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By Hansheinz Portisch, Harold Margolin

A surface expansion was found to occur sometime after etching in Ti-A1 alloys containing 9.5 to 12.5 wt pct Al. The structure formed, grew, and disappeared with tzrrze. The surface expansion was followed by microscope observations and interferometric and lattice parameter measurements. Activation energy measurements for the growth of the "expansion structure" and chemical analysis indicated that the phenomenon occurred as a result of hydrogen pzckup during etching. It is proposed that hydrogen initially enters octahedral sites of Ti3Al coherent with a Ti and later shifts to the tetrahedral sites. It is postulated that expansion occurs when hydrogen enters the tetrahedral sites. The expansion structure disappeared, it is proposed, because of diffusion of hydrogen from the surface into the body of the alloy and because of loss of coherency of Ti3Al. In examining Ti-A1 alloys, Ence and arolinl observed markings on the surface of specimens. These markings did not appear after electropolishing only, but rather appeared only after etching. The markings appeared to grow as a function of time after etching and later seemed to disappear. Although the markings had some similarity to precipitates, showing, frequently, a Widmanstatten type of arrangement, the observation that other microstructural markings continue to be seen within the new structure suggested that it was actually not a precipitate. The source of this structure was unknown and an attempt was made in the present investigation to develop some understanding of its nature. It has been labeled expansion structure. 1) EXPERIMENTAL PROCEDURE A) Alloys. Alloys in the range 6.5 to 14.5 wt. pct A1 were studied. Bars, 4 in. sq, forged from Bureau of Mines (73 Bhn) titanium consumably arc-melted 4-lb ingots,' as well as 50-g arc-melted buttons of desired aluminum contents were used. The 50-g buttons also used Bureau of Mines titanium (73 Bhn) and aluminum of 99.99 pct purity. Buttons containing up to 8.5 wt pct A1 were hot-rolled from a furnace at 900' . Those with higher aluminum contents were hand-forged on a titanium anvil, and heated with an oxygen-hydrogen torch in the region of 1200" to 1300°c. Frequent reheating kept the samples at the desired temperature range. After a reduction of about 30 pct, the samples were water-quenched. To eliminate any contamination picked up either during hot rolling or forging, at least 1 mil of the surface of the sample was taken off. B) Heat Treatment. Prior to heat treatment all alloys were vacuum-annealed to remove hydrogen. Samples were annealed at 900' until a vacuum of 10'5 mm Hg was established. After this treatment, the samples were wrapped in molybdenum sheet and heat-treated in argon-filled quartz capsules, which were broken under water or iced brine at the conclusion of the heat treatment. All heat treatments under dynamic vacuum were performed in a rapid-quench furnace. This consisted of a molybdenum-lined quartz tube attached to a vacuum system and through a stopcock to a beaker of water. At the completion of the heat treatment the vacuum stopcock was closed, the furnace shut off, and dropped below the quartz tube. Then immediately the inlet stopcock was opened and water admitted until the tube was filled. The steam formed was allowed to escape through the inlet stopcock. This method was used in heat treatments up to llOO°C. C) Metallography. Specimens for metallographic examination were ground, then electropolished using a Disa Electropol machine with a perchloric acid electr01te. Specimens were etched with R-etch.3 A standard etching time of 3 min was used, with the specimen being agitated during immersion. D) Sample Preparation for X-ray Analysis. Samples 0.2 to 0.5 mm in diam were produced from heat-treated rods which were turned to 2 mm diam on a lathe and then rotation-etched. An etchant consisting of 1 pt HF, 7 pt HN03, and 12 pt HzO was satisfactory. With the rod rotating in a vertical position at 50 to 100 rpm, a needle with uniform dimensions could be obtained. Care had to be taken to insure that the rod was at the center of rotation, otherwise cavitation developed. If a small unevenness developed, it was possible to grind it off with a fine emery paper. E) X-ray Diffraction. All X-ray work was done on a North American Phillips X-ray diffraction apparatus and a Jarrell Ash microfocus X-ray unit. The Phillips unit was used with a copper target and nickel filter. The Jarrell Ash unit was fitted with a cobalt target and iron filter. For the Phillips unit 35 kva and 20 ma were used, whereas for the microfocus unit with the 100-p fixed-focus gun 40 kv and 1.5 ma were used. It was found that alignment of cameras on the Jarre11 Ash unit was very critical. The X-ray beam contains an intense area which is not the beam center. The cameras were aligned with the intense region by monitoring the beam coming out of the camera with a Geiger counter. Adjustments were made until a maximum intensity was obtained. A Phillips diffractometer with a Brown chart recorder furnished some of the lattice parameter data. The divergence slit up to 80 deg 28 was I deg; above 80 deg, a 4-deg opening was used, while the scatter slit was1 deg and the receiving slit had a 0.003-in. opening. The general scanning rate was 1 deg per min, while peaks of special interest were rescanned at -j deg per min. For elevated-temperature X-ray diffraction a Uni-cam High Temperature Camera with a film diameter

Jan 1, 1969

By C. A. Hartnagel

During- the past 10 years the annual production of petroleum in New York has averaged close to 5,000,000 bbl., the total for the period being 49,881,000 bbl. In 6 of the 10 years, the production was slightly in excess of the 5,000,000 mark. The 1944 production of 4,697,000 bbl. represents a 7 per cent decline from the previous year. Of the total 1944 output, the Allegany County district, which includes two small areas of Steuben County, contributcd 3,614,065 bbl., a decline of 5 per cent from 1943, and the contribution of Cattaraugus County, which represents the northern extension of the Bradford pool of Pennsylvania into New York was 1,082,935 bbl., a decline of more than 14 per cent. Since March 1942, the posted price of New York crude oil has remained at $3.00 per bbl. On lug. I, 1944, a Federal subsidy of 75¢ per bbl. was granted to oil producers, thus making the price actually $3.75 per bbl. Since all of the oil produced in New York comes under the designation "stripper well operations," it is entitled to the Federal subsidy. During the last few years there has been little change in the number of wells drilled annually. In the Allegany field, which accounts for three fourths of the oil produced in the state, 1240 wells, including water-intake wells, were drilled during 1944 as compared with 1223 in 1943. There was no marked increase in the number of wells drilled after granting the subsidy of 75¢ per bbl. of oil on Aug. I, the increase being but 14 wells during the last half of the year over the preceding six months. In flooding operations it is not to be expected that even a substantial increase in the price of crude oil will be reflected quickly in an increase of the number of wells drilled or in a marked increase in production of crude oil. In flooded areas, oil is obtained through a program extending over a number of years. This program involves the drilling of the water or input pressure wells, drilling of the oil wells, building up the oil flood to maximum production, and finally the watering out of the well when the amount of oil produced in proportion to the water becomes so small that pumping is no longer profitable. The various operations may extend over a period of 10 years or more, during which time the price of crude may have fluctuated greatly. Although the rate of production can be controlled to a limited extent, it is evident that a flood when once begun must be continued regardless of the price of crude. During the past seven years New York crude has had a price range from $1.68 per bbl. in 1938 to the present price of $3.75 per barrel The field pattern now in general use for wells in a flood project is the "five-spot." Under this arrangement, the lease is divided into squares with a water well at each corner and an oil well in the center. In the all-over pattern of the lease each oil well is acted upon by four water wells and each water well supplies part of the pressure to four oil wells. Spacing between the input water wells and the oil wells usually varies from zoo to 225 ft. or, on an acre basis, there is one oil well and one water well for each 2 1/2 acres. In recent years there has been a tendency to increase

Jan 1, 1945

By J. W. Spretnak, V. Kandarpa

Stress -induced ordering of carbon atoms is studied in a series of Fe-Mn-C alloys. A prominent peak is found in the vicinity of 280°C at frequencies of the order of 1.0 cps, with an associated activation energy of 37 kcal per mole. The height of the peak is linearly rekzted to the concentration of carbon in solution. The distortion of octahedral holes by manganese atoms appears to be predominant over carbon-carbon pair interactions. RELAXATION by stress-induced ordering of point defects is expected whenever the introduction of these point defects produces distortions which have a lower symmetry than that of the lattice. Under zero stress, the isolated point defects occupy the crystallographic-ally equivalent positions in the lattice, as these represent states of equal energy. However, if the defect sites are asymmetric, application of an uniaxial stress will split the energy states, and a redistribution of the defects among various states will take place. This is the case of the internal friction peak called the Snoek peak,1 resulting from isolated interstitials in bcc metals. The interstitial sites in this case have tetragonal symmetry. In the case of fcc and hcp lattices, such an effect is not expected from isolated point defects because of the symmetrical nature of the interstitial sites. However, internal friction peaks arising from interstitial diffusion have been reported both in hcp2,3 and fcc4-8 lattices. These peaks are often explained on the basis of stress-induced ordering of interstitial solutes, caused by the deviation of interstitial sites from their cubic symmetry through the presence of nearby defects. In the case of fcc lattices, evidence for interactions of both the substitutional-interstitial4,6,13 and interstitial-interstitial types5'798'14 have been presented by various investigators. The purpose of the present investigation was to study the internal friction peak attributed to the diffusion of interstitial carbon atoms in high purity austenitic manganese steels and to account for the peak in the light of the existing models. MATERIALS The Fe-Mn-C alloys used in the present investigation were made in two different ways, designated as Type I and Type 11. Type I alloys were made from high purity Fe-Mn alloys obtained in the form of 0.04- in.-diam wires from Materials Research Corporation, Orangeburg, N.Y. These alloys were carburized to different levels using gas mixtures of H2 and CH4 at 1000°C. Type I1 alloys were made in this laboratory starting with zone refined iron, spectrographically pure manganese, and spectrographically pure carbon. They were melted in an argon arc melting furnace and drawn into 0.04-in.-diam wires. All the wires were annealed at about 900°C for 3 hr prior to the internal friction experiments. After the measurements of internal friction, the phases in the samples were identified by X-ray diffraction and the carbon determined by the combustion method. EXPERIMENTAL PROCEDURE In the present work, a classical Ke-type pendulum was used. The details of the equipment were described previously by D. T. Peters.9 Dry helium at 40 torr was used in all the experiments. The internal friction, measured as the logarithmic decrement of the torsion amplitude of vibration was determined as a function of temperature, from ambient to about 500°C. The background internal friction was assumed to have the form of the exponential of the inverse temperature and was subtracted from the raw data. The height of the peak was measured at the position of the maximum in the plot of the internal friction versus temperature. The activation energies of the peaks were measured by the peak shift method. The internal friction values for an alloy were obtained as a function of temperature at different frequencies of vibration. The position of the peak changes with frequency, the higher the frequency the higher the peak temperature. The activation energy of the process associated with the peak is obtained using the formula

Jan 1, 1970

Arizona ROBERT E. TALLY, Chairman CARL E. ~IILLS, Secretary-treasurer, P. 0. Box 1462, Jerome. Ariz. W. S. BOYD THOMAS H. 0. O'BRIEN F. W. MACLENNAN Boston Meets first Monday each winter month GAL~N H. CLEVENG~, Chairman HOLCOMB J. BROWN, Vice-chairman F. I,EROY FOSTER Secretary-treasurer Room 8-219, Mass. lnst: of Tech., Cambridge Mass. A. E. WELLS H. A. WENTWORTH

Jan 1, 1928

By Laurence Pellier

Electron microscopical studies were made of the effect of sensitization at 1200oF on a Type-.104 stainless steel with high carbon and low nitrogen and oxygen contents, after solution annealing and after cold working. The loci of the carbide precipitates in the early stages of sensitization were followed in dry stripped plastic replicas. Some observations were made by direct electron transmission on thinned films. Intragranular dislocations showed a high degree of stability through the annealing necessary to produce sensitization. I HE present work was undertaken to determine the effect of sensitization, at 1200°F, for 1/2 hr, on the electron microstructure of a Type-304 stainless steel with high carbon, and low nitrogen and oxygen contents, after solution annealing and after cold working. Many electron microscopical studies of sensitization of 18-8 stainless steels have already been made. Most of them utilized extraction replicas, from which the morphology and composition of the precipitated carbides could be established.'-" ry stripped replicas were seldom used for such studies, although it was demonstrated that they are applicable, in general, to EurveYs of the general microstructure of many alloys' and, in particular, to the observation of precipitated carbides in austenitic stainless steels.3

Jan 1, 1963

By T. W. Watson, D. R. Flynn

Measurements have been made of the thermal conductivity and electrical resistivity of two specimens of 0.005-cm (2-mil) Be-Cufoil over the temperature range -140° to +200°C. The thermal cmductivity of Be-Cu Alloy 125 was found to be significantly higher than that of Alloy 25, which had a higher impurity content. The thermal conductivity and electrical resistivity values obtained were in concordance with the Smith and Palmer relation for copper alloys which states that ? = 0.0239 (T/p) + 0.075 where A is thermal conductivity (W cm-' deg-'), p is electrical resistivity (microhm-cm), and T is absolute temperature (OK) , indicating that the Smith and Palmer relation can be used to predict the thermal conductivity of this type of Be-Cu alloy over the temperature range -140" to + 200°C to within an accuracy suitable for most engineering applications. THE National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, Md., requested the National Bureau of Standards to measure the thermal conductivity of 0.005-cm Be-Cu foil which was to be used to fabricate antennae for use in Radio Astronomy Explorer space craft. It was felt that measurements had to be made on the actual antenna material, rather than on a thick bar of similar material, since the cold-working and age-hardening properties of the alloy would make it very difficult, if not impossible, to place a thick bar in the same metallurgical state as the 0.005-cm material. As discussed in Section 111 of this paper, the thermal conductivity of many copper alloys can be computed rather accurately from electrical resistivity data using an empirical relation developed by Smith and palmer' and further confirmed by owell.' However, there has been very little work done on correlating thermal and electrical conductivities on Be-Cu alloys. We were reluctant to assume the validity of the Smith-Palmer relation on Be-Cu alloys because of the very large mass difference between beryllium and copper. As will be seen, however, our experimental results indicate that the Smith-Palmer relation is valid for the two alloys on which we made measurements. I) DESCRIPTION OF SAMPLES Samples of Be-Cu Alloy 25 and Be-Cu Alloy 125 were furnished to NBS in the form of rolled strip material, 0.005 cm thick by 5.08 cm wide. The Be-Cu Alloy 25 was purchased by NBS in the form of a continuous length of flat strip. The Be-Cu Alloy 125 was furnished to NBS by Goddard Space Flight Center in the form of two lengths of strip that had been formed into "tubing" of about 1.2 cm diam, with one side of the strip overlapping (but not connected to) the other side by about 90 deg. This "tubing" had been opened up to be flat and then rolled onto spools of about 3 cm diam. When unrolled, the strip would spring back into tubular form. Samples of both of the Be-Cu alloys were chemically analyzed by the NBS Analytical Chemistry Division. The beryllium content was determined quantitatively by the phosphate-gravimetric method to be 1.83 wt pct for Alloy 25 and 1.80 wt pct for Alloy 125. The two alloys were also examined by a general qualitative spectrochemical method for metallic elements. The Alloy 25 specimen contained between 0.1 and 1.0 wt pct Al, Co, Fe, and Si and between 0.01 and 0.1 pct Ni. The Alloy 125 specimen contained between 0.1 and 1.0 pct Co and between 0.01 and 0.1 pct Al, Fe, and Si. Other metallic elements present were in amounts less than 0.01 pct. The NBS Engineering Metallurgy Section measured the tensile strength, elongation, and Knoop hardness of both the Be-Cu Alloy 25 and the Be-Cu Alloy 125. These are given in Table I. The NBS Engineering Metallurgy Section also prepared photomicrographs of the two alloys; these are shown in Figs. 1 and 2.

Jan 1, 1969

By Richard Pearce

H. M. Howe, Boston, Mass. (Communication to the Secretary): One by one our venerated idols are shattered, our cherished beliefs are filched away. Mr. Pearce's interesting experiments on the effect of an intermixture of coal in expelling arsenic from roasting copper-ores seems at the first blush to spike one of the great cannons of our faith. Plattner, however, is so positive that coal does lead to the expulsion of arsenic that we may well pause before accepting Mr. Pearce's results as final, and ask whether there is not some explanation of the discrepancy between them and Plattner's statements. Plattner states that while ferric arseniate decomposes easily under the action of carbonaceous matter with expulsion of arsenic as arsenious oxide (As2O3) and sub-oxide of arsenic (it is now generally thought, I believe, that this supposed sub-oxide is really but a mixture of metallic arsenic and arsenious oxide); cupric arseniate, on the other hand, undergoes this decomposition with difficulty, usually forming a certain proportion of arsenide of copper. Now, may not the whole matter lie just here? Mr. Pearce experimented on an ore containing its arsenic as enargite, sulph-arsenide of copper. This, in roasting, would probably give rise to arseniate

Jan 1, 1890

By F. L. Robertson, C. H. Bacon, J. W. Till

A description is given of the development of a process for making low sulphur steel on furnaces fired with 2 1/2 pet sulphur oil. Slag and metal are analyzed at melt. Slag weight is estimated. A simple method for calculating necessary lime additions for making 0.025 and 0.035 pct sulphur steel is given. DURING the last 15 years John Summers & Sons have been confronted increasingly by the problem of producing a low sulphur steel from high sulphur materials. The principles adopted, the processes used, the data collected on a furnace specially set aside to study this problem, and speculation on future developments are dealt with in this paper. This study is limited to two melting shops which make sheet steel only, of the following analysis: C, 0.06 pct; Mn, 0.33; S, 0.04, 0.035, 0.03, and 0.025; and P, 0.02 and 0.015. All the processes described have reference to the manufacturing of this steel and are not necessarily applicable, without modification, to other steels. The raw materials used are given in Table I. Development of Process About 1934, Schenck's work on phosphorus was applied to frame quantitative rules for the removal of phosphorus, with great success. We could however, neither in our own work nor in the voluminous literature, find any assistance to frame quantitative furnace rules to remove sulphur. Perhaps, we should have persevered with Schenck's outstanding chapter on sulphur in The Physical Chemistry of Steelmaking, but we missed the importance of one (Ss) sentence on p. 478. "Evidently this ratio -------- is [S] the important quantity to be considered from the point of view of chemical reaction; it is clear that the sulphur content of the steel alone, as frequently given in the literature cannot suffice for judging the success of the reaction unless special details are given regarding the sulphur charge and the amount of slag."' We were not however very successful in getting values for Schenck's "n" that agreed with (S) arrived at by our direct analysis. [S] In addition to Schenck's work much attention was given to V value. The formula selected for V was: (SCaO) — 1.57 (2 P2O5) (S SiO2) After plotting many charges a curve was obtained, based upon the relationship between the percentage sulphur in the finished steel and V value, Fig. 1. For a long time this was used as standard with about a 60 to 70 pct success on producer-gas fired furnaces, if all uprising scrap was used and no bought scrap used. An inspection of this curve shows clearly that it is not a quantitative manufacturing process, and that it was not sure enough to go to the trouble and expense of doing stage analysis for P,O,,

Jan 1, 1952

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation's supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation's need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation's supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation's need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951

By Edna A. Dancy, Gerhard J. Derge

Jan 1, 1963

The regular activities of the Institute are financed mainly by income derived from members' dues, from advertising in MINING AND METALLURGY, and from the sale of publications to the public. In addition, collateral activities and special projects are financed each year by means of income from endowed funds controlled and administered by the Institute. In the aggregate, the principal sums of these endowments amount to more than $530,000. An active effort is being made to increase the endowment funds of the Institute through a standing committee, of which H. T. Hamilton is chairman, and of which the other members are: W. H. Aldridge, George D. Barron, Cleveland E. Dodge, D. C. Jackling, Henry Krumb and J. V. W. Reynders. This committee feels that there exists a tremendous opportunity for the Institute to be of ever-growing service to the public, to the mineral industries, and to the profession. It welcomes suggestions as to names of men of means who are vitally interested in the mineral industries, and to whom the opportunity to make a contribution or bequest might appeal favorably if presented in the proper light by the committee.

Jan 1, 1941

By B. D. Smith, K. H. Coats

Experiments in which calcium chloride displaced sodium chloride from four cores showed the extent of asymmetry in the resulting effluent concentration profiles. These results provided a check on how validly the mixing process is modeled by a differential (i.e., not finite-stage) capacitance mathematical model. The effluent concentration profile from two consolidated cores exhibited considerable asymmetry, while two unconsolidated cores yielded nearly symmetrical profiles. All runs resulted in breakthrough of the 50 per cent concentration significantly before one pore volume was injected. In addition, velocity appreciably affected the effluent concentration profile from a Torpedo sandstone core. The differential capacitance model matched the data significantly better than a simple diffusion model. The capacitance model allows determination of the amount of dead-end pore space in a porous matrix and the effect of velocity on the rate of diffusion into this space. An experimental program yielding insight into the physical validity of the capacitance effect is described. INTRODUCTION Axial dispersion — the mixing accompanying the flow of miscible fluids through porous media — has been the subject of many relativeiy recent studiesl-13 and a comprehensive review of the topic has been given by Perkins and Johnston.14 This dispersion is of practical interest in studies of the miscible displacement process, fixed-bed chemical reactors, and the adsorption of solutes from a flowing stream onto the surface of a porous medium. In the latter case, the effect of dispersion must be considered when adsorption parameters are determined from the nature of concentration profiles. In general, early studies of dispersion assumed applicability of a simple diffusion equation and were concerned with correlation of the experimentallv determined "effective" diffusion coefficient with system properties over a large range of the latter. Recent have been concerned with the deviations between the asymmetrical effluent concentration profiles observed and the symmetrical ones predicted by the diffusion model. In the present study, effluent concentration profiles were obtained from consolidated and unconsolidated cores. These profiles were compared with those predicted by a differential (i.e., not finite-stage) capacitance model. Solutions to the simple diffusion model, for three sets of boundary conditions, were compared with one another and with the experimental profiles. SUMMARY OF PREVIOUS WORK The reader is referred to Perkins and johnston14 for an extensive review of studies of dispersion in porous media. Many investigators have employed the simple diffusion model characterized by Eq. 1 below: The dispersion coefficient D for unconsolidated systems is correlated by u is interstitial velocity and dp is particle diameter. Since heterogeneity of the sand pack affects the mixing, this equation is also expressed as where a is proportional to the degree of heterogeneity and is about 3.5 for random packs of unconsolidated sand.l4 Eq. 3 holds for 2 For a Do homogeneous (regular) type of packing, should be 1 or less.6 Aris and Amundson6 and Carberry and Bretton consider o to be the number of particle lengths per mixing cell in the finite-stage model. Data from consolidated cores indicate dp to be about 0.36 cm for outcrop rocks, Torpedo sandstone having a reported value of 0.17 cm.15 For v /Do less than about 2, the effect of molecular diffusion must be considered and the total dispersion coeffi-

Jan 1, 1965

By H. T. Bowman

FOR more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the 1860's it was recognized that the process would benefit by some type of instrumental control.1 However, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower's eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham3' A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient monoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. CARBON-FEO RELATIONSHIP In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by McCutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a different method than were those

Jan 1, 1942

By W. F. Domis, F. von Gemmingen, F. Garofalo

The effect of rain size on the creep behavior of an austenitic iron-base alloy has been studied at 1300° F under conditions of constant stress. The average grain diameter varied between 9 and 190 p (ASTM 10.7-2). The subgrain size and apparent activation energy for creep were not found to depend in any systematic manner on gain size. Grain hozmdary serrations were observed in all specimens tested. The variation of the secondary-creep rate, 2,, with the pain diameter, 1, is given by: es = K(213m + 1 )/l.]; 1, is the grain diameter zohere is reaches a minimum. Results in the literature shoujthat 1,increases as the temperature increases. At low creep temperatures is is therefore proportional to 12, at intermediate temperatures <, exhibits a minimum, and at high creep temperatures is is proportional to 1/1. The dependence ofis on the stress, u, is given by: t, = A" (sinh acrln, a and n show little variation with 1. The dependence of A" on 1 is given by: A" = KA[(21k + 13)/1]. For 1 » >>lmn = 4, and at constant values 01- isat lozu stress levels, the steady-state stress is given by the Hall-Petch relation. The variation of c, with grain size is believed to he associated particularly with grain boundary generation of dislocations which becomes more important with increasing temperatures. SEEMINGLY inconsistent experimental findings have led to a certain amount of confusion concerning the effect of grain size on creep behavior. The confusion is attributed to a lack of test results obtained over sufficiently wide ranges in grain size, stress, and temperature. Experimental results presented in this paper and results available in the literature1-5 show a consistent behavior and lead to a unified concept for the dependence of secondary-or steady-state creep rate on grain size. In accordance with this concept, which is substantiated experimentally, secondary-creep rate should increase with increasing grain diameter at low creep temperatures, leading to greater creep strengths for fine-grained materials. At intermediate temperatures the secondary-creep rate should decrease to a minimum and then increase as the grain size is increased. At high creep temperatures the secondary-creep rate should decrease with increasing grain size, leading to greater creep strengths for coarse-grained materials. Whether a temperature is high or low for creep in a metal or alloy depends primarily on its melting temperature. MATERIAL AND TEST PROCEDURES The material tested was an austenitic iron-base alloy of the following composition (wt pct): C, 0.005; N, 0.017; Mn, 1.26; Ni, 14.21; and Cr, 17.18. Two 15 -lb ingots were forged and hot-rolled to 5/8-in.-diam bars which were then cold-rolled and cold-swaged to a diameter of 0.49 in. These were sectioned into 3-in.-long blanks and heat-treated at various temperatures to obtain different grain sizes. The procedures employed and the results obtained are summarized in Table I. The secondary treatment at 1400° F followed the primary treatment without intermediate cooling to room temperature. This final treatment was employed to minimize various effects arising from heating to different temperatures during the primary treatment, particularly differences in intragranular dislocation structure, segregation of interstitial atoms at grain boundaries, and density of grain boundary ledges. The intragranular dislocation structure was examined by electron transmission metallography after each of the treatments described in Table I. Isolated dislocations and a few tangles were observed but no evidence of subgrains was found after any of the treatments. No grain-size effect was evident on the density and distribution of dislocations. Stabilization of grain boundary structure is particularly important because, as will be discussed later, grain boundaries influence high-temperature creep behavior. Magnetic-permeability measurements after each treatment and

Jan 1, 1964

By C. G. Cheriton

The Bathurst mining district is located near the town of Bathurst on the north shore of the province of New Brunswick in eastern Canada. This region is the northeasterly extension of the Appalachian mountain system. The area is heavily forested and covered with a fairly uniform layer of glacial gravels and boulder clay. The relief is low, increasing to a few hundred feet in the north west and several hundred feet in the extreme southwest. Thus, rock outcrops are scarce and occur mostly along streams and ridges. These factors made conventional prospecting difficult and resulted in the district becoming an excellent place for the application of regional geological studies, air photo techniques, airborne and gound geophysical methods and soil sampling. Late in 1952, The Brunswick Mining and Smelting Company discovered a very large base metal sulphide body presently known as their No. 6 orebody. Early in 1953, another and even larger sulphide body was discovered and is known as the No. 12 ore body. Mining exploration was very active thoughout 1953 and in 1954, The American Metal Company discovered the orebodies which have been developed into The Heath Steele &apos;Mines. The location of these deposits is shown on figure one. In the latter part of 1954, The Anaconda Company became interested in the district and decided to make a geological study of this new and promising base rrietal area. The following paper presents the story of the application of modern geological and geophysical techniques, leading to the discovery of a large sul-nhidp liodv. The Bathurst district is generally underlain by the Tetagouche group of Middle Ordovician rocks.

Jan 1, 1961

By J. W. Downey, A. E. Dwight, R. A. Conner

THE MgCu2 type Laves phase has been observed in the thorium-osmium and thorium-iridium systems. Two alloys corresponding to ThOs2 and ThIr, were prepared by arc melting a 5-g charge in a water-cooled copper. crucible. Both alloys were very brittle. X-ray diffraction patterns were obtained using filtered Cu and Co radiation with a Straumanis-type DeBye-Scherrer camera. The a,, values as shown in Table I were obtained by a Nelson-Riley extrapolation. The structure belongs to space group Oh7-Fd3m. Relative intensities for each of these compounds were calculated on the assumption that 8 thorium atoms occupy (a) positions and 16 osmium or irid-ium atoms occupy (d) positions. The calculated intensities are the product of the Lorentz-polarization factor, the multiplicity factor and F&apos;, the structure factor, neglecting the absorption and temperature

Jan 1, 1959

By A. Raja, C. C. Harris

Apparatus for maintaining constant — but adjustable — pulp level and rate of froth removal are described. The results of preliminary experiments into the effect of scraping speed on the rate of solid and liquid recovery with a semi-batch system are presented. Glass spheres restricted to a narrow size range is the solid under investigation. Graphical methods for estimating the mass of recoverable material and the zero error are given. The semi-batch procedure1 is extensively used in laboratory flotation testing, though the method is subject to variability of moderate severity. Raffinot2 concluded from a statistical study of the difference between replicate tests, that the ptincipal source of errot was the test itself and not sampling or chemical analysis. These differences can be ascribed principally to changes in pulp volume and reagent concentration, and uncontrolled rate and depth of scraping. Semi-batch testing has been criticized1 on these grounds as a means of investigating flotation kinetics. This paper discusses and describes modifications to laboratory flotation equipment which reduce the number of manual operations and lead to improved control. Kinetic studies were the primary reason for developing the apparatus described. It should, however be a useful aid in normal flotation testing. Some preliminary results of experiments are presented.

Jan 1, 1967

By Arthur F. Taggart, A. W. Thomas, T.C. Fitt

It was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a component of the pulp, of a mass solubility of the general order of a fraction of a milligram to I 5 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.= The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends. to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. Experimental Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well be~ond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipitation from hydrochloric acid solution of arsenic-free zinc, and was washed as lot I. Lot 3 was prepared by heating a portion of lot 2 in absence of air at 1200° to r300°C. for one hour."

Jan 1, 1943

By Arthur F. Taggart, T. C. Fitt, A. W. Thomas

It was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a component of the pulp, of a mass solubility of the general order of a fraction of a milligram to I 5 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.= The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends. to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. Experimental Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well be~ond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipitation from hydrochloric acid solution of arsenic-free zinc, and was washed as lot I. Lot 3 was prepared by heating a portion of lot 2 in absence of air at 1200° to r300°C. for one hour."

Jan 1, 1943