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By John Chipman, Daniel Dutilloy

The equilibrium of gaseolis H2O-H2 mixtures with liquid iron-phosphorus alloys in the range 0 to 3 pct P is used to establish the increuse of the activity coefficient of oxygen, in the presence of phosphorus. Two different sampling techniques are used. THE importance of oxygen as a refining agent in steelmaking operations makes it desirable to improve our understanding of its behavior. Phosphorus which is always present in the ores has adverse effects on steel properties and its removal is necessary. The present study was undertaken to evaluate the interaction of oxygen and phosphorus in molten iron. Bookey, Richardson, and welch1 have studied the phosphorus-oxygen equilibria in liquid iron in the presence of lime. They used a mixture of hydrogen and water vapor to control the oxygen potential and worked with crucibles made of tetracalcium phosphate and lime. At low phosphorus concentration, i.e., at high oxygen, they observed a marked deviation in their results. They tentatively ascribed this to a large negative effect of oxygen on the activity of phosphorus. This was then included by chipman2 in his review of interactions in liquid iron. Pearson and Turkdogan 3 have later reported an interaction parameter They equilibrated a mixture of hydrogen and water vapor with an iron-phosphorus alloy contained in an alumina crucible and sampled the melt by suction in a silica tube. The solubility of oxygen in iron-phosphorus alloys has been studied by Levenets and Samarin.4 They reported an interaction parameter

Jan 1, 1961

By Rossiter W. Raymond

The most important event in the history of mining in the United States was the discovery of gold in California, which led to the rapid development, not only of a new industry, but of a new empire. The settlement of the Pacific slope was making but slow progress under the inducements of a scanty commerce in furs and hides. The liberal grants offered by the government to agricultural pioneers in Oregon had attracted to the Willamette valley and other favored points in that territory a limited population; hot the government of the Mexicans in California was positively unfavorable to enterprise. It is true that gold was known to exist in the country. Rumors of it were current among the trappers, and placers had actually been worked in what is now Los Angeles County; but the padres of the neighboring mission of San Fernando had discouraged the business as demoralizing to their flocks; and the existence of the precious metal was not widely known; still less was its distribution northward suspected. The discovery of gold, January 19th) 1848, at Sutter's saw-mill, on the south fork of the American River, afterward famous as Coloma, in Eldorado County, was the beginning of the new epoch. This discovery was made by James Wilson Marshall, a partner in the mill, who observed in the debris washed down by the tail-race a glittering fragment of a mineral unknown to him. Suspecting it to be gold, he sought for further specimens, and obtained, in the course of a few days, several ounces of it. Tests subsequently

By Charles Wert

THE diffusion and precipitation of carbon and nitrogen in a iron have previously been investigated using the internal friction as a measuring tool.' Most of this work has been done on rather pure iron; no effect was observed which would indicate that either of these phenomena is affected by the rather small amounts of impurity found in these samples of iron. Fastz observed, however, that both the diffusion rate and the aging properties of nitrogen in iron were sensibly changed by the addition of Vz pet Mn. The diffusion rate at a given temperature is reduced and the nucleation of nitrides is apparently changed somewhat. He observed no such changes for carbon in this alloy. Later Dijkstra and Sladek" extended these observations on nitrogen to other alloys of iron. They found that metals other than manganese also influence the behavior of nitrogen in iron; chromium, molybdenum and especially vanadium affect the diffusion and precipitation of nitrogen even more than manganese does. Their results have been verified in all essential details by this author, who finds in addition that small additions of nickel have about the same effect on the diffusion of nitrogen as the same amount of manganese. The present work was undertaken to study the effect on carbon in iron of these alloying elements. The alloys used had two sources. The material used as a "standard" (designated Fe in this paper) in the measurements was some iron supplied by J. K. Stanley, of Westinghouse Electric Corp., who reported 0.01 pct 0, as the only major impurity. He also made up an alloy of 0.26 pct Ni and one of 0.9 pct Mo using this same iron as a base. They were supplied by him in 2 lb billets, which were sawed into rods and cold formed into 0.030 in. wires for measurement. The alloys of chromium, manganese, and vanadium were prepared by the metallurgy section of the Institute for the Study of Metals, University of Chicago, by adding these metals in turn to vacuum melts of National Research Corp. iron. The small castings prepared in this way were also cold formed into 0.030 in. wires. After these wires had been prepared they were decarburized for 30 min at 730°C in wet Hz. After this treatment, no trace of carbon (as measured by internal friction) could be found. All specimens were then carburized for about 15 min at 710°C and water quenched. By this treatment the internal friction at 40°C was raised to a Q-' ~ 0.015. The diffusion of carbon in these alloys was studied by observing the shape and position of the internal friction peak at 0.9 cycles per sec. These measurements were made using a torsional pendulum in a manner described earlier.' The data are plotted in Fig. 1. It is seen that there is no apparent difference in internal friction between the various alloys. This is in marked distinction to the broadening and shift-

Jan 1, 1953

By W. G. Mine

In September, 1953, seismographs were installed in the Crowsnest Pass area of Alberta and British Columbia to study the 'bumps' which were occurring in the coal mines at Fernie and Coleman, and to investigate the possibility that they might be related to minor earthquakes in the area. During the initial phase of the work, three seismographs were operated at widely separated stations, two in the region of coal mines at Coal Creek and Coleman and one at Turner Valley, distant from any mining operations. Some earthquakes were recorded at all three stations and, in addition, many small disturbances were recorded by the seismographs located near the mines, especially -by the instrument at Goal Greek. A closer network of radio-linked seismographs was then in-stalled near Fernie, the records of which definitely established that the small disturbances were occurring in the mine workings, both active and inactive. No relationship was established between bumps and local earth-quakes in the area. This work was initiated as a -co-operative effort with the Fuels Di-vision of the Mines Branch, Department of Mines and Technical Surveys, which has undertaken a study into the phenomena of ground stress relief in underground mine workings.

Jan 1, 1958

By D. G. Westlake

Levine has concluded that prismatic slip in titanium is controlled by two distinct thermally activated processes in the temperature ranges O° to 220°K and 220" to 300°K. We feel that his evidence is not convincing. He has drawn a curve through the plot of activation volume u* vs temperature T with a break at 22WK, Fig. 2. We believe that considering the possible experimental error apd the fact that there are only four points between 4° and 196°K, one could be justified to represent these points by the smooth curve we show as a solid line in Fig. 12. Levine believes that (8rf/aT)+ is discontinuous at 220°K, but he hints that he recognizes the possible doubt. We doubt seriously that the results shown in Fig. 1 indicate a discontinuity at 220°K. Certainly if he were justified in drawing a straight line through only four points on Fig. 2, we are even more justified in drawing straight lines through the seven points between 77" and 297°K on Figs. 1 and 3, because a straight line touches all seven of his circles. If his measurements of t were so precise that his decision to draw two curves in Fig. 3 is valid, then the experimental technique is deserving of further mention. We have drawn a smooth curve through the results in Fig. 3 and used this and the curve in Fig. 12 to obtain the values of shown in Fig. 13. Finding continuous is a contradiction of Fig. 4, which deserves comment itself. Levine obtained the solid circles in Fig. 4 using Fig. 2 and a smooth curve through the points shown in Fig. 3. We have replotted these solid circles in Fig. 14. We submit that there is no basis for his two straight lines (dashed in Fig. 14), and therefore have superimposed the curve that we believe is indicated. Certainly, there is reasonable doubt that a discontinuity in dH/dT exists at 220°K, even when one accepts Fig, 2. Furthermore, if one draws the straight lines indicated by least-squares treatments of the results presented as open circles in Fig. 4, their intersection is at about 196°K, not at 220°K as shown. Thus the alleged agreement between Figs. 3 and 4 with respect to "break" temperatures is not apparent. In Fig. 9, Levine has drawn a straight line very much different from the one indicated by a least-squares treatment. Obviously, he has done this because he recognized that H = 0 when T = 0. He is consistent in drawing the low-temperature curves in

Jan 1, 1968

By J. Wiese, K. Corin, Z. Song

"Relating flotation performance to the electrochemical characteristics of a pulp is complex both in fundamental research and in practice. In the case of thiol collectors, different Eh values in the flotation system can result in the formation of the dimer or the metal thiolate which may or may not enhance the hydrophobicity of the mineral. Reducing or oxidizing conditions in a flotation system, viz. changing the Eh value, are usually manipulated to achieve an optimum flotation response by control of pH and dissolved oxygen levels in the system. A variation in pulp potential may also be achieved by the addition of potential modifiers such as sodium hydrosulphide (NaHS), sodium hypochlorite (NaClO) or hydrogen peroxide (H2O2). There exists anecdotal evidence which suggests that the addition of small amounts of H2O2 to the flotation process can improve sulphide mineral recovery. The objective of the present study was to investigate the effect of the addition of the potential modifier, H2O2, on sulphide mineral recoveries and grades in the flotation of sulphide minerals from two copper bearing ores from China and compare the results to those obtained for a PGM bearing ore South Africa. Batch flotation tests were conducted using the three different ores at the natural pH of the different systems, in the presence of a xanthate collector and the absence and presence of H2O2 as a potential modifier. The results indicate that the addition of carefully controlled low concentrations of H2O2 resulted in improvements in flotation performance. INTRODUCTIONElectrochemical potential as a control parameter in the flotation of sulphide minerals has been widely studied (Allison et al., 1972; Gardner and Woods, 1979; Ross and Van Deventer, 1985; Chander, 2003; Woods, 2003; Javadi, 2013). There is concensus that in order to be recovered during flotation, sulphide minerals require a suitable redox environment. During the flotation process thiol collectors and sulphide minerals are involved in electrochemical reactions which result in the formation of hydrophobic species at the mineral surface (Finkelstein and Goold, 1972; Rand and Woods, 1984). Sulphide minerals act as semiconductors and electrons are transferred during the interaction of the mineral with collector. The resultant potential difference and its magnitude are responsible for the transfer of electrons and the rate of the reaction (Bard and Faulkner, 2001; Fuerstenau et al., 2007). Reducing or oxidizing conditions in a flotation system, viz. changing the Eh value, may be manipulated to achieve an optimum flotation response by control of pH and dissolved oxygen levels in the system (Heyes and Trahar, 1979). The use of potential modifiers viz. reducing or oxidizing agents which include H2O2, NaClO, and NaHS, is an alternative method by which to control the potential of the pulp in a flotation system which may or may not promote the flotation of desired minerals (Rao, 2004). The oxidizing agent, H2O2, undergoes a cathodic reaction which can result in the enhanced flotation of valuable minerals. The potential of the system is increased which results in a shift in the mixed potential of a mineral. The magnitude of the over-potential influences the rate of the oxidation process and thus the flotation response of sulphide minerals (Kocabag and Guler, 2008). Equation 1 shows the proposed oxidation of xanthate by H2O2 (Lipkina and Streltysn, 1970)."

Jan 1, 2018

By R. A. Swalin, B. W. Roberts

ONSIDERABLE controversy has centered about the existence of an order-disorder transformation in alloys in the composition vicinity of 75 atomic pct Ni and 25 atomic pct Cr. All the evidence to date for such a transformation is of a rather indirect nature, since direct X-ray confirmation is difficult to obtain as a result of the small difference in X-ray scattering factors between nickel and chromium. As a result, superlattice lines would be very faint if present. Several investigators1-5 have observed anomalies in the electrical resistivity vs temperature curves of alloys in the vicinity of 25 atomic pct Cr. The observed change is characterized by a rather broad resistivity peak at about 540°C. A discontinuous drop in resistivity is normally associated with ordering. However, Taylor and Hin-ton4 have rationalized that the discrepancy could conceivably be caused by changes in the Brillouin zones upon ordering. The same investigators measured the specific heat as a function of temperature and have also observed anomalies in the vicinity of 540°C. Nordheim and Grant5 have proposed, because of the absence of superlattice lines and the absence of a discontinuity in the resistivity vs temperature curve, that long-range order is improbable and that the results could be better explained by short-range ordering. To date, however, the question has not been resolved satisfactorily. Neutron diffraction techniques provide a method for partially resolving the question since nickel and chromium have considerably different atomic scattering factors in the case of neutrons and, therefore, superlattice peaks, if ordering occurs, should be readily discernable. The results of a neutron diffraction investigation* coupled with a dilatometric in- vestigation are reported here. An alloy containing 28.0 atomic pct Cr was prepared from carbonyl nickel and electrolytic chromium in the form of a 1-in. diam x 10-in. ingot. Melting was done in an alumina crucible and casting in a graphite mold. The ingot was homogenized at 1250°C for seven days, after which a 5-in. long piece was cut into shavings in order to obtain a suitable neutron diffraction sample. Hardness samples and samples suitable for dilatometric analysis (% in. diam x 2 in.) were prepared from the remainlng piece. The neutron diffraction sample, along with a hardness sample, was annealed at 501°C for seven days, at which time the temperature was lowered to 479°C and held at this temperature for twenty-four more days. The hardness was observed to increase from 133 to 147 Vhn during the course of the annealing treatment, in qualitative agreement with Nordheim and Grant." Neutron diffraction traces taken at room temperature and at 42 °K are shown in Fig. 1. The insert shows the trace taken at room temperature with short counting times and thus only fair statistical accuracy. No evidence for superstructure reflections of Cu3Au-type ordering is observed. The statistical accuracy of the 4.2°K trace was improved by using longer counting periods. Several weak intensities are observed at small angles, including an aluminum reflection from the cryostat assembly and a very

Jan 1, 1958

By Charles H. White

Methods in colorimetry are based on the assumption that the intensity of the' color of a definite volume .of solution is directly proportional to the quantity of the color-producing substance present. In the preparation and examination of colored solutions there are three ways in which the depth of color may be varied. These variables are : (1) the quantity of' the coloring matter; (2) the quantity of the solvent, or the dilution ; and (3) the thickness or depth of that portion of the solution examined. With these three variables as a basis, three general methods in colorimetry have been devised, all of which have been used in the determination of carbon in steel. In the first method, the quantity of the solution is kept the same for both the unknown steel and the standard, and the sections compared are of equal thickness, while the quantity of the standard is varied until the color obtained is of the same intensity as that produced by a definite quantity of the unknown steel. In laboratories where this method is used there is prepared and kept for permanent use a series of solutions with varying amounts of the standard, representing the percentages of carbon from the lowest to the highest demanded in that laboratory. These standard solutions are kept in bottles or test-tubes of equal diameter, and are arranged in series from the faintest to the most intense color, so that it is a simple matter to find the place of the unknown steel in the series, when the solution is of a definite volume and is contained in a tube of the same diameter as the standard tubes. In the second method, equal quantities of the standard and of the unknown steel are dissolved, the standard is diluted to a definite volume, and the solution of the unknown steel is di-

Jan 1, 1907

By Donald Ofte

LIQUIDUS temperatures of molten alloys were measured in an oscillating-cup viscosimeter by observing the abrupt increase in the alloy viscosity when the apparatus was cooled below the alloy liquidus temperature. The liquidus transformation can be an elusive thermal effect in an alloy system where a small amount of material is involved in a low-enthalpy liquidus reaction, or where other unfavorable physical conditions interfere. Using the viscosity technique, liquidus temperatures were measured in binary alloys of plutonium with cerium, gallium, and iron, as well as ternary Pu-Ce-Co alloys. The previously described oscillating-cup viscosimeter1 is a torsion pendulum consisting of a right circular, cylindrical tantalum cup fitted to a rigid shaft which, in turn, is suspended by a torsion fiber in a highvacuum system. When the torsion pendulum is placed in oscillation the viscosity of the liquid contained in the cup is a function of both the decay of the oscillation caused by the viscous drag of the liquid contained in the sealed tantalum cup, and the period of the oscillation. The period is measured by a photo-electrically operated timer to the nearest thousandth of a second. Prior to each measurement, the apparatus is held at temperature between 5 and 18 hr to assure thermal equilibrium throughout the 8 to 10-cc alloy sample. When the cup, filled with a liquid metal, is oscillating. only a very thin outer layer of the fluid is in motion. This moving annulus represents the liquid's contribution to the moment of inertia of the torsion pendulum. When the viscosity increases, more liquid is placed in motion, and the slight increase in the moment of inertia causes a corresponding increase in the period of oscillation.

Jan 1, 1967

By M. J. Blackburn

The ordering reaction and its effect on dislocation awangements in alloys based on Mg3Cd has been studied by transmission electron microscopy. Ordering occurs by the growth of ordered domains until they impinge, thus producing an antiphase domain boundary (APB) network. In the disordered alloy, slip is confined to the basal plane while in the ordered condition slip occurs on the basal, prism, and pyramidal planes. Superdislocations have been identuied on these planes and their origin and expected spacings are discussed and compared with the observations. The APBs between the dislocation pairs have been resolved and have proved useful in the identification of superdislocations. Observed slip structures are related to the changes in mechanical properties produced by ordering. At high temperatures magnesium and cadmium form a continuous series of disordered hexagonal solid solutions. At lower temperatures three ordering reactions occur; two based on the compositions Mg3Cd and MgCd3 are transformations to DO19-type superlattices while alloys based on the composition MgCd transform to a B19 lattice. The ordering process in alloys near the composition Mg3Cd has been studied by several workers'-4 and it has been shown to be a first-order type transformation. The variation of mechanical properties with the degree of order and temperature have been reported in some detail by Stoloff and Davies.5 It was shown that the disordered alloy was stronger and less ductile than the ordered alloy, the differences being attributed to changes in the number of active slip planes and to the presence of short-range order in the disordered alloy. In this investigation the ordering reaction has been qualitatively followed by transmission electron microscopy. The effect of this ordering transformation on the dislocation arrangements in deformed specimens has been studied in some detail. EXPERIMENTAL Alloys were melted in a stainless-steel crucible under a flux and chill cast; both melting and casting were performed in an argon atmosphere. The ingots were hot-rolled and tensile specimens cut from the resultant strips. Some large-grained specimens were grown by the strain-anneal method. Heat treatment was carried out in inert atmosphere furnaces and in oil baths at the lower temperatures. Thin foils for transmission electron microscopy were produced by electropolishing in a cooled solution (temp = -40°C) containing 50 cu cm of nitric acid and 180 cu cm of methanol at a potential of 10 v. The ordering reaction was followed by transmission electron microscopy, X-ray, and electrical resistivity measurements but this paper will be concerned chiefly with the electron-microscopy results. Much of the work described in this paper was performed on an alloy containing 26.10 at. pct Cd although two of the micrographs are taken from work on a 25.55 at. pct Cd alloy. RESULTS i) The Quenched Solid Solution. Specimens which were quenched from above the critical temperature showed diffuse superlattice reflections. sark-field analysis on these reflections failed to reveal the presence of ordered domains and thus the superlattice reflections were assumed to arise from regions of short-range order. Quenching from temperatures of 400" to 450°C results in the formation of dislocation loops and helical dislocations. Such defects have been observed and analyzed in detail in several hexagonal metals6-' and as the crystallography and interactions of such loops appear similar in this alloy they will not be reported in detail. Fig. 1 shows a high density of loops

Jan 1, 1968

By C. J. Ramsburg

The construction and operation of by product coke-oven plants in America are essential to strong national defense and of the greatest importance to many widely diversified undertakings as well as to safety and health. Carbonization Process Coal used under a boiler or in a locomotive is consumed by combustion. Coal used in a by-product oven is distilled or carbonized, meaning that heat is applied to the coal, out of contact with air, causing a distillation that removes the volatile matter in the coal in the form of gas and vapor, leaving coke as a final product. From the gas and vapor distilled from the coal, many valuable substances can be secured, known as by-products. Hence the name "by-product oven." The simplest example of this principle can be shown by means of an ordinary clay pipe. If powdered coal is placed in the bowl of the pipe, the opening of the bowl is plugged with clay, and the bowl placed in a flame, the bowl will become hot, transferring the heat through the wall of the bowl to the coal within. When this coal attains a temperature of about 750°F., gas will begin to pour out of the pipe stem, and this gas may be lighted. A black liquid also will exude from the stem of the pipe, This is tar mixed with certain other products. What remains in the bowl after distillation is coke. A coke oven corresponds to the bowl of the pipe. A modern oven of the latest type is a refractory brick chamber approximately 42 ft. long and 14 ft. high, averaging 18 in. in width. The oven is filled with coal through closable charging holes in the oven top. Each end of the oven consists entirely of a self-sealing door, the removal of which permits the finished coke to be discharged by means of a power-operated pusher machine. The ovens are built in batteries, and the heating is effected by gas burned in vertical flues in the oven walls, each set of flues heating the walls of two adjacent ovens. Such ovens carbonize a charge of approximately 18 tons of coal in 18 hr., or have a daily throughput of 24 tons per oven, producing about 17 tons of coke. In times of need, the output may be increased by raising the temperature of flues, thus shortening the coking time. There is one great essential difference in principle between distillation in a clay pipe and in a coke oven. In the 18-in. oven, the distillation proceeds from two parallel walls held at a high temperature (over zooo°F.) and instead of all the coal being heated at once, the distillation is a progressive one creeping inward. The average travel of this heating is 35 in. per hour from each vertical wall, and as the volatile products are formed progressively they must push away from the interior toward the wall through the previously formed hot coke, then up the walls and Over the top of the coal charge, finally escaping through the outlet pipe. This results in a cracking of the components into many different and valuable substances not formed when the carbonizing temperature is low.

Jan 1, 1942

By G. Birkbeck, T. C. Wells

Pearlite morphology in three commercially produced, low-carbon steels has been studied using optical and electron microscopy. A reduction in the cooling rate from 600° to 6°C per hr increased the interlamellar spacing but had little effect on pearlite content. The form of the lamellae was also assessed in terms of a new parameter, the ratio of lamellae length to interhmellar spacing. The variation of this parameter with cooling rate depended on steel composition. For each steel, it would appear that an optimum cooling rate exists at which lamellar pearlite can be produced to the greatest extent, though not necessarily the same extent in different steels. PeARLITE morphology depends principally on steel composition, prior austenite grain size, and either cooling rate or isothermal transformation temperature. Alloying with manganese,'" fine grain size,374 and slow cooling rates reduce the likelihood that a well-developed lamellar structure will be produced. Instead, imperfect structures usually consisting of partly globular carbides are formed in a ferrite matrix. Such structures have been described as granular.1,2,5 degenerate,6 or semi4-pearlite. Manganese additions also progressively lower the eutectoid temperature and the carbon concentration at the eutectoid so so that, for a given carbon content. the pearlite fraction is increased as manganese is added. While the effects of manganese are understood in a general way, quantitative studies of pearlite morphology have been carried out mainly on steels of eutectoid composition;9 little quantitative data is available for low-carbon steels. Certain anomalies exist in the behavior of steels containing -1.5 pct Mn, however. The pearlite morphology in niobium-treated steel differs from that which is generally accepted as typical of low-carbon/manganese steels in that a reasonably well developed lamellar structure is sometimes observed. In the present work, the effects of changes in cooling rate from 600° to 6°C per hr on the pearlite morphology in three commercially produced, low-carbon steels have been studied by both optical and electron microscopy. I) MATERIALS The steels were of the following types: 1) 0.1 pct C, 0.4 pct Mn steel (En 2, a composition similar to specification SAE 1010); 2) niobium-treated, 0.2 pct C, 1 1/2 pct Mn steel (BS 968:1962); 3) silicon-killed 0.2 pct C, 1 1/2 pct Mn steel (En 144, a composition similar to SAE 1320). The chemical analysis for each steel is given in Table I. To facilitate the comparison of pearlite morphology in the three steels, steels 1 and 3 (which were obtained as 1/2-in. plate and 1-in.-diam bar, respectively) were hot-rolled in the laboratory to $ in. thickness, finishing at around 850°C. The BS 968:1962 was received as 1/8-in. plate finished at 885°C and was not further worked. Specimens from each steel were heat-treated in vacuo at 950°C for 1 hr and cooled at rates of 600°, 60°, and 6°C per hr. 11) EXPERIMENTAL Pearlite contents were determined by point counting (500 points) on longitudinal sections mechanically polished and etched in 2 pct nital. Pearlite morphology is usually considered in terms of interlamellar spacing. For pearlite colonies randomly distributed in space and having a true, constant interlamellar spacing So Pellissier et al.9 determined the distribution curve for the apparent spacings of the lamellae on a random section plane. The areal fraction fs of the pearlite colonies occupied by apparent spacings up to a limiting value S is given by:

Jan 1, 1969

By C. J. Ramsburg

The construction and operation of by product coke-oven plants in America are essential to strong national defense and of the greatest importance to many widely diversified undertakings as well as to safety and health. Carbonization Process Coal used under a boiler or in a locomotive is consumed by combustion. Coal used in a by-product oven is distilled or carbonized, meaning that heat is applied to the coal, out of contact with air, causing a distillation that removes the volatile matter in the coal in the form of gas and vapor, leaving coke as a final product. From the gas and vapor distilled from the coal, many valuable substances can be secured, known as by-products. Hence the name "by-product oven." The simplest example of this principle can be shown by means of an ordinary clay pipe. If powdered coal is placed in the bowl of the pipe, the opening of the bowl is plugged with clay, and the bowl placed in a flame, the bowl will become hot, transferring the heat through the wall of the bowl to the coal within. When this coal attains a temperature of about 750°F., gas will begin to pour out of the pipe stem, and this gas may be lighted. A black liquid also will exude from the stem of the pipe, This is tar mixed with certain other products. What remains in the bowl after distillation is coke. A coke oven corresponds to the bowl of the pipe. A modern oven of the latest type is a refractory brick chamber approximately 42 ft. long and 14 ft. high, averaging 18 in. in width. The oven is filled with coal through closable charging holes in the oven top. Each end of the oven consists entirely of a self-sealing door, the removal of which permits the finished coke to be discharged by means of a power-operated pusher machine. The ovens are built in batteries, and the heating is effected by gas burned in vertical flues in the oven walls, each set of flues heating the walls of two adjacent ovens. Such ovens carbonize a charge of approximately 18 tons of coal in 18 hr., or have a daily throughput of 24 tons per oven, producing about 17 tons of coke. In times of need, the output may be increased by raising the temperature of flues, thus shortening the coking time. There is one great essential difference in principle between distillation in a clay pipe and in a coke oven. In the 18-in. oven, the distillation proceeds from two parallel walls held at a high temperature (over zooo°F.) and instead of all the coal being heated at once, the distillation is a progressive one creeping inward. The average travel of this heating is 35 in. per hour from each vertical wall, and as the volatile products are formed progressively they must push away from the interior toward the wall through the previously formed hot coke, then up the walls and Over the top of the coal charge, finally escaping through the outlet pipe. This results in a cracking of the components into many different and valuable substances not formed when the carbonizing temperature is low.

Jan 1, 1942

By H. R. Aldrich

THIS paper is not a treatise on the theory and practice of magnetic surveying. It merely presents a diagram upon which have been plotted observations taken with the simplest form of magnetic instrument, the lowly dip needle, over a large area astride the Lake Superior syncline of northern Wisconsin. The exposures of the underlying formations are not sufficiently great in number nor fortunate in distribution to have provided the fuller understanding of the geology which has been secured by the use of the magnetic observations as an auxiliary tool or accessory in the hands of the geologist. The diagram (Fig. 2) in large part speaks for itself if studied in connection with the geological map (Fig. 1) for which it is the main control. It is presented to demonstrate the extent to which the use of such methods may aid in the solution of geological problems in a covered country. The diagram is probably unique in assembling the expression of such a wide range of formations, affected by so wide a range of secondary processes, and deformed by so many different structures in terms of magnetic variation. Few geologists outside of the Lake Superior country have had any first-hand experience in the taking of magnetic observations and the interpretations of the results in terms of geological conditions; nor have the Lake Superior men gone with the methods far afield from the mere tracing of iron formations. In more recent years the oil companies have gone heavily into investments in magnetometers, balances, and dip needles in the quest of concealed structural anomalies which are the favorable loci of petroleum accumulation. But these geophysicists come back from the fields with their collections of observations facing the question of interpreting the geological meaning of their magnetic anomalies.

Jan 1, 1928

By William E. Wallace, S. J. Page, B. L. Razzaboni, C. A. Hill, Pamela Mike, P. Bolsaitis, M. J. Keane, Val Vallyathan

"Respirable quartz cytotoxicity, as measured by erythrocyte hemolysis and pulmonary macrophage release of lactate dehydrogenase in vitro, is neutralized by boiling in water in glass test tubes for 10 to 40 minutes. The cytotoxicity is reduced to near zero by boiling l to IO mg quartz per milliliter water. For greater concentrations of quartz in water the hemolytic potential after 40 minutes of boiling approaches that of native quartz. Replacing the medium with fresh water midway through boiling results in full detoxification through 20 mg quartz per milliliter water. Pre-boiling the medium with silica reduces the detoxification effect. Detoxification persists after mild drying at l 10°C for 8 hours, and persists after three days of resuspension in water at room temperature.INTRODCJCTIONResearch underway to determine interactions of quartz and other mineral dust surfaces with pulmonary fluids and alveolar macrophages in culture led to the observation that when dusts were autoclaved in aqueous suspension, their cytotoxic effects on macrophages were suppressed, in some cases fully and even after several days incubation with the cells. This finding was in direct contradiction to earlier results from both short term macrophage lysosmal enzyme release assays, as well as longer term cytotoxicity assays from macrophages in culture; in those studies, dusts were steam autoclaved at 121°C with no liquid water but with steam present. 1.2 However detoxification under boiling conditions has been reported in other research. 3 It was decided to use the hemolysis assay to further investigate these findings, because of its sensitivity simplicity and cost.RESCULTS AND DISCCISSIONRespirable quartz dust used in this study was taken from a stock of crystalline silica, Min-U-Sil; obtained from Pennsylvania Sand Glass Corporation, fractionated in air with a particle classifier. The small size fraction retained for use was 80% less than S micrometer particle diameter, with an area equivalent median diameter of 1.24 micrometers as estimated by automated image analysis. The silica was at least 98.S mass percent silica as determined by X-ray energy spectrometric analysis; and the crystalline form was alpha-quartz as determined by X-ray diffraction. It's specific surface area was 3.97 square meters per gram as determined by nitrogen adsorption isotherm methods. I"

Jan 1, 1990

By Robert Sisselman

Dramatic changes have been effected since 1955 in the mode of iron ore shipments within the U.S. In 1955, less than one percent of ore consumed in domestic blast furnaces-approximately 125 million long tons-consisted of pellets. Five years later, in 1960, some 94.8 million tons of ore were consumed, 14% in the form of pellets. Projections for 1980 reinforce confidence in this most economic of blast furnace feeds, and set U.S. pellet consumption at 151.2 million tons. In the last decade, pellets caught fire in other countries. By 1969, world production reached 96 million tons. This compares strikingly with present world output of 154 million tons.

Jan 9, 1973

By J. B. Rather

The use of sulfuric acid in refining illuminating oils antedates the beginning of the petroleum industry in America by many years. It was used as early as 1792 by Tower in refining "coal oil" in the British Isles, and by 1860 there were 53 refineries in the United States manufacturing "coal oil," most of them using sulfuric acid as a refining agent. Following the completion of the Drake well in 1859, many of the "coal oil" refiners began to use petroleum for manufacturing illuminating oil, and their methods and equipment were adapted so far as possible to this new raw material. The value of sulfuric acid in refining L'coal oil" having been established, this reagent was immediately tried and found to be satisfactory in refining petroleum. Notwithstanding the tremendous advances in petroleum technology since that time, sulfuric acid remains today the most valuable and most widely used means for refining petroleum products. Early Methods of Disposal of Acid Sludge With the almost immediate expansion of the petrolrum industry came the problem of disposing of the acid sludge produced in the refining operations. While in 1859, the year of the discovery of the Drake well, a patent was granted for sludge separation and separated acid concrntration, most of the earlier refiners, and rnany of their successors, felt that separation and recovery of spent acid was uneconomical. Accordingly, many of then) disposed of the sludge in any way that seemed expedient nt the time. It was huricd in the refinery grounds, harged and tlurnped at sea, run into neighboring streams, or dumped into sewers. Some optimists carted it to open pits in the hope that it would eithcr sink into the ground or evaporate. Not so many years ago, the superintendent of nn eastern refinery, who was using the open-pit method of disposal, lost, a sludge cart, with horse attached, in such a pit. The horse was recovred almost immediately, but its availability for further use was reduced to zero by the loss of its hair.

Jan 1, 1928

By Robert M. Keeney, Jay Lonergan

The electric smelting of manganese ore and the production of ferro-manganese did not exist as an industry, in the United States or elsewhere, previous to the outbreak of war in 1914. Ferromanganese had been produced, electrically, during times of high prices by two companies at Niagara Falls and by several European companies, but the production was spasmodic, and none was electrically produced when ferromanganese sold at from $35 to $40 per ton. Thus the electric smelting of manganese ore must be considered as a development caused by the high prices prevailing during the years 1916, 1917 and 1918, and the necessity of smelting domestic ore in order to fill the ferromanganese requirements of the steel industry of the United States, which increased from 189,088 tons in 1914 to 356,356 tons in 1918. The electric furnace is well adapted to smelting domestic ore because it can be located in small units near the source of ore supply. In 1918, the ferromanganese production of the United States was 333,027 tons, of which about 7 per cent., or 23,000 tons, was produced in the electric furnace. The electric furnace not only assisted materially in the development of a domestic-ore supply but made a considerable saving of coke, as it requires about 11/4 tons of bituminous or lignite coal per ton of ferromanganese compared with a blast-furnace consumption of 2.9 tons of coke per ton of ferromanganese. Some of the plants in the United States that smelted manganese orc in the electric furnace during the war and in 1920 are listed in Table 1. From early in 1919 to about February, 1920, little ferromanganese was produced in the electric furnace. During this period the price of ferromanganese (78 to 82 per cent. manganese) was about $100 per ton. During the first half of 1920, several plants resumed operation when the price of ferromanganese (76 to 80 per cent. grade) gradually increased to $200 per ton, delivered.

Jan 1, 1922

By Jay Lonergan, Robert M. Keeney

The electric smelting of manganese ore and the production of ferro-manganese did not exist as an industry, in the United States or elsewhere, previous to the outbreak of war in 1914. Ferromanganese had been produced, electrically, during times of high prices by two companies at Niagara Falls and by several European companies, but the production was spasmodic, and none was electrically produced when ferromanganese sold at from $35 to $40 per ton. Thus the electric smelting of manganese ore must be considered as a development caused by the high prices prevailing during the years 1916, 1917 and 1918, and the necessity of smelting domestic ore in order to fill the ferromanganese requirements of the steel industry of the United States, which increased from 189,088 tons in 1914 to 356,356 tons in 1918. The electric furnace is well adapted to smelting domestic ore because it can be located in small units near the source of ore supply. In 1918, the ferromanganese production of the United States was 333,027 tons, of which about 7 per cent., or 23,000 tons, was produced in the electric furnace. The electric furnace not only assisted materially in the development of a domestic-ore supply but made a considerable saving of coke, as it requires about 11/4 tons of bituminous or lignite coal per ton of ferromanganese compared with a blast-furnace consumption of 2.9 tons of coke per ton of ferromanganese. Some of the plants in the United States that smelted manganese orc in the electric furnace during the war and in 1920 are listed in Table 1. From early in 1919 to about February, 1920, little ferromanganese was produced in the electric furnace. During this period the price of ferromanganese (78 to 82 per cent. manganese) was about $100 per ton. During the first half of 1920, several plants resumed operation when the price of ferromanganese (76 to 80 per cent. grade) gradually increased to $200 per ton, delivered.

Jan 1, 1922

By C. W. Sherman, John Chipman

IN the mathematical statement of the law of mass action, the activity of each substance consumed or produced in a reaction is used to obtain a numerical constant which is characteristic of the equilibrium of that reaction at the given temperature. The activity in many cases is equal to, or proportional to, the concentration. If this is the case, any units denoting concentrations, such as weight percentage or mol fraction, may be substituted in the equilibrium expression. It is even permissible to use mixed units provided only that each unit is that used in defining the activity of the corresponding substance. The indiscriminate use of concentration units in writing equilibrium constants sometimes leads to very erroneous results. On the other hand, what appear to be contradictory results from similar investigations often might be resolved if the activity is the quantity that is used to determine the equilibrium constant for the reaction in question. De-sulphurization serves as an important illustration. Sulphur in lron and Steel The control of the sulphur content of the finished product is one of the oldest and broadest problems in the metallurgy of iron and steel. In general, this control must be exercised through the action of a slag, and for this reason experimental studies of the distribution of sulphur between slag and metal have assumed considerable importance. Under slags of the type found in the basic open-hearth furnace the ratio (% S)/[% S] does not in general exceed about 8. Under blast-furnace conditions, however, de-sulphurization ratios of 50 to 100 are readily obtained, and under laboratory conditions using similar slags, the ratio may be as high as 400. The fact that blast-furnace metal is much more readily desulphurized than is molten steel rests upon two distinct phenomena. The first of these is connected with the slag reaction. In the open-hearth furnace, the equilibrium in the following reaction places a definite limit on the sulphur content of the slag: S + 0-- = 0 + S- - where the symbols underlined indicate elements dissolved in the liquid metal, while slag constituents are represented as ions. The high oxygen content of the open-hearth bath prevents this reaction from proceeding far enough to effect good desul-phurization. In the blast-furnace process, however, the oxygen activity is limited by the presence of carbon in the metal and in the coke bed and the controlling reaction becomes: S_+O- + C_=S- + CO(gas) [2] The second phenomenon which contributes to the easier desulphurization of blast-furnace metal is the effect of high concentrations of other elements. These elements, notably carbon, silicon, and phosphorus, increase the thermodynamic activity of sulphur several fold. As a result of this increase, the escaping tendency of sulphur from the metal phase is increased and its removal facilitated. Previous Studies It becomes, therefore, a matter of importance to determine the effects of various elements upon the activity of sulphur in the melt. The experimental approach to this problem has been made through the equilibrium between sulphur in the melt and gaseous atmospheres containing hydrogen and hydrogen sulphide. The reaction and its equilibrium constant are written as follows: S + H2(gas) =H2S(gas);K1 = -- [3] Pn2 • as where the symbol a, represents the activity of the sulphur in solution in the metal. The understanding of the chemical behavior of sulphur in steel and pig iron rests on a firm knowledge of the binary system Fe-S. A number of studies of the equilibrium have given closely agreeing results from which the activity and free energy of the dissolved sulphur may be found. The recent paper by Sherman, Elvander, and Chipman1 includes a discussion and quantitative comparison of the results of several of the significant researchesr-" on dilute solutions of sulphur in iron. The results of this study indicate that the relationship between the ratio Ph,s/p+ and the percentage of sulphur in solution is not a linear one. This

Jan 1, 1953