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By J. M. Floyd

The theory, construction and applications of oxygen sensors employing high-temperature electro- chemical cells with solid electrolytes are briefly reviewed. The application of disposable probes to measurement of the oxygen potential in matte and slag baths in tin, copper, and nickel smelting operations is described. Examples discussed include end-point determination in smelting and slag-cleaning operations, pilot-scale investigations of process chemistry to assist in the development of smelting strategies, and measurements in operating smelters to improve the efficiency of operation.

Jan 1, 1984

By A. Vignes, J. P. Sabatier

A study of ternary diffusion at 1315°C in the Fe-Co-Ni system covering the entire ternary phase diagram has been carried out. Experimental values of the four interdiffusion coefficients DFeNico,DFeCoCo, DFeCoNi were computed at 33 points of the ternary diagram. The limiting values of these coefficients on the three sides of the ternary diizgram have also been determined. This set of data is presented as a contour map on the ternary isotherm for each of the four coefficients. Assuming that the Fe-Co-Ni system can be considered as ideal, the phenomenological coefficients Lk ij (with k = Fe) have been computed and the Onsager reciprocal relutions verified. It is shown that, in the Fe-Co-Ni system, the diffusion process can also be described by only two interdiffusion coefficients DFeFe and DCoNiFe, the second cross diffusion coefficient DCoFeNi being equal to zero and the second direct difusion coefficient being given by The values of the cross interdiffusion coefficients and of the Onsager coefficients are explained in terms of atomic mobilities of the three components with the help of a kinetic calculation due to Lane and Kirkaldy.8 It is shown that all the results are explained if the tracer difusion coefficients of the three components are such that DFe > DNi ~ DCo in complete agreement with experimental data on the three binary systems. DIFFUSION in a ternary alloy system is basically and significantly different from diffusion in binary alloys. In binary diffusion, there is just one independent composition variable and only one coefficient Dij is needed to describe the interdiffusion process. In ternary diffusion, we must allow for cross interaction between two independent species, and four interdiffusion coefficients are necessary to describe the transport process. Kirkaldy et al.1,2 have determined interdiffusion coefficients in the systems, Cu-Mn-A1 and Zn-Cu-Al. Guy and Leroy4 have reported intrinsic diffusion coefficients for the r phase at 1300°C of Co-Ni-Cr alloys as a function of composition using the analysis of Philibert and Guy.3 Interdiffusion coefficients were measured at three different compositions at 850°C in the single phase copper-rich corner of the Cu-Zn-Mn system by Dayananda and race.5 Zie-bold and Ogilvie6 have determined interdiffusion coefficients in the single-phase field of the Cu-Ag-Au system at 725°C. Preliminary results on diffusion at 1136°C in the system Fe-Co-Ni have been reported.7 In this study, data are reported on a more complete determination of interdiffusion coefficients in the Fe-Co-Ni system in the entire ternary at 1315°C. There is complete solid solubility with the fcc structures at 1315ºC, and this system can be considered as nearly ideal. This approximation allows the computation of the Onsager phenomenological coefficients. These values can then be used to test a kinetic calculation of the Onsager L coefficients in ternary substitutional solid solutions due to Lane and Kirkaldy.8

Jan 1, 1970

By H. Vance

In 1932, as in 1931, the East Texas area outside the Gulf Coast exerted ' its influence over the entire petroleum industry. Practically 60 per cent of the oil wells completed in the United States during 1932 were in this area, development being chiefly confined to the East Texas oil field in Upshur, Gregg, Rusk, Smith and Cherokee counties. This East Texas area is geologically an interior salt dome basin, along the western edge of which are located the fault line fields as represented by Mexia and Powell. Production occurs on salt domes in the interior of the basin as represented by Boggy Creek and possibly Van, although no salt has actually been discovered in drilling at Van. Shore line conditions on the east side of this basin along the flanks of the Sabine uplift have been responsible for the East Texas oil field. Many known salt domes in the center of this basin have been tested but as yet have failed to produce oil in commercial quantities. The main producing horizon throughout the area is lowermost upper Cretaceous and is known locally as the Woodbine sand. The East Texas Oil Field Development.—Approximately 6000 producing wells were completed during the year in the East Texas oil field. No accurate estimate of the total initial production of these wells is available because few initial production tests were made as the wells were completed. The writer estimates the average initial production of these completed wells at 2500 bbl. per day while flowing wide open through tubing. Based on this estimate, the total initial production of the wells completed during the year is 15,000,000 barrels. At the close of 1932 there were approximately 9500 completed wells in the East Texas field. Of this number 176 were without pipe line connections. The oil produced from these unconnected wells could be marketed for $0.30 per barrel while the price paid for oil run from the connected wells was $0.75 per barrel.

Jan 1, 1933

I. N. KNAPP, Ardmore, Pa. (written discussion *).-The writer would first call attention to the fact that the mid-Continent field was credited from 1900 to 1915 with a production of about 641,000,000 bbl. of oil with-out any burdensome water troubles being reported. In fact, the authors say the conditions were not acute until about two years ago when the unusual conditions in the deeper oil fields were first encountered. The writer disclaims any personal knowledge of the district mentioned but, from the experience he has gained in directing drilling in various fields by both the cable-tool and the rotary methods and also in plugging and cementing wells, he fails to see how the analysis of water trouble given in the paper under discussion could be of any practical assistance in solving the problems so vaguely outlined. Possibly it might induce academic discussion, if not limited to practical operating conditions. A recent bulletin of the Bureau of Mines gives definite and practical statements that can be easily understood by one skilled in the art of drilling wells and heading off water troubles. From an operating standpoint subsurface knowledge must be based on logs of completed wells. Absolutely no one can have such knowledge as that indicated in Fig. 1 of the paper in question without drilling wells, and no one can question such facts when disclosed by the drill. Under classification of water the paper states "This water (primary) cannot be exhausted from the sands, but its encroachment can often be checked and so directed that wells need not be abandoned, until most of the available oil is secured." This is a live question to the writer. A couple of years ago he had some wells drilled and found the conditions comparable with sands A and D of Fig. 1 with B and C left out; but nothing in the paper, so far as can be found, indicates how this water encroachment is or can be checked or directed particularly under the High heads named.

Jan 5, 1919

By J. Winter, W. C. Setzer, A. J. Goldman

ANISOTROPY in cold worked tempers of commercial aluminum alloys is manifested in deep drawn products as protuberances or ears 45 deg to the rolling direction. This reflects the {123}(412) rolling texture.' In fully annealed material, 0 to 90 deg ears in and per-

Jan 1, 1970

By R. F. Mehl, C. E. Birchenall

R. E. Hoffman and D. Turnbull—The authors have presented evidence which they have interpreted as indicating that the rate of self diffusion is not intrinsically more rapid at grain boundaries than within the grain. Grain-size effects which apparently exist are attributed rather to impurities concentrated at the grain boundaries. In view of our own experiments and the existing evidence, we believe that the support for this hypothesis is not convincing. We have in progress an investigation in which the rate of self diffusion of silver is being measured over an extended temperature range in both single-crystal and polycrystalline specimens. The results of the single-crystal experiments and some preliminary data on fine-grained polycrystalline specimens have already been reported:' and it is anticipated that a complete report will be published in the near future. The self-diffusion coefficient of large-grained polycrystalline silver (1 grain per sq mm) has previously been measured by Johnson" between 730" and 940°C. The diffusion coefficients which we have measured in single crystals (210 plane normal to diffusion direction) agree within experimental error with values calculated from an extrapolation of Johnson's curve down to temperatures as low as 500 °C. However, it has been demonstrated that the overall self-diffusion rate in fine-grained polycrystalline specimens (initial grain size of 0.003 cm) becomes measurably larger than the overall rate in a single crystal at a temperature of 600°C, and the discrepancy between the two rates becomes greater as the temperature is further decreased. In fact, it has been possible to obtain satisfactory penetration curves for polycrystalline specimens using the sectioning technique at temperatures as low as 400°C. At this temperature, the penetration is 50 to 100 times greater in the polycrystalline specimens than in a single crystal. Fisher" has developed an analysis whereby the ratio of the rate of the unit diffusion process at the grain boundary to the corresponding rate within the grain can be calculated from the penetration curves and an assumption as to the width of a grain boundary. This analysis applied to our data indicates that the unit process at the grain boundary is faster by a factor of 10' at 475°C when the grain boundary width is taken to be 5. The silver used in most of these experiments was obtained from the Handy and Harmon Co. and listed as 99.97 pct pure. Preliminary experiments on 99.999 pct silver from the Jarrel-Asch Co. indicate a grain-size effect of the same order of magnitude as in the less pure silver. Nominally, these purities are as good, at least, as that of the carbonyl iron used by the authors, but of course if an impurity effect does exist its magnitude might be very dependent upon the nature of both major and minor constituents. The authors have cited the work of other investigators who have found no grain-size effects. Neither Steigman, Shockley and Nix" nor Maier and Nelson8 were able to correlate self-diffusion coefficients of copper with grain size. However, all their measurements were performed at or above 750°C; and on the basis of our work with silver, no grain-size effect would be expected at temperatures above about 0.7 of the absolute melting temperature unless the grain size were exceedingly small. Likewise, in the investigation of the self diffusion of lead by Seith and Keil,14 the lowest temperature at which the diffusion coefficient was measured in polycrystalline specimens was 207°C, which is still sufficiently high so that the lack of a grain-size effect is not surprising. Finally, in those experiments on iron from which they concluded that there was no grain size effect, Drs. Birchenall and Mehl seem to have no information as to the actual grain sizes immediately prior to and following the diffusion anneal. Without this information, we believe that their own experiments offer little support for their hypothesis. F. S. Buffington, I. D. Bakalar, and M. Cohen—The results given in this paper agree in order of magnitude with those tentatively reported by us.27 However, significant differences exist in the two sets of data, and it may be well to make an explicit comparison. The diffusion studies at M.I.T. were conducted on somewhat higher purity iron (99.98 pct Fe) than the grades used by the authors, but this is undoubtedly not the answer. Fig. 4 shows the diffusion results of both laboratories for the gamma phase, omitting the authors' data on the commercial steels, while fig. 5 presents a similar comparison for the alpha phase. The divergence is much more marked in the latter case than in the former. In connection with the M.I.T. determinations, all of the runs in the gamma range and those above 800 °C in the alpha range were conducted with specimens having a relatively thick (0.002 cm) electrodeposit of radioactive iron. This practice minimizes any possible error due to extraneous diffusion that may occur during the heating to and cooling from the operating temperature. An exact solution of Fick's law for these boundary conditions was used in calculating the diffusion coefficients. At a later time, three runs were made below 800°C, using very thin electrodeposits similar to those of the authors, and the points fell considerably below the values expected from the extrapolation of the results based on the specimens with the thick deposits (compare dash-dot line in fig. 5). However, in the runs with the thin deposits, deviations of 100 pct were found between the individual specimens, whereas the maximum deviation with the thick deposits was less than 25 pct. Accordingly, it is not known at the moment whether the M.I.T. points below 800 °C should be given as much weight as those above 800°C. If this were done, the frequency factor would be of the order of 400 cm2 per sec, which is quite high. In other metals, the frequency factor for self diffusion lies between about 0.1 and 10 cm2 per sec. As the points below

Jan 1, 1951

By H. K. Birnbaum

The effect of 1ow-temperature stabilization anneals on the structure of the 0 phase Au-Cd alloys and on the diffusionless transformations observed in these alloys was examined by X-yay diffraction techniques. A phase separation in the ß-phase region was proposed to account for the experimenta1 results. The effects of quenching from elevated temperatures on the transformation behavior of these alloys were shown to be consistent with the proposed mechanism. IT has been shown that the high-temperature ß phase (CsCl structure) of the Au-Cd alloy system transforms to a phase having an orthorhombic (D2) ß&apos; structurel1-3 for compositions near 47.5 at. pct Cd and a tetragonal (4/m, m, m) ß" structure* in the vicinity of 50.0 at. pct Cd. Both transformations are diffusionless, crystallographically reversible, and occur on cooling at about 60° and 30°C respectively. The temperature interval from the beginning to the end of the transformation is of the order of 5°C in each case. Although the transformations are normally athermal, some of them have been reported to occur isothermally.= wechsler6,7 has shown that the effects of quenching a 49.0 at. pct Cd alloy from elevated temperatures are consistent with the retention of a nonequilibrium number of lattice vacancies. Annealing of these quench effects results in a broadening of the X-ray reflections.8 After a suitable quench, the 47.5 at. pct Cd alloy transforms to a phase having not the p&apos; orthorhombic structure but another structure which has properties similar to that of the ß" tetragonal structure.5.9 This change in the type of transformation has also been obtained after long anneals in the ß-phase region at about 70oC10 The present investigation was primarily concerned with the structural changes accompanying the above transformation phenomena. The change in transformation product and accompanying physical changes during an anneal in the ß phase have been termed stabilization effects. Experimental Procedure —The results reported in this investigation were obtained with the use of a Norelco diffractometer fitted with a temperature-controlled cryostat. The specimen temperature was controlled to better than ± 0.l°C during the measurements. CrKa radiation monochromated electronically with the use of a scintillation counter and pulse height analyzer was utilized. Specimens containing 47.5 and 50.0 at. pct Cd were prepared by sintering filings obtained from homogenized ingots of the proper alloy composition. (Gold of 99.999 pct purity and cadmium of 99.98 pct purity were used). All heat treatments were carried out with the specimens capsulated in vacuum ( < 10 % mm Hg) or in a He-H gas mixture. The quenching technique used in these experiments was to drop the pyrex capsule which contained the specimen from the annealing furnace into water, the temperature of which was controlled. The pyrex capsule shattered on contacting the water resulting in a relatively rapid quench. After the heat treatment, the specimens were mounted in the diffractometer and were left undisturbed in the diffractometer specimen holder during each sequence of measurements. EXPERIMENTAL RESULTS A) Low-Temperature Annealing—The transformations which were considered "normal" for these alloys were those obtained athermally during furnace cooling at approximately 50°C per hr after an elevated temperature anneal. Under these experimental conditions, the specimens were observed to transform to phases having structures whose diffraction patterns could be indexed as the ß&apos; orthorhombic structure for the 47.5 at. pct Cd and as the 0" tetragonal structure for the 50.0 at. pct Cd alloys. The transformation temperatures on cooling were approximately 60" and 30°C, respectively. Under the "normal" conditions both transformations were observed to go to completion, i.e., the entire volume of the ß phase was transformed to the product phase. In some specimens an extremely weak ß 110 reflection was observed at 20°C indicating that a small amount of retained ß was present. The effect of low-temperature annealing on the nature of the diffusionless transformations was examined for the 47.5 and 50.0 at, pct Cd alloy. The specimens were annealed in evacuated capsules at temperatures in the vicinity of 600°C (as specified in Table I) for 24 hr and were then cooled to 100°C at a rate of 50°C per hr. The specimens were then removed from the capsules and mounted in the diffractometer without allowing the specimen temperature to drop below 80°C. Annealing at the low temperatures was accomplished in the diffractometer by means of the cryostat which was mounted around the specimen. During the low-temperature anneals the lattice parameter, integral breadth of the reflections, and ratios of the integrated intensities of the fundamental and super lattice reflections for the 0 cubic phase were periodically determined. After annealing for the required time, the specimens were slowly cooled in the diffractometer and the diffraction patterns were recorded as a function of temperature. The specimens were cooled until the phase transformations were completed, following which the specimens were heated and diffraction

Jan 1, 1960

By D. M. Jamieson, M. P. Pearse, E. R. A. Plumstead

In 1948 the shaft sinking record in the Republic of South Africa was held by the Van Dyk Consolidated Mines Ltd. for a ventilation shaft with a footage of 461 ft sunk during the month of August 1941. This record remained for some ten years; but in the ensuing nine years it was broken no less than 13 times. Table I gives shaft sinking records throughout the world for the 21 years, 1940 to 1960. History shows that the wide, deep, timbered rectangular shaft had passed its peak of popularity by 1948, although it still had a great deal to commend it, both from the sinking and operational points of view. In sinking, it is easy to clean manually, and water can be handled by bailing when wet ground has to be negotiated; its shape also lends itself to equipping concurrently with sinking. In operation it provides the most convenient "in line" hoisting arrangement, and if the ventilation requirements so demand, it offers the simplest solution in that it can be divided into upcast and downcast sections. Furthermore, in the case of a multi-level mine, the shaft compartments can be reduced conveniently if the full area of the shaft is not required to serve all levels.

Jan 4, 1963

By Frank Firmstone

. In the early decades of the past century the method of starting iron blast-furnaces by " scatlolding-down" seems to have been in universal use for coke-furnaces and, at least in this country, for charcoal-furnaces also. It was likewise used at some of the early anthracite-furnaces, as is stated in the important " Reminiscences" printed by the late Samuel Thomas.&apos; It had been generally superseded in Great Britain as early as 1850, by some variations of the plan now used, and was rarely used when Percy wrote.2 On the Continent it was still followed ill the 60&apos;s; and was elaborately described by Valerius in 1852. I have never read any statement as to when and by whom " scaffolding " was first dispensed with, but the following extracts from journals of my father seem to fix an authentic date for an instance in this country: " [Pittsburg] July 12, 1838.—Went with Major Wade to his foundry,etc., and he gave me a letter to D. Tyler, Esq., Farrandsville, Agent Boston Coke & Iron Co." " [Lockhaven, Pa.] July 18, 1838.—Heard there was a flat-boat going to take some gentlemen up to Farrandsville. Got on boat and to Farrandsville, 5 or 6 miles, in 1 hr. 30 min. Dined, and then delivered my letter to Ma Tyler, who showed me much attention, and everything belonging to the furnace, and had the water turned on the wheel that I might see the blowing-cylinders at work. There are two cylinders, 6-ft. stroke, -56 in. in diameter, but they find that one makes more than enough blast for the furnace. The furnace has 16-ft. boshes, 7-ft. tunnel-head, and is 47 ft. high, 3 tuyeres, and 3 heating-ovens [hot blast-ovens]. A

Jan 1, 1908

By J. E. Harris, J. A. Whiteman, A. G. Quarrell

The graphitizing reaction has been studied in a number of Fe-C-Si alloys in the temperature range 550° to 725°C. The TTT relationships exhibit "C" curve behavior except where nuclei, either foreign or graphite itself, are present before the start of the reaction. It is suggested that the rate -controlling process is diffusion of carbon through ferrite. For the reaction to proceed at the observed rate it is calculated that the matrix surrounding the particles must deform plastically; experimental evidence for this deformation is presented. It is well-established that the decomposition of austenite to pear lite occurs at a maximum rate at an intermediate temperature.l-5 This "C curve" be- havior, which has been reported in a number of other systems,5-10 is a consequence of the relatively low rate of nucleation of the pearlite at small degrees of undercooling of the austenite. The cemen-tite phase in the pearlite is, in turn, metastable with respect to graphite and if steels are held for prolonged periods at elevated temperatures decomposition of the pearlite occurs. It is difficult to predict the shape of the subcriti-cal graphitization TTT (time, temperature, transformation) diagram for, in this case, undercooling does not occur. However, the free-energy change for the reaction does decrease with increasing temperature" (Fig. 1) and it is thus anticipated that the rate of nucleation will fall as the temperature approaches that of the eutectoid. In addition, a decreasing growth rate with increasing temperature is predicted in some circumstances with pure Fe-C alloys. However, apparently similar conditions exist for first-stage graphitization in the austenite range (malleabilization) but no evidence for C curve behavior has been presented in the extensive liter-

Jan 1, 1965

By C. S. Barrett, A. Smigelskas

J. T. NORTON*—I think Mrs. Smigelskas Fischer has done a splendid job in working out the pole figures from rather difficult photograms which are common to beryllium. Is there not a mistake in Fig 2 in that the pole figures B and C have been interchanged? A. SMIGELSKAS FISCHER (authors&apos; reply)—Yes, there is such an error in the labeling of the pole figures of Fig 2. The correct plane for Fig 2b and 2c is the plane in parenthesis above the figure numbers and not that in the figure subtitle. J. T. NORTON—Also, I would like to mention another method of obtaining the data for pole figures which would be particularly applicable to this problem. It is a method which has been published only

Jan 1, 1950

By Walter Showak

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

Jan 1, 1962

By Henry N. Doyle

Basic procedures in the mining industry have changed only slightly over the centuries since metals and fossil fuels became an essential part of man&apos;s economic and cultural life. Mining techniques of the 20th century bear a close resemblance to those of the ancients: exploration, ore breakage and removal, hoisting, and processing. The great advances, however, have been in equipment and machinery of greater size and speed which allow greater efficiency in each of these operations, with a corresponding reduction in manpower requirements. Yesteryear production was measured in pounds per man-day; today a giant and complex, but highly efficient, continuous mining machine can remove as much as eight tons of material a minute from the coal face. If our energy and metal demands of the future are to be met, and at this time it can be assumed that coal will continue to supply a significant part of the energy demand, other dramatic and spectacular technologic advances must be accomplished. Along with mechanization, however, public policy will require the industry to place greater emphasis on health and safety protection, as has been well demonstrated by recent actions of Congress. Together, fossil fuels and metals formed the basis for the industrial revolution-coal to develop power and metals to transform power into useful energy. Strangely enough, however, the mining industry the world over has lagged behind the continuous social changes brought on by the industrial revolution, such as preventive health and industrial hygiene services, and other programs directed to the well-being of the worker. In some countries this resistance, to change may have led in part to the nationalization of the coal industry. Whether this disinclination to social change in the industry of the United States reflects managerial attitudes, inept labor leadership, government neglect, or economic relationship would be the subject of an interesting study. Doubtless the mores of miners and their resistance to change, as well as their geographic isolation from other industrial groups, may have had a strong influence on these factors. In every major coal mining country the accident rate in the coal industry is substantially higher than other industrial groups, and the cost of pneumoconiosis compensation in some countries is greater than the combined costs for all other occupational diseases from all other industries. The high social cost of occupational accidents and diseases may have been a factor in the closing of the industry in at least two countries. Despite diminishing manpower needs, the industry is faced with critical manpower shortages. Miners once reared their sons to be miners; now it appears that the opposite is true. This factor alone, however, does not explain an acute labor shortage in the industry. Traditionally, the industry drew much of

Jan 1, 1976

By J. E. Hilliard

AS is well-known, the length per unit volume, Lv, of any lineal feature (such as grain edges in a polycrys-talline specimen) can be estimated from a count of the number of point intersections with a random plane of polish. Specifically:&apos; Lv = 2NA in which NA is the expected number of intersections per unit area of the plane. As with all other measurements in quantitative metallography, the estimation of Lv is subject to a sampling error, the magnitude of which will depend on the number of observations. The analysis is usually performed by counting the number of intersections falling within a closed test figure of known area applied to a succession of different areas on the plane of polish. The test figure can be drawn directly on the screen of a projection microscope or else superimposed on the image of the structure by means of a reticule in a focusing eyepiece of an ordinary microscope. The use of micrographs is very inefficient unless, as in the present study, these are also needed for some other purpose. Consider an analysis in which n applications are made of a test figure within which the expected number of intersections is N. The expected total number of intersections counted is then given by NT = nN If (N) is the standard deviation in N for one application of the figure and if the latter is applied to non-overlapping regions so that the N&apos;s are independent in the statistical sense, then the standard deviation in Nt is given by: a(NT) = a(N)vn Eliminating n from Eqs. [2] and [3] we obtain: Thus, k will be a constant for a given specimen and test figure. From Eqs. [ I] and [4] we find As is to be expected, therefore, the fractional error in the estimation of Lv is inversely proportional to the square root of the total number of intersections counted. It is very desirable to have at least a rough estimate of k before starting an analysis, since it will then be possible to decide in advance by use of Eq. [5J how many counts should be made in order to achieve the desired accuracy in Lv. Without such information the investigator, unless lucky, will either do needless (and tedious) work or else obtain a result with too large an error. It is very easy to calculate k for the limiting case of N — 0, i.e., when the test figure is vanishingly small. In this case there is a negligible probability of two or more intersections falling within the figure. There are therefore only two possible outcomes: a count of one with a probability of, say, p and a zero count with a probability of (I-p). Thus and Therefore: We might expect k to depend on N and therefore on the size of the test figure. Such a dependence was observed2 in the analogous case involving the estimation of grain-boundary area per unit volume by a count of the number of intersections of a test circle with traces of the boundaries on the plane of polish. In this case the theoretical value of k at the limit N — 0 was 1.41. It was also predicted that k would display an initial sharp decrease with increasing N. Experimentally, k was observed to decrease to a value of 0.62 at N - 6 and thereafter remain approximately constant. Furthermore, the value of k for N > 6 was found to be insensitive to the form of the structure provided no pronounced anisotropy or grain-size variation was present. In order to determinewhether k would exhibit a similar dependence on N in the estimation of grain-

Jan 1, 1967

By T. K. Perkins, O. C. Johnston

Because of the influence of dispersion on miscible-displacement processes, diffusion and dispersion phenomena in parous rocks are of current interest in the oil industry. This paper reviews and summarizes a great deal of pertinent information from the literature. Porous media (both unconsolidated packs and consolidated rocks) can be visualized as a network of flow chambers, having random size and flow conductivity, connected together by openings of smaller size. In such a porous medium, the apparent diffusion coefficient D is less than the molecular diffusion coefficient Do, as measured in the absence of a porous medium. For packs of unconsolidated granular material the ratio D/D, is about 0.6 to 0.7. For all porous rocks, both cemented and unconsolidated, the ratio of diffusion coefficients can also be represented as D/Do = 1/FF where F is the for- mation electrical resistivity&apos; factor and 4 is the porosity. If fluids are flowing through the porous medium, dispersion may be greater than that due to diffusion alone. At moderate flow rates the porous medium will create a slightly asymmetrical mix zone (trailing edge stretched out), with the longitudinal dispersion coefficient approximately proportional to the first power of average fluid velocity (if composition is nearly equalized in pore spaces by diffusion). If the velocity in interstices is large enough, there will be insufficient time for diffusion to equalize concentration within pore spaces. In this region, longitudinal dispersion increases more rapidly than fluid velocity. At low velocities in interstices, transverse dispersion is characterized by a region in which transverse diffusion dominates. If the fluid velocity gets high enough, there will be a transition into a region where there is stream splitting with mass transfer but with insufficient residence time to completely damp-out concentration variations within pore spaces. There are several variables that must be con- trolled to get consistent longitudinal and transverse dispersion results, viz., (1) edge effect in packed tubes, (2) particle size distribution, (3) particle shape, (4) packing or permeability heterogeneities, (5) viscosity ratios, (6) gravity forces, (7) amount of turbulence, and (8) effect of an immobile phase. INTRODUCTION Diffusion and dispersion in porous rocks are of current interest to the oil industry. This interest arises because of the influence of dispersion on miscible-displacement processes. In a recovery process utilizing a zone of miscible fluid, there is the possibility of losing miscibility by dissipating the miscible fluid or by channeling or "fingering" through the miscible zone. Diffusion and dispersion are two of the mechanisms that may lead to mixing and dissipation of the slug. On the other hand, dispersion may tend to damp-out viscous fingers which may be channeling through the miscible slug. 58 Hence, dispersion may be detrimental or beneficial (if it prevents fingering through the miscible zone). Therefore, it is doubly important that we understand these processes. In this paper we review, summarize and interpret a great deal of information from the literature. In particular, we will briefly discuss molecular diffusion in miscible fluids. Then we will discuss what differences to expect for diffusion in a porous rock. If there is movement of the fluid through the rock, then there may be an additional mixing or "dispersion". Furthermore, the dispersion longitudinally (in the direction of gross fluid movement) and transverse to the direction of fluid movement will not be equal. We will discuss both types of dispersion as well as several variables which can affect dispersion (viscosity differences, density differences, turbulence, heterogeneity of media, etc.). This group of variables has sometimes led to difficulty when comparing literature data. DIFFUSION OF MISCIBLE FLUIDS If two miscible fluids are in contact, with an initially sharp interface, they will slowly diffuse into one another. As time passes, the sharp interface between the two fluids will become a diffuse

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of gas-solid reactions with special attention given to the hydrogen reduction oj dense spheres of hematite. This reduction process must pvoceed through a sequence of transport and chemical .reaction steps acting in series. Under typical experimental conditions, none oj the individual transport and reaction resistances may be neglected in the development of a physically significant model. A linear vate of thickening oj the product layer, usually taken as evidence of interface-controlled .reuction, may be observed even though transport resistances play a dominant role in the over-all kinetics. The temperature and pressure dependencies of all terms have been carefully evaluated in order to .make fill use oj arailable expe-inzental data in evaluation oj the model. FOR obvious technological reasons, the kinetics of reduction of iron oxides has become the subject of intensive experimental and theoretical investigation during recent years. Continuing efforts to construct mathematical models to describe the kinetics of reaction between a gas stream and a granular bed of solid particles have demonstrated the necessity of a thorough understanding of the reaction kinetics of a single particle within the system as a prerequisite to the construction of physically significant models of complex, reacting systems. This paper presents a critical examination of the transport and chemical-reaction processes involved in single-particle oxide reduction and develops the mathematical expressions necessary to evaluate their importance. Comparison of theoretical predictions with experimental results contributes important new understanding of the complex nature of this process. The reduction process has been studied under a wide range of experimental variables, and it is not surprising that apparent conflicts in observation and interpretation appear in the literature. The interested reader is referred to the reviews of Themelis and auvin"? and Manning and philbrook3 for a description of much of this work. The course of reaction commonly has been followed by measuring the oxygen weight loss from the particle as a function of time. A number of authors have suc- cessfully correlated their data in terms of a model which assumes that the reduction process is controlled by the rate of reaction at a single, sharply defined, advancing interface. According to this model, the interface will advance linearly with time. A mathematical model for gaseous reduction in a packed bed developed by the present authors in an earlier paper4 recognized that reduction must proceed through the series hematite (Fe203), magnetite (Fe30,), wiistite (Fe,O), and finally metallic iron. The reduction scheme permitted a stepwise topochemical reduction of the individual particles to metal or to the lowest oxide thermodynamically possible for the local gas composition in the bed. The limiting situations of theoretically dense and very porous oxide structures were considered. On the basis of available experimental evidence, the simplifying assumption was made in each case that all product layers would thicken linearly with time. A generalized single-particle model has now been developed to determine the significance of transport resistances in the product layers and in the gas film surrounding the particle. The analysis shows that the interplay of transport and chemical resistances is such that an apparently linearly advancing interface may be observed despite the fact that the reaction may be under significant transport control. Attention thus far has been focused on the development of a model for the topochemical behavior of dense spheres of hematite in atmospheres capable of reducing them completely to metal. The formation of successive product layers of iron, Fe,O, and Fe304 is assumed to follow the mechanism originally described by dstrijm.&apos; All oxygen removal from the core occurs at the iron/Fe,O interface, intermediate oxide layers being propagated by sol id-state diffusion without change in the oxygen density of the core. Since fractional reduction is operationally defined in terms of oxygen weight loss, the kinetics of the over-all reduction of FeZ03 to iron is properly studied in terms of the gas-solid reaction occurring at the iron-wiistite interface. The fractional reduction of a partially reduced oxide sphere is given by: here refers to the radial position of the iron/Fe,O interface. This model is not universally applicable because, as explained in the earlier paper,4 a consideration of porous particles or of dense particles in atmospheres not capable of reducing wiistite must allow for the possibility of gaseous reduction at interfaces other than the one between iron and Fe,O. However, evidence that certain hematite specimens actually do follow the dense-pellet mechanism developed here is provided by the data of cewan&apos; and of Bogdandy and

Jan 1, 1967

By J. F. Martin, L. M. Melnick, R. Rapp, R. C. Takacs

Recent studies on the determination of hydrogen in steel have shown that the hot-extraction method for removing hydrogen from a solid sample is preferable to its removal from a molten sample by vacuum fusion or by fusion in vacuum with tin. A number of techniques are available, however, for determining the hydrogen so extracted. They include: thermal conductivity, gas chromatography, pressure measurement before and after catalytic oxidation of the hydrogen to water and removal of the water, and pressure measurement before and after diffusion of the hydrogen through a palladium membrane. These techniques have been evaluated on the basis of initial cost, maintenance, speed and accuracy of analysis, and applicable concentration range. The results of this study showed that the palladium-membrane technique is best suited for routine use. FOR some time investigators have been concerned with the origin, form, and effect of hydrogen in steel. In such stdies&apos;, the analysis for hydrogen constitutes one of the most important phases. It is quite apparent that the results for hydrogen concentrations in a given steel are dependent on the method of obtaining the sample, storage of the sample until analysis, preparation of the sample, and analysis of the sample, including all the facets inherent in the calibration and operation of an apparatus for gas analysis. There are a number of means available for determining hydrogen. This is a critical study of some of the more common techniques in use today. In most conventional melting and casting methods, hydrogen concentrations of 4 to 6 parts per million (ppm) in steel are quite common. Because of the undesirable effects of hydrogen on steel there has been increased use of techniques such as vacuum melting,&apos; vacuum casting, and ladle-to-ladle stream degassing, which lower the hydrogen content to levels on the order of 1 to 2 ppm. Therefore, the method used for determining hydrogen in steel must be sensitive and precise. In any analytical procedure for gases in metals there are two distinct operations—the extraction of the gas from the metal and the analysis of the extracted gas. To extract the gas from the steel, three methods have been employed: 1) fusion of the sample with graphite at high temperature; 2) fusion with a flux, such as tin, at a lower temperature; and 3) extraction of the hydrogen from the solid sample at a temperature below the melting point of the steel. Fusion with graphite is the least-acceptable method. The blank in this method is higher and more variable than in either of the other two methods. The hydrogen fraction of the total gas composition usually is between 10 and 50 pct; thus, a larger analytical error is possible. The vacuum-tin fusion4 extraction of hydrogen is probably the most rapid method in use today; the extraction time is usually about 10 min. However, with this system a bake-out of the freshly charged tin for 2 hr is necessary and a change of crucible and a charge of fresh tin are required after each day of operation whether one or thirty samples have been analyzed. In addition, frequent checks of blank rates are required since CO and Na are continually being given up by the steel samples dissolved in the tin bath. The composition of the gas in this method lends itself readily to analysis; although the hydroge concentration may fall to as low as 50 pct, more often it is above 90 pct, thus allowing a more precise analysis (because of less interference from other gases). In 1940 ewell&apos; published the hot-extraction method for extracting hydrogen from the solid sample, comparing analysis for hydrogen extracted at 600°C with similar analysis for the gas extracted at 1700°C by fusion with graphite. Good agreement for hydrogen was obtained between these two methods, provided sufficient time was allowed for extraction at the lower temperature. carsone obtained good results in his comparison of this hot-extraction method with vacuum-tin fusion. Subsequent work by Geller and sun7 and Hill and ohnson&apos; has shown that steel samples should be heated to at least 800°C to effect the release not only of the diffusible hydrogen but also of the "residual" hydrogen that may be present as methane. Since the rate of evolution of hydrogene9l0 depends on such factors as sample size and composition, thermal history, and extent of cold work, a fixed extraction time is not possible. Extraction times of 30 min are normal, but 2 hr are not unusual. Induction or resistance heating may be used in the hot-extraction method. With resistance heating the

Jan 1, 1964

By V. M. Karve, K. K. Majundar, K. V. Viswanathan, J. Y. Somnay

The effect of calcium, magnesium, iron (both ferrous and ferric) and aluminum ions, which are commonly encountered in a typical beryl ore, was studied in the flotation of pure beryl, soda-feldspar and quartz. The vacuumatic flotation technique was employed. With sodium oleate as collector and in the absence of any activator, beryl floated in a pH range of 3 to 7.5, whereas feldspar and quartz did not float at any pH up to 11.5. The pH range of flotation increased in the presence of the ions studied. With calcium and magnesium ions beryl floated from 3 to 11.5 pH and beyond, soda-feldspar floated beyond pH 6 and quartz floated beyond pH 8. Ferrous ion activation was found to be similar to that of calcium and magnesium. Activation by ferric and aluminium ions was found to be complex and the lower and upper critical pH for all the three minerals was around 2 and 10 respectively. These studies indicated the possibility of separation of beryl from feldspar and quartz even in the presence of calcium, magnesium and ferrous ions between pH 4 and 6. Flotation tests on a mixed feed of pure minerals in a 10 g cell revealed that beryl can be selectively floated from feldspar and quartz if ferric ion is reduced to ferrous state or if it is complexed. Beryl occurs mostly in pegmatites, and hence is associated with feldspar, quartz and micas and small amounts of other minerals such as apatite and tourmaline. The separation of beryl from these minerals is difficult because all the silicates accompanying beryl have more or less the same physical properties. Specific gravities of beryl, feldspar and quartz are 2.70, 2.56 and 2.66 respectively. Electrostatic separation has been suggested but no work has been reported. &apos; The adsorption of sodium tri-decylate tagged with Cl4 on beryl, feldspar and quartz reveal similarity in surface properties. Much work has been reported on the flotation of beryl from ores, either directly or indirectly as a by-product, but little is known about the fundamental aspects of beryl flotation. Kennedy and O&apos;Meara3 laid emphasis on prior cleaning of the mineral surfaces with HF. Mica is removed first by flotation of beryl with oleic acid, around neutral pH. Runke4 introduced calcium hypochlorite conditioning in a final separation stage for activating beryl in a mixed beryl-feldspar concentrate, and after washing to remove the hypochlorite, floated beryl with petroleum sulphonate. The Snedden and Gibbs5 procedure is somewhat similar to that of Kennedy and O&apos;Meara. Emulsified oleic acid is used as collector. Recently Fuerstenau and Bhappu6 studied the flotation of beryl, feldspar and quartz with petroleum sulfonate in the presence of activators and stressed the importance of iron in the flotation of beryl. From the studies conducted in this laboratory, it was found that feldspar and quartz as such do not float with sodium oleate, but in practice selective flotation of beryl from feldspar and quartz in an ore is found to be impossible with sodium oleate as collector. A glance at the chemical analysis of typical beryl ore indicates the presence of several ions like Ca ++, Mg++, Al + + + and Fe+++ in abundance and Ti++++ and Mn++ in traces. Hence, in an attempt to explain the behaviour of feldspar in the beryl flotation, the effect of Ca++, Mg++, Al+++ and Fe+++, which are known as gangue mineral activators7&apos;8 has been investigated. Materials and Methods: Lumps of beryl ore (hand picked) were boiled with 10% sodium hydroxide and washed with distilled water. They were further boiled many times with 10% hydrochloric acid till no positive test for iron was obtained with ammonium thio cyanate. This was followed by thorough flushing with double distilled water. The lumps were crushed in a porcelain mortar and pestle under water. The minus 65 + 100 mesh fraction was used for testing and was always stored under distilled water. Pure feldspar and quartz were similarly prepared and the minus 65 + 100 mesh fractions collected. Inorganic ions tried as activators were ca++, Mg++ , Fe++, Fe ++ and A1 +++ . Calcium nitrate, magnesium chloride, ferrous ammonium sulfate, ferric ammonium sulfate and aluminum nitrate of G.R.E. Merck grade were used. B.D.H. technical grade sodium oleate was used as a collector. The vacuumatic flotation technique developed by Schuhmann and Prakash was used for studying the effect of pH on flotability. 7 The indications given by this work were confirmed by using 10 g miniature cell.&apos;

Jan 1, 1965

By A. Mitchell, T. Bagshaw

A recent paper by Thomas1 has presented new data on the solubility of hydrogen in solid silver at 1 atm pressure in the temperature range 600° to 963°C. However, no data is reported in the literature on hydrogen solubility in liquid silver. The Sieverts technique which has been described previously2,3 was used in the present work. Charges of approximately 160 g were melted in Morgan "purox" recrystallized alumina crucibles and purified helium was used for the determination of the "hot volume" during each experiment. A chemical analysis of the silver indicates that the impurity content (Cu + Al) is less than 0.02 wt pct. Hydrogen solubility in the temperature range 963° to 1200°C was investigated. The results of three experiments are shown in Table I. Fig. 1 shows an Arrhenius plot of the present work together with the solid-state data of Thomas, Steacie, and johnson,4 Eichenauer et al.,5 and Siegelin et al.6 The following expression has been derived from the Arrhenius plot of the present data: log (solubility of hydrogen, cm3 per 100 g) = 2.154-3512.0/ToK The heat of solution derived from Fig. 1 is 31,150 cal per g mole H2 compared with the value of 33,020 cal per g mole H2 obtained by Thomas and 12,000 cal per g mole H2 obtained from the data of Steacie. It was observed that hydrogen evolution took place when the silver melts were solidified under 1 atm of hydrogen, which would not be expected from an extrapolation of the results of Steacie. Schenck and Lange7 have observed that, for several transition metals at their melting points, the ratio of the hydrogen solubility in the liquid to that in the solid lies in the range 2.1 to 3.1. The present results and those of Thomas are in accord in this respect having a ratio of 2.8. &apos;C. L. Thomas: Trans. TMS-AIME, 1967 vol. 239, pp. 485-96. 2T. Bagshaw and A. Mitchell: I. Iron Steel Inst., 1966, vol. 204, p. 87. &apos;M. Weinstein and J. F. Elliott: Trans. TWS-AIME, 1963, vol. 227, p. 382. &apos;E. W. R. Steacie and F. M. G. Johnson: Proc. Roy. Soc. (London), Ser. A, 1928, vol. 117, pp. 662-79. &apos;W. Eichenauer et al.: Z. Metallk., 1958, vol. 49, pp. 220-25. 6W. Siegelin et al.: Z. Elektrochem., 1957, vol. 61, pp. 359-66. &apos;H. Schenck and K. W. Lange: Arch Eisenhuettenw., 1966, vol. 37, no. 9, pp. 739-48.

Jan 1, 1969

By Irving Cadoff, Jack Medoff

THE linear thermal expansions of oriented single crystals of zinc were measured in the range from 20" to 416°C using a Leitz HTV optical lever differential dilatometer. The single crystals, supplied by Dr. J. J. Gilman, General Electric Research Laboratory, Schenectady, N.Y., were prepared from 99.999 pct-purity zinc, and were in the form of rods approximately 2 in. long by 0.15 in. in diameter having the following orientations: x = 1.5, 12, 20, 30, 37.5, 49, 60, 73, and 82 deg where x is the angle between the specimen axis and the (0001) plane of the crystal. From the family of expansion vs temperature curves, the instantaneous expansion coefficients were calculated at 100°C intervals, and Fig. 1 shows a plot of these derived coefficients for each orientation. Coefficients were obtained from the raw data using the chord-slope method. The curves in Fig. 1 indicate a positive temperature coefficient for low x, a negative temperature coefficient for high X, and an expansion coefficient invariant with temperature, amounting to about 43 x 106, for a crystal orientation of approximately 52 deg. From the available data, it is possible to arrive at the values for the axial thermal-expansion coef- ficients a, and a, by extrapolating the curve of the expansion coefficient vs orientation to zero and 90 deg orientations. More precise values for a, and a, are obtained if the instantaneous coefficients are plotted against the square of the cosine of the orientation angle, as shown in Fig. 2. The extrapolated terminal points of the best straight line through the data points of such a plot define the axial coefficients at that temperature. The theoretical justification for the linearity of this curve comes from inspection of a rearranged form of the general anisotropic equation for expansion: ax=a, + (a, -a,)cosZx [1I in which a, is the expansion coefficient in the "c" or [0001] direction and a, the expansion coefficient in the "a" or [ll50] direction. From Fig. 2, the axial coefficients at 100°C, for example, were found to be a, = 13.9 x 10&apos;6 and a, = 62.4 x 10"6 per "C. In the same way, the coefficients were determined for 20", 200°, 300°, and 400°C. This data is summarized in Fig. 3. It is of interest to observe the common intersection of the curves in Fig. 3, which seems to bear out the earlier observation, from Fig. 1, of a

Jan 1, 1964