. Johnson, J. D. Wood

The diffusion coefficients of zinc in single-crystal zinc and carbon in single-crystal and poly crystalline nickel were measured by means of radioactive tracer techniques both with and without the application of ultrasonic vibrations under conditions such that the temperature of the sample was closely controlled. The results of this investigation indicate no enhancement of diffusion in any of the samples. It is suggested that previously reported enhancement may have been due either solely to temperature increases caused by ultrasonic vibrations or in combination with changes in the boundary conditions. A number of observations have been reported in the literature in which it has been implied or inferred that the application of ultrasonics enhances diffusion (see, for example, Refs. 1-5). The present study was undertaken in an attempt to observe this effect under carefully controlled conditions, particularly with regard to measurement and control of the temperature of the sample. Two different types of systems were studied; these were the self-diffusion of zinc and the diffusion of carbon in nickel. EXPERIMENTAL For diffusion with ultrasonic energy applied, the samples were included as part of a resonant ultrasonic system operating at 58.5 kcps. The ultrasonic generators used were rated at 100 and 250 w and could be tuned over a frequency from 10 to 100 kc. A PZT (lead titanate/lead zirconate) ceramic transducer provided the driving vibration. This system requires no metallurgical joining of the specimen to the acoustical transmission line since the ultrasonic driver and the follow-up section clamp the specimen in position by means of a constant pressure of 50 lb developed by an air cylinder. The ultrasonic driver and follow-up section, both made of titanium, were 4 in. in length from clamping point to the end in contact with the specimen. Using the relationship given by Mason,6 A = V/f, the resonant wavelength, A, in titanium is calculated to be 3.3 in. at a frequency, f, of 58.5 kc, taking the velocity of sound in titanium, V, as 1.95 X 105 in. per sec. The 4-in. driver and follow-up section, therefore, are each 4.0/3.3 =1.21 times the resonant wavelength. Clamping pressure must be applied at stress nodes of the transmission line in order to preserve resonance. Therefore, a specimen length of 0.58 times the wavelength in the specimen was required to place the clamping pressure application points at stress nodes exactly three wavelengths apart. A stress antinode was contained in the center 3 in. of the specimen. A small PZT ceramic disc attached to the follow-up section provided an output voltage proportional to the intensity of the standing wave. This output voltage was monitored on an oscilloscope and the ultrasonic system was tuned to resonance by varying the frequency until the output signal was a maximum amplitude. The amplitude of the output signal was maintained constant throughout the diffusion anneal. A split cylindrical stainless-steel chamber, which was purged with argon prior to and during the runs, was placed around the specimen. The chamber in turn was surrounded by a movable furnace whose temperature could be controlled to 7C. Heat exchangers were used to cool the driver, follow-up section, and ultrasonic transducer. Great care was taken to obtain the true specimen temperature in all cases. Several different methods were tried; the most successful was that in which the thermocouple was held in contact with the midlength of the specimen by means of an asbestos insulating pad and wire straps. In the case of zinc, single-crystal specimens of 99.999 pct purity were used. The samples were 0.25 by 0.25 in. square and of the proper length for resonance, that is 1.1 in. long with the c axis parallel to the long dimension of the specimen for the case of diffusion perpendicular to the c axis and ultrasonic motion parallel to the c axis, and 1.9 in. long with the c axis perpendicular to the long dimension of the specimen for the case of diffusion parallel to the c axis and ultrasonic motion perpendicular to the c axis. In each case, one of the rectangular faces was electroplated with a thin film of zinc containing Zn The constant pressure used to clamp the specimen in place in the ultrasonic system caused some deformation in some of the samples. For these samples the deformation was concentrated in either end of the specimen; thus, for all samples (both zinc and nickel) the center in. was cut from the specimen after the diffusion anneal to be used for sectioning and counting. The nickel single-crystal samples, of 99.999 pct purity, were used in the form of rods 0.25 by 0.187 by 2.07 in. long with the (100) direction parallel to the rod axis. The polycrystalline nickel samples of 99.97 pct purity had an average grain diameter of 0.007 in. and were used in the form of rods 0.25 by 0.125 by 1.87 in. long. The direction of ultrasonic motion was parallel to (100) direction (bar axis) for the single-cqstal samples and parallel to the bar axis for the polycrystalline specimens. A thin film of c14 suspended in methanol was applied to the diffusing face of the specimen. Two specimens were butted together lengthwise for each diffusion anneal to minimize oxidation. After diffusion, a precision lapping device similar to the one described by Goldstein7 and a radiation detector were used to obtain a plot of specific activity vs penetration distance for each specimen. (A scintil-

Jan 1, 1969

TWENTY-FOUR of the 28 local sections and the two divisions of the Institute were represented at the meeting. Three sections failed to appoint delegates and two of those appointed failed to attend the delegates' meeting proper. Four sessions were held, two on Monday and two shorter adjourned ses-sions on Tuesday and Wednesday. Even at the end many things remained to be said and, in view of the amount of time the delegates lost from technical ses-sions the feeling was general that next year it would be advisable to hold their meeting the day before or day after the general meeting. Every part of the country was represented from Boston to Los Angeles and Seattle to Washington. All phases of Institute work and policy were taken up in the most informal way and the delegates will carry back to the sections, as they brought to headquarters, many ideas that will prove useful and stimulating. The time was divided between reports by the delegates on section activities and reports by officers of the In-stitute and of the various joint activities on the work at headquarters : A. D. Flinn told of the work of Engi-neering Foundation; W. V. Brown discussed the Em-ployment Service; J. A. Sohon explained what the Library is doing; T. T. Read told how the sections could help MINING AND METALLURGY ; H. Foster Bain discussed Institute affairs in general and asked and answered questions. An interesting new feature of the meeting was the appearance by request of Directors Turner and Smith of the U. S. Bureau of Mines and U. S. Geological Survey to answer inquiries as to the needs and work of their Bureaus. So much attention had been paid this year by the western sections to the diminished funds made available at Washington for research on mining problems that many questions came up. The accom-panying figures epitomize the answers.

Jan 3, 1928

By W. L. Austin

The only essential difference among the three methods of collecting the precious metals from their low-grade ores by fusion is comprised in the nature of the vehicle in which those metals are concentrated. If lead- or coppper-ores are used, the processes are respectively lead- or copper-smelting; but when the sulphide of iron forms the matrix in which the gold and silver are collected, the process is known as pyritic smelting. The latter method presents rarely any advantages when lead- or copper-ores are available at rates which permit profitable treatment. Pyritic silver-smelting, defined by Percy as " the smelting of silver-ores, which are either free from lead or do not contain it in sufficient quantity to collect the silver, in conjunction with pyrites, in order to produce a regulus in which the silver may be concentrated," is not, as the name would imply, confined to ores of this metal alone, but embraces auriferous silver-ores, or even gold-ores simple. This method of collecting the precious metals from lowgrade dry ores, employed at Freiberg by Barthel Kohler in 1585, does not appear, up to the present, to have been introduced into this country on a working scale. And yet the possibility of getting rid in a single operation of all the earthy or siliceous gangue of a lowgrade ore and concentrating the precious metals in a matte without loss of lead (which includes gold and silver) by slagging, or volatilization, at the same time producing a highly siliceous slag, very nearly if not quite as clean as is usual in lead-smelting, certainly commends itself. In some parts of the country, owing to the com-

Jan 1, 1888

By AIME AIME

THE Institute of Metals Division of this Institute held a joint meeting with the American Foundry- men's Association on Oct. 5-9, at Syracuse, N. Y. The registration at this meeting was about 150. There were four meetings in all, three of which were in con- junction with the American Foundrymen's Association. This combination works out very nicely and gives the I Division a number of practical foundry papers that it would not get otherwise. The sessions were well attended and the discussion was active. The session on Monday morning was of a general nature and consisted of the following subjects : " Refractory Problems in the Non-ferrous Electric Furnace Casting Shop, " "Temperature Control of Non-ferrous Alloys," "Atomized Coal System of Non-ferrous Melting," "Material Handling in a Brass Foundry." On Tuesday morning, the session was on "Aluminum and Its Alloys." The paper on permanent mold castings created a large amount of discussion, in fact so much that it had to be renewed after the close of the regular program. Aluminum is assuming a more important place every year and adds greatly to the program as a whole. One of the most remarkable meetings that this Division has ever had was held on Tuesday at noon in the form of a Round Table discussion, headed by G. K. Elliott, chairman of the Division, Cincinnati, Ohio. Mr. Elliott divided the members present, numbering about 80, into groups as they were seated at the tables. Each of these groups suggested a topic for discussion. They were as follows : "Fluxes on Market ;" "Simplification of Alloys;" "Pyrometric Control;" "Effect of Gas- sing Metal and Control;" "Barium Sulfate Added to Electric Furnace to Create Slight Oxidation to Remove Aluminum and Silicon;" and" Nickel in Brass."

Jan 1, 1925

By Nathaniel Herz

The formula very frequently used for computing the economical size of pipe to transmit compressed air is that of D'Arey, as follows: D = cV w1l Where, D = the volume of compressed air delivered in cubic feet per minute, at the final pressure. c = an experimental coefficient determined for the various sizes of pipe, d = the diameter of the pipe in inches. 1 = the length of the pipe in feet. p, = the initial gauge-pressure in pounds per square inch, p2 = the final gauge-preesure in pounds per square inch. w1 = the density of the air, or the weight in pounds per cubic foot at the initial pressure, p1. The most common case is that in which the given quantities are: the quantity of air required, the length of the pipe, and the initial pressure. The method of solution is to assume a pressure-loss and to compute the remaining factor, cd5, thus giving the size of pipe corresponding to the assumed loss of pressure. It is always desirable to try two or more pressure-drops, in order to find the combination that is most satisfactory, since often a small change in the size of pipe will reduce or increase the loss of pressure several pounds. An alternative method is to assume a size of pipe and calculate the corresponding pressure-drop. Each method involves a series of tedious calculations to arrive at the most economical solution, and also requires the use of tables giving the constant, c, the density of the air, w1, and often, for convenience, a table giving the values of the expressions p1-p2 and c J I hare constructed a graphic chart, Fig. 1, for the solution of

Jan 1, 1913

By AIME AIME

INSTITUTE members attending the Annual Meeting in New York who want to see one of the mining engineers' newest aids, photoelastic stress analysis, are due for an interesting afternoon on Thursday, Feb. 15, when open house: will be held at the Columbia University mining laboratory. Information as to the direction and distribution off stresses in mine structures, which has been developed by Professor Bucky, associate professor at the Columbia School of Mines, and David Sinclair, research assistant, is useful in the design of pillars and in the placing of openings relative to working places such as gangways and haulage levels.: This work has been sponsored during the last ten years by the Engineering Foundation.. It is fully reported in T. P. No. 1140.

Jan 1, 1940

By Sherwin F. Kelly

FRONTIERS of geological knowledge retreated further this past year before an ever-widening geophysical attack, as governments and endowed institutions continued to take an increasing practical interest in the geophysical line of approach to the study of earth phenomena. A year ago I opened this annual review with a brief account of the efforts to discover what formations lie concealed beneath the deep sediments which form the superficial portions of the Continental Shelf off the eastern United States. That work was but the beginning, and 1938 saw its continuation and expansion. With the assistance of a Guggenheim Fellowship, Maurice Ewing pushed his researches in the development of instruments and techniques for deep-sea seismic refraction studies. Ewing's early refraction profile from the Virginia Capes to the edge of the Continental Shelf has been followed by a similar traverse in Great Britain from the coast of Cornwall to the edge of the Continental Shelf southwest of England. This showed that the thickness of the sedimentary mantle and the rates of slope of the basement surfaces there are comparable to those in the Virginia Cape district.

Jan 1, 1939

By Robert Hunt

(New York Meeting, February, 1913.) I HAVE frequently stated that while the chemical composition of steel is important, yet even greater importance is connected with the mechanical and heat treatment of the metal. During the past year I encountered such a positive example of that fact that I deem it worth putting upon record. A prominent railway system divided an order for open-hearth steel rails between two steel works, both of which are under the control of the one corporation; giving to one about 18,000 tons, and to the other 7,500 tons of the same section and to be made under the same specifications. The rolling results obtained in the two mills varied so widely that a study of the figures is intensely interesting and serves to illustrate the advantages obtained by careful ingot casting, and, quite as pertinently, the possible benefits of careful subsequent heating and rolling with moderate reductions in the rolling process. The smaller order was rolled complete in four installments during the same months that the larger order was being made in six separate installments; but, to permit of exact comparisons, the totals of the four installments (completing the order with the mill which I will call A) are given with the totals of the first four installments of the larger order, made by the mill designated as B. These rolling results are:

Jan 5, 1913

By R. A. Corley, W. R. Wilcox, J. R. Teviotdale

Chemical vapor deposition of hafnium carbide yielded whiskers, needles, dendrites, faceted crystals, and adherent coatings. The gas stream compositiom and the mass transfer conditions determined the habit of the deposit. The deposits were obtained at temperatures ranging from 1100" to 1800°C. HAFNIUM carbide has the highest melting point of any binary compound; therefore, its various potential applications are a subject of vital interest to the aerospace industry. The experiments described herein were performed to investigate the chemical vapor deposition of hafnium carbide with particular interest being placed upon the possible production of high-strength single-crystal whiskers for composite materials. In 1931 Moers 1 used a gaseous mixture of HfC14, Hz, and toluene to vapor deposit crystalline hafnium carbide on a tungsten filament heated to 2400°to 2800°C. More recently Lepie 2 deposited hafnium carbide on graphite using HfC14 and methane in a helium gas carrier. The pyrolytic depositions described here were accomplished in graphite tubes by using various gas mixtures and dopants. The resulting crystal habits included whiskers, needles, needle dendrites, bulbous dendrites, faceted crystals, and smooth, adherent poly-crystalline layers. EXPERIMENTAL The depositions were carried out in an induction-heated graphite tube, 1.2 cm ID, which was contained in a vertical 9-cm-ID quartz tube. (A more detailed account of the experimental procedures and results is given in Ref. 3.) Refractory oxide fiber and tubes and graphite felt were utilized jointly and singly for therma1 insulation. A typical temperature distribution is shown in Fig. 1. The reactant gases were introduced at the top and removed at the bottom of the tube. Table I summarizes the experimental conditions and results. Many deposition habits were obtained. X-ray analyses showed that they possessed the hafnium carbide structure. Almost invariably these formed well above the point of maximum temperature in the graphite tube. The habit depended strongly on the gas composition. In a series of runs (e.g., run A) using HfC14 and toluene in H 2, hafnium carbide coatings, Fig. 2, were reproducibly obtained at the position where the tube wall was 1400°C, and bulbous dendrites, Fig. 3, were

Jan 1, 1969

By J. W. Onuscheck

The oxygen-fuel oil burner lance is a very useful tool at the Monessen B.O.F. It increases the overall flexibility of the operation. An additional 15,000 to 20,000 ingot tons can be produced at a given hot metal supply. It helps overcome sporadic drops in hot metal thermal values and/or supply. It results in increased yield, in particular, on high carbon heats where much yield was lost on reblow triggered slag reactions. The burner has also been adopted as a standard tool to aid burning in new vessel linings. Overall, steelmaking performance has improved with the use of standard preheat practice. Scrap charges up to 50 percent have been used routinely in times of extreme hot metal shortages, but the performance is weak in some categories. Development of a single step oxy-oil process is in progress. In this process, scrap and hot metal are charged as in the normal B.O.F. practice, but fuel oil is fired with the refining oxygen.

Jan 1, 1972

By AIME AIME

HOLDING the annual dinner-dance of the Institute at the Waldorf-Astoria had become such a tradition that there was widespread regret when it became known that the demolition of the building to make way for a huge office structure would perforce bring to an end the long and enjoyable series of gatherings our Institute had held there. This year the . Commodore was the place at which it was held and the commuters on the New York Central and the New Haven railroad systems, at least, found it a more convenient place for them. Except for the famous "Hoover" dinner, which will probably set a mark for all time, it was the largest dinner the Institute held, 1000 being present, and it taxed the facilities of the hotel to the utmost.

Jan 1, 1930

By F. P. Dewey

(Read at Amenia Meeting, October, 1877.) AT the Wilkes-Barre Meeting of the Institute, Dr. J. Lawrence Smith, in the course of his remarks on some peculiarities in the composition of irons, alluded to the so-called " buckshot" iron, and exhibited a specimen of this material. He said that when the small granules, or shot, were separated from the mass, they could be flattened under the hammer, and inferred that these particles had been decarburized by the blast before sinking into the hearth of the furnace, and thus we had the exceptional production of wrought iron in the blast furnace. I have recently obtained a characteristic specimen of this variety of iron from one of the furnaces at Orbisona, Pa. Considerable uncertainty existed as to its true nature and the conditions of its production. Its weight seemed to preclude the idea that it contained much or any slag, yet its lack of strength indicated that it was not homogeneous cast iron. At times considerable quantities had been produced, which could only be utilized by charging in the furnace and remelting. The specimen, on the freshly fractured surface, appeared to consist of flattened globules of iron cemented together by a bluish material which one would naturally suppose to be slag, and qualitative examination for lime strengthened this supposition. It was quite difficult to obtain drillings, as there was a tendency to split in several directions as soon as pressure was applied ; but enough was obtained to undertake quantitative determinations. They were found to consist of two portions-one attracted by the magnet, and the other not. By repeated separation the magnetic portion was found to be 94.44 per cent., and the non-magnetic 5.56 per cent. Analyses of these gave the following results :

Jan 1, 1878

By John B. Cook

Most of today's open pits take the form of conical-shaped excavations in the relatively flat or undulating terrain surrounding them. Ore is usually hauled uphill from the pit bottom by truck, rail, or skip to crushing, beneficiation, railroad loading, and stockpiling facilities near the edge of the pit. There are, however, a few orebodies whose locations in mountainous terrain causes special problems that generate different technical solutions. LAMCO's 10.5 million metric tons per year high-grade iron mine in the Nimba Range in tropical Liberia is probably one of the most extreme of these exceptions (Fig. 1). At Nimba there is a 2,000-ft difference in elevation between the upper- most levels of the orebodies and the start of the railroad below at the foot of the mountain. Haulage to the crusher is usually downhill at grades of up to 12% dictated by the topography of the rugged terrain. Ore is transported from the crusher down the mountainside by a conveyor sys- tem 10,096 ft long, whose average grade is 18%. The belt is braked by asynchronous generators, feeding power into the local network. The original crusher must be relocated at a lower elevation outside the final pit limit to allow that part of the mountain on which it now stands to be excavated. HISTORY The LAMCO Joint Venture is owned 75% by the Liberian-American- Swedish Minerals Co. (LAMCO) and 25% by Bethlehem Steel Corp. LAMCO is comprised of a 50% interest by the Liberian Government and 50% interest by Liberian Iron Ore Ltd (Fig. 2). This joint venture was launched to develop the high-grade iron ore deposits of the Nimba Range.

Jan 1, 1969

FRANK N. SPELLER,? Pittsburgh,. Pa.-Mr. -Hayward's paper again draws attention to the fact that copper in steel is not the enemy that a good many of us it one time thought it was. He shows clearly that steel with over 0.75 per cent. of copper is as dependable, under the :conditions which he describes, as the same steel without copper. I might add that you-can weld copper-steel- satisfactorily up to that point; in fact, we have succeeded in welding pipe by the lap weld process up to 1 per cent. copper. Notwithstanding the date that have been presented on the effects of copper on the physical properties and corrosion of steel, a maximum copper limitation is still found in many specifications. In some cases the limit is extremely low, such as below 0.05 .or 0.03: per cent., or thereabout. That is a relic of days gone by, and I think the practice should be discouraged. E. F. CONE, New York; N. Y.-Not so many years ago steel-casting makers were very particular as to the amount of copper that existed in the pig iron that they used. They would not use copper-bearing pig iron unless mixed with non-copper iron. I do not know what the practice now is in the particular foundry where I was metallurgist at one time,

Jan 4, 1918

By Arthur A. Center

World production of electrolytic zinc has shown an increase for each year since 1932. Production up to 1936 was summarized in my earlier paper [Trans. A.I.M.E. (1936) 121, 453-4641, and this present paper carries the subject through 1943. During this time of increase, it is safe to say that the average purity has been raised more or less continuously, and the amount of four-nines metal has been in- creased. While the period reflects preparations for and the carrying on of the present war, electrolytic zinc proved its value in many industries as a peacetime metal in the years from 1919 to 1940. World production (Table I) increased from about 594,000 tons in 1936 to around 858,000 tons in 1943; United States production increased from 127,171 tons to 329,903 tons for the same years. Total production of primary zinc in the United States is given in the first column of Table I; retort production of primary zinc, obtained by difference, in the last column. The curves drawn from these figures are shown in Fig. I. They represent continuations of the curves in the earlier paper that cover commercial production of electrolytic zinc from its inception in 1915 to 1935. The earlier paper gave data for total world production and foreign retort production (calculated therefrom) and showed curves of electrolytic vs. retort production

Jan 1, 1944

By Richard P. Rothwell

THE communication which I have to lay before my fellow-members of the Institute, is no elaborate paper, nor the statement of any great discovery ; it is simply the record of convenient methods of conducting topographical surveys, and of keeping the notes of the same; methods that have grown out of practical experience, and have saved me many a day's labor by facilitating office and field work, and at the same time secured a greater degree of accuracy than is obtained by the methods now in general use. I assume it as granted that no topographical map is worthy of the name, except it represent the elevations and depressions of the surface by means of horizontal or contour lines. In the Ordnance Survey of Great Britain, the contour lines are traced for every fifty feet vertical height, I believe, by running out the line with level and compass through all its meanderings on the surface ; this, of course, is a very tedious, though accurate process, but "in the woods," where many of our surveys have to be made, it would be practically impossible. Some time ago, I made an extensive and quite elaborate topographical survey and contour map of the southern portion of the Cahaba coal-field, in Alabama, the object of the survey being to

Jan 1, 1875

By H. H. Podgurski, J. C. M. Li, Y. T. Chou, F. N. Davis, R. A. Oriani

When an Fe-2 pct A1 alloy is nitrogemted at 500ºC with a gus tnixture (NH3-H2) in which the nitrogen activity has been kept Lou] enough to avoid the formation of iron nitride, a two-phase alloy is generuled which consists of AlN particles and a ferrite phase cotaining a heavy network of dislocations. The amount of nitrogen contained in such an alloy, when equilibrated with the nitrogenating atmosphere, far exceeds both that needed to satisfy the normal solution requirements of a Fe and that needed to convert all of the aluninuwi to AlN. This excess nitrogen is accounted for as being trapped on dislocations, adsorbed at the ferrite -AlN interface, and as an en-Iuznced lattice solubility in strained ferrite. This excessive uptake of nitrogen had previously been attribuled by other investigators to the formation of a nonstoichiornetric aluminum nitride. Isotope exchange experiments revealed various amomts of exchargeable N14 present in the originally nitrided samples that could not be removed by reduction with HS at 500ºC. This exchangeable nitrogen has been identified us that bound to the AlN -ferrite interface. Estimates of inter facial areas in alloys containing -3 pct by weight of A1N are as high as 10 sq m per g of alloy. ThE first1 of this series of papers described the experiments forming the basis for the elucidation of the mechanism of the formation of aluminum nitride particles within an Fe-A1 alloy. It was found that not only are dislocations necessary for the nucleation of the AlN particles but also the nitriding reaction in turn produces a dense network of dislocations in the ferrite matrix. It was also observed that nitrogen in excess of that needed for the formation of stoichiometric AIN is taken up by the alloy without the formation of an iron nitride. The present paper is an analysis of the excess nitrogen sorbed by the nitrided Fe-A1 alloy which considers the structure generated by the formation of the aluminum nitride particles. Because of the high density of dislocations, this system has proved to be quite useful in studying nitrogen-dislocation interactions. Wriedt and Darken2 have already reported such studies in a cold-worked ferritic steel. EXPERIMENTAL Nitrogen Sorption. The specimens of this alloy were cold worked (50 pct reduction) to 0.011 in. thickness and chemically cleaned in a 2:1 concentrated phosphoric acid-50 pct hydrogen peroxide solution before nitrogenation. The flowing nitrogenating atmosphere (11 pct NH3-89 pct H2) was established before the ni- trogenating temperature was reached. The same gravimetric and gas-flow equipment described in an earlier paper1 was also used in this investigation. Changes in nitrogen concentration were followed gravimetrically when establishing the isotherms. In the isotope exchange experiments, concentration changes were followed volumetrically. In some instances chemical analyses (Kjeldahl method) were used to check for material balances in both the gravimetric and volumetric procedures. Our objective was to obtain reversible nitrogen sorption isotherms for alloys equilibrated with NH3-H2 gas mixtures over a large range of nitrogen activity* and temperature. The *Defined as equal to PN H /P3/2 ,where P corresponds to partial pressure in atmospheres. Actually the nitrogen activity, aN, in the alloy equals K PNH3 /p3/2H2, where K is the equilibrium constant for the reaction NH3 = N + 3/2H2. upper limit for nitrogen activity was below that which would produce iron nitride; for reasons which will become apparent later, most of the sorption studies were made in the temperature range between 400" and 500'C. The alloy sample studied most extensively in this investigation was given a series of successive reductions (100 pct H2) and nitrogenating treatments at 500°C to attain a stabilized structure. Presumably some dislocations were lost during these treatments. Throughout most of the sorption studies, temperature was held at ± 1°C and the gas-phase composition was held to k0.2 pet NH3. Based upon the results of numerous diffusion experiments with this alloy* the 'Results to be published in a third paper of this series. times chosen for equilibration were considered more than adequate, Nitrogen Isotope Exchange. The first exchange experiments were carried out by circulating a measured quantity of H2 and NH3* (with a predetermined isotopic *The NH3 was synthesized over a synthetic ammonia iron catalyst using H2, and N2, enriched with N15. AS the NH3 was formed it was removed continuously from the gas phase by circulating the mixture through a refrigerated (78ºK) trap. When most of the nitrogen had been converted to NH3, it was distilled from the trap into a glass storage vessel. composition, N15/N14) over a nitrided specimen at 450°C in a closed glass system. Attempts to reach the exchange limit isothermally, i.e., an isotopic ratio (N15/N14) in the gas phase identical with the extractable nitrogen in the nitrided alloy, were futile. The exchange rate between the gas phase and the alloy was too slow, involving many days. To circumvent the slow exchange with the gas phase, measured amounts of N15 and N14 were introduced into the alloy by nitrogenating with an NH3-H2, mixture at 500°C containing an N15/N14 ratio of 7.76; the charged specimens were then sealed by allowing an oxide film to form over them in air, and in this final condition the specimens were subjected to 500°C in vacuum for various times during which isotope exchange was allowed to proceed within the specimen. It was estab-

Jan 1, 1970

By T. F. Witherbee

In a paper read at the Lake Superior meeting, August, 1580, an account was given of the successful use of Rendrock. and Monaky powder upon a .scaffold- and salamander in the furnace. On April 5th, 1881,' the same trouble called for like treatment, which, though not so immediately successful, was on the whole more instructive than the first trial, and points, I trust, to a reasonably sure remedy for all such difficulties. Up to December 4th, 1880, foundry and mill iron were made from Old Bed and Sew Bed magnetite, and Kearney red hematite, when a return was made to Bessemer iron, from an inferior quality of New Bed ore as compared with that used during first blast. January lath, 1881, New Bed, Chateangay, and East-shaft, a newly-opened Bessemer deposit of Messrs. Witherbee, Sherman $ Co., were first used, and continued up to February 13th, on a fuel charge of 80 per cent. anthracite and 20 per cent. coke, the product on the three ores being about 10 tons more per day than on New Bed alone. From this time until March 11th all coal was used, and New Bed, Chateaugay, and East-shaft ores, up to February 224 and from that date Chateaugay and New Bed, the product falling off 9,8, tons per day as a result of not using coke. It is fair, however, to state that the furnace was not in good condition during this period, being over-burdened, and the New Bed ore was, temporarily, uncommonly poor, for reasons of no particular interest here. It required to properly flux it at least 140 per cent. of limestone; and 101 per ent. was actually used. March 11th, all Chateaugay ore aid 80

Jan 1, 1882

By T. F. Witherbee

IN a paper read at the Lake Superior meeting, August, 1880, an account was given of the successful use of Rendrock and Monaky powder upon a scaffoldn and salamander in the furnace. On April 5th, 1881, the same trouble called for like treatment, which, though not so immediately. successful, was on the whole more instructive than the first trial, and points, I trust, to a reasonably sure remedy for all such difficulties. Up to December 4th, 1880, foundry and mill iron were made from Old Bed and New Bed magnetite, and Kearneyy red hematite, when a return was made to Bessemer iron, from an inferior quality of New Bed ore as compared with that used during first blast. January 18th, 1881, New Bed, Chateangay, and East-shaft, a newly-opened Bessemer deposit of Messrs. Witherbee, Sherman & Co., were first used, and continued up to February 13th, on a fuel charge of 80 per cent. anthracite and 20 per cent. coke, the product on the three ores being about 10 tons more per day than on New Bed alone. From this time until March 11th all coal was used, and New Bed, Chateangay, and East-shaft ores, up to February 22d, and from that date Chateangay and New Bed, the product falling off 9 6/10 tons per day as a result of not using coke. It is fair, however, to state that the furnace was not in good condition during' this period, being over-burdened, and the New Bed ore was, temporarily, uncommonly poor, for reasons of no particular interest here.. It required to properly flux it at least 140 per cent. of limestone; and 101 per cent was actually used. March 11th, all Chateangay ore and 80

Jan 1, 1882

By B. E. Eakin, R. T. Ellington

An apparatus and a procedure for determining the viscosity behavior of hydrocarbons at pressures up to 10,000 psia and temperatures between 77 and 400° F are described. The equipment is suitable for measuring viscosity of either the liquid or vapor phases or the fluid above the two-phase envelope for systems exhihiting retrograde phenomena, according no the phase state of the system within these ranges of temperature and pressure. Equations are developed for calculation of viscosity from the experimental measurements, and new data for the viscosities of ethane and propane at 77° F are reported. INTRODUCTION With the advent of higher pressures and temperatures in industrial processes and deep petroleum and natural gas reservoirs, demand has increased for accurate values of physical properties of hydrocarbons under these conditions. Proportionately, more frequent occurrence of natural gas and condensate-type fluids is encountered as fluid hydrocarbons are discovered at greater depths. This increases the importance, to the reservoir engineer, of being able to predict accurately the physical properties of light hydrocarbon systems in the dense-gas and light-liquid phase states. Reliable gas viscosity data are limited primarily to measurements made on pure components near ambient temperature and at low pressures. Few investigations have been reported for high pressures, and except for methane, data on light hydrocarbons are subject to question. This is demonstrated by the large discrepancy between sets of data on the same component reported by different investigators. For mixtures in the dense gas and light liquid regions and for fluids exhibiting retrograde behavior there are very few published experimental data. Viscosity data for methane have been reported by Bicher and Katz,1 Sage and Lacey,12 Comings, et al,3 Golubev,3 and Carr,3 with good agreement among the last three sets of data. Comings, Golubev and Carr utilized capillary tube instruments for which the theory of fluid flow is well established. The theory permits calculation of the viscosity directly from the experi- mental data and dimensions of the instrument alone. Sage and Lacey, and Bicher and Katz used rolling-ball viscometers. The theory of the rolling-ball viscometer has not been completely established, and these instruments presently require calibration by use of fluids of known viscosity behavior before viscosities of test fluids can be measured. To obtain accurate data it is necessary that the rolling-ball viscometers be calibrated by use of fluids of density and viscosity similar to the test fluids, a difficult selection for the gas phase. From the methane data and experimental tests on various natural gases, Carr developed a correlation for predicting the PVT behavior of light natural gases.2,3,4 This correlation was based on data for a very limited composition range; its application to rich gases and condensate fluids is questionable. The object of this investigation is to develop an instrument which can be used to obtain viscosity data at reservoir temperatures and pressures, for rich gases, condensate-type systems above the two-phase envelope and light liquid mixtures. These data will be used in an effort to develop correlations to represent the viscosity behavior of these fluids. APPARATUS In a previous viscosity study Carr2 utilized a modified Rankine capillary viscometer configuration," Fig. 1. In this instrument the gas to be tested is forced through the capillary tube in laminar flow by motion of a mercury pellet in the fall tube, the measured displacement time being that required for the mercury slug to move between the brass timer rings. The viscometer is constructed of glass and mounted in a steel pressure vessel. The test gas pressure in the viscometer is balanced by an inert gas (usually nitrogen) in the vessel. Excellent results have been obtained with instruments of this type, with Carr2 and Comings5 reporting repro-ducibilities of 99.5 to 99.3 per cent and an estimated absolute accuracy of 99 per cent. However, these instruments have limitations which have precluded their use for liquids. The need for maintaining a balance between pressures of the test fluid and inert gas in the viscometer vessel presents operating problems, and requires charging the test fluid to the viscometer very slowly. The principle drawback to the Rankine unit is behavior of the mercury slug which provides the pressure differential across the capillary. When even trace quantities of propane or heavier hydrocarbons are present in the test gas, the mercury tends to subdivide