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By G. Sachs, G. Espey

It is well known that high residual stresses are created in tubing by the sinking process, in which no internal tool or mandrel is used.l-4 In this process, the wall thickness is usually slightly increased.4,5 In tube drawing with a plug, the residual stresses are gradually reduced with increasing reduction of wall, and, by the conventional approximation methods of stress measurement, no stress is detected in tubing in which the wall reduction is over 50 per cent of the total reduction in cross-sectional area.l,6 It has also been observed that higher stresses are set up by the use of wide-angle dies than by acute dies.? 'he actual stress distribution in drawn tubing has been investigated by a few workers,7"9 but has not been related to the conditions of the drawing process. Some attempts have been made to correlate accelerated cracking tests for stresses in brass products with the magnitude of the circumferential stresses and the condition of the metal. l-10 Materials and Preparation The material used in this experiment was commercial cartridge-brass (70 per cent Cu, 30 per cent Zn) tubing in the straightened and annealed condition.† This tubing was of various outside diameters and had a wall thickness of 0.032 in. It was sunk to 1/2-in. outside diameter by means of an experimental 10,000-lb. hydraulic draw-bench, with a maximum drawing speed of 8 ft. per minute. All dies were of 1/2-in. diameter. Various die materials and contours were used in order to study the effect of die design on residual stresses in the tubing; the specifications for the dies are given in Fig. I. Castor oil was used throughout as lubricant. Chattering occurred in sinking some of the tubing, particularly when dies having the more acute angles were used, but the tubes showing chatter marks did not differ markedly from those with a smooth surface regarding the magnitude of residual stress. The source of the chattering has not yet been revealed. The wall of the tubing becomes thicker during s nking, as previously observed.4,5 The increases in wall thickness were 3, 7 and 9.5 per cent on the average for 6, 20 and 33 per cent reductions in diameter, no effect of the contour being noticeable. The reductions mentioned throughout this investigation do not consider this fact, but are reductions of the outside diameter. For the evaluation of the residual stress two fundamentally different methods were used. The approximation methodl,ll of splitting a certain length of tubing was employed to obtain a bird's-eye view of the effect of various drawing conditions on the circumferential stress measured by the diameter change occurring On splitting. For

Jan 1, 1942

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 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 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 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 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 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 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

By E. Keller

Some years ago the writer's attention was called to the fact that rolling-mill scales from auriferous copper do not have the gold content proportional to the gold contained in the copper from which they are derived.' So, later, he made a few simple experiments, which are described herewith. In order to test the gold movement on the changing surface of a copper plate under the influence of oxidation, plates 6 in. by 8 in. by 1 in. (15.2 cm. by 20.3 cm. by 2.5 cm.) of converter copper, refined, of 99.29 per cent. purity, and leaded copper with a content of 95.65 per cent, copper, were obtained. Ten cuts were made through the thickness of the plates along the longitudinal center and the silver and gold content ascertained in each of the 10 samples in both plates, as shown in the accompanying illustration. The assay results, recorded in Tables 1 and 2, show that the gold distribution is relatively uniform in both plates, while silver has greater variations, especially in the leaded plate. The plates subjected to oxidation were placed in a red-hot muffle for about 2 hr., two small scarifiers being used as supports. Arranged alongside each other, they nearly filled the width of the muffle, and so were practically under equal conditions of heat and draft. The accurate observance of the time was not possible, however, because of other work, but the time of the exposure of each plate in a pair was identical. At the end of each period, each plate was plunged into water and completely freed of scale, which was carefully collected, dried, weighed, and analyzed. Samples of the plates had also been taken of the molten metal and duly analyzed. Table 3 contains the analytical data for the two plates and their several sheets, or layers, of oxide scales. These figures show that in the oxidations of the converter copper the silver is fairly uniform, while the gold is highly irregular and especially low in the first layer. In the oxidations of the leaded copper plate, the silver and gold contents are variable; however, this irregularity is due to two different causes. The

Jan 1, 1919

By F. H. Willcox

In Bessemer-steel practice, air is blown through a bath of iron, or projected strongly upon its surface to burn out silicon, manganese, and cafbon. Toward the end of the blow, when the iron is not protected from oxidation by these elements and the excess of air becomes great, there is oxidation of the iron. In open-hearth practice, the same difficulty is experienced with dissolved gas and oxides in the product, though not to as great or severe a degree as in the Bessemer process because the oxidizing conditions grow less severe as the end of the heat is approached, and if the bath is allowed to boil for a time it undoubtedly frees itself from a large part of the gas and oxides which have been absorbed in the earlier part of the process. Basic open-hearth steel is usually assumed to contain a larger proportion of oxides than acid open-hearth steel, but it may be said that all steel, Besserner and open-hearth, contains more or less oxide of iron dissolved in the fluid metal at the end of the "blow" or "heat." That certain metals are solvents for their respective oxides has been shown, in the case of copper, by Heyn, and, in the case of iron, by Law. It is indicated that the solubility of iron oxide in iron increases with the purity and temperature of the metal. This confirms what is observed and known by operating men, and these observations may be summarized as follows: 1. Cast iron. is rarely subject to oxidation, as is logical from its composition. 2. Normal steel, unless deoxidizers are added, contains blow holes. 3. Steel known to be oxidized is full of blow holes. 4. The addition of deoxidizers prevents, to a greater or less degree, the formation of blow holes in normal steel. With these observations in mind, it is logical to deduce that the cause of blow holes lies in part in the presence of dissolved oxide of iron in the molten steel and its consequent reaction with the carbon of recarburizers, when these are added, to form gases. (Another factor in the origin of blow holes is, of course, the solubility of gases themselves in the steel and

Jan 1, 1917

By P. S. Kotva

Dislocation substructures in superalloy matrices of varyzng co)npositions have been studied. In general, it has been found that the alloys can be classified into ''high", ''medium", and "low" stacking fault energy classes based on the type of dislocation substructure observed in the matrix and that the substructure can be correlated to the stacking fault energy. The effect of different types of dislocation substructure and dislocation reactions on the intragranulur precipitation of carbide phases has been studied. In a Ni-Cv-Mo-Fe matrix, precipitation of MC carbides in association with stacking faults has been observed. In most superalloys, solid-solution strengthening and precipitation hardening are the chief mechanisms employed to achieve strength. The latter contribution to strength is usually achieved by the precipitation of / in certain wrought alloys. Insufficient attention has been given to the problem of obtaining strength in su-peralloys by controlling precipitation of carbides on imperfections within the matrix. The present work was undertaken to investigate the dislocation substructure in various superalloy matrices, to study the effect of such substructure on subsequent precipitation of carbides in the matrix, and to investigate whether certain modes of precipitation of carbide phases found in austenitic stainless steels2"4'6 would occur in nickel-base alloy matrices with dislocation substructures of the same type as those found in austenitic steels. 1) EXPERIMENTAL TECHNIQUES Five-pound heats of the various alloy compositions reported here were vacuum-cast. The ingots were given light deformation by rolling to break up the as-cast structure and then homogenized for 24 hr. HASTELLOY alloy X (nominal composition: Ni-2OCr-17Fe-8Mo-0.05C) was homogenized at 2150°F and In-cone1 625 (nominal composition: Ni-20Cr-5Fe-8Mo-3.5Cb-0.05C) was homogenized at 2280°F. Fabrication of 0.004-in. sheet was achieved by cold rolling with intermediate annealing treatments being carried out at the same temperature as those used for homogeniza-tion. Each solution anneal was followed by quenching. The aim of this procedure was to redissolve as much of the primary carbide phase as possible. Samples of the 0.004-in. sheet were cut and encapsulated in quartz capsules and then heat-treated in the tube furnaces. Thin foils were prepared using an ethanol-10 pct perchloric acid bath at 32°F and at a voltage of 22 v. A "window" technique was employed. Observations were made on a JEM-7 electron microscope operating at 100 kv. 2) EXPERIMENTAL RESULTS a) Types of Dislocation Substructure. Fig. 1 shows a schematic correlation between stacking fault energy, SFE, and the type of dislocation substructure observed in various matrices of nickel- and cobalt-base alloys. A precise quantitative determination of stacking fault energy is not implied in the figure but the correlation between stacking fault energy and the type of dislocation substructure obtained allows alloys to be divided into three classes in analogy with the classification employed by Swann and ~uttin~' for binary alloys of copper. Class I alloys are associated with a "high" SFE and show a cellular substructure of dislocations as typified by the micrograph of a thin foil of pure nickel deformed 4 pct at room temperature in Fig. 2. With decreasing SFE the tendency toward cell formation is lessened and dislocations tend to be arranged in coplanar groupings. Examples of this class of alloys with "medium" SFE are provided by the mi-crostructure of solution-heat-treated, quenched, and deformed thin foils of HASTELLOY alloy X, "Waspaloy" (prior to any aging), and Inconel 625. Fig. 3 shows a thin-foil micrograph of an alloy of Inconel 625 composition, solution-heat-treated, quenched, and deformed 5 pct at room temperatures. No evidence of any cell structure can be obtained in materials of "medium" stacking fault energy, Fig. 3, even after severe deformation. The stacking fault energy of the alloy shown in Fig. 3 is, however, not low enough to make the dissociation of dislocations visually obvious. As stacking fault energy decreases further, with successive addition of solute in the matrix, there is an increased tendency toward dissociation of dislocations and cross slip becomes progressively more difficult. Eventually, when the stacking fault energy is "low" enough, complete dissociation of dislocations is seen to occur as shown in Figs.

Jan 1, 1969

By Robert L. Slobod

In much of the work reported in the literature on long cores. true connate water value, probably have not been obtained because of insufficient flow of 011 to attain equilibrium. A -.satisfactory method for establishing connate water in long cores has been developed in which oil flow is maintained until no additiona1 water is displaced. INTRODUCTION Long cores have been used by sev-erals investigators in an effort to evaluate the efficiency of oil recovery for various producing schemes. The effects of many variables such as rate of displacement. pressure drop, volume of displacing medium, gas-oil ratio, inter-facial tension, and others have been investigated, and the merits of gas drive have been compared with water drive. In the older experiments no connate water was used. but in the more recent stndies the philosophy of the experiment calls for a core containing oil and connate water (irreducible water) as the starting point of the experiment. The method generally used to establish this condition in long cores involves dynamic' displacement wherein one or more phases are forced through the core. flow being maintained at a constant rate or at a constant pressure until a steady state is reached wherein there is no change of saturation with time. It is one purpose of this paper to point out that in much of the work reported in the literature true connate water values probably have not been obtained. The reason for this failure is pointed out. and a method for obtaining more reliable connate water values on long cores is presented. It is impossible at this time to completely evaluate the effect on the conclusions in the earlier papers resulting from the failure to obtain true connate water in the long cores, but some data are presented which indicate that serious errors may he present in many cases. MATERIALS AND APPARATUS Cores cut front outcrop sandstones (Strawn. Torpedo, and Elgin sandstones) with permeabilities of the order of 300 md were used. The major experiments were made with a core 18-in. long and 2-in. in diameter. Cores of the same diameter but only 12-in. long were used in a few tests? and in some work a core I-in. in diameter and 11-in. long was used. These materials were all somewhat bentonitic. 'To reduce the effect of such constituents, one of the cores (Torpedo No. 10) on which the most work was performed was acid extracted at the start of the experiment. Brine containing 50,000 ppm chloride and naphtha (Stoddard's Solvent) were used as the water and oil phases, respectively. The core was mounted in a rubber sleeve which forms the inner lining of a brass cylinder. In this arrangement2 the rubber sleeve is forced against the core by applying pressure to water in the annular space between the rubber sleeve and the brass cylinder wall. The core is therefore sealed in rubber so that all fluids introduced at the input end of the core flow through the core. With this equipment the core may be easily removed for inspection and analysis. Also, other cores may be introduced for study with no extra time for preparation such as is required when plastic mounting is used. When pressure or conductivity measurements are desired at intermediate points along tile length of the core, the brass cylinder comprising the outer jacket of the core holder is cut into section, of the desired length. Each section is then made up as an individual unit with its own rubber sleeve (see Fig. 1). The individual units are then butted up against a ring of plastic or other insulating material which carries an electrical contact for resistivity measurements and an opening which can be used for the measurements of fluid pressures. The individual units are forced tightly against the plastic ring separators and held in place with several tie rods. Inlet and outlet end butts of the same diameter as the core and several inches in length are provided to control the introduction and withdrawal of fluids and to complete the arrangement for sealing the core within the rubber sleeve. Fluid flow is maintained either by applying pressure to the liquid confined in a reservoir or by the use of a gear pump. The latter is preferable where continuous flow at a moderate rate over a long time interval is desired since a small volume of liquid can be readily recirculated using filters to prevent plugging of the core. EXPERIMENTAL The oven-dried core is weighed and is then completely saturated with brine

Jan 1, 1950

By G. Das, S. V. Radcliffe

The substructural features developed in tungsten as a function of annealing temperature (up to 2200°C) and type of material [undoped and doped powder metallurgy (PM) tungsten and electron beam melted tungsten] have been investigated by transmission electron microscopy. For doped PM tungsten wires, characteristic "par-ticulate" substructural features developed rapidly with increase in annealing temperature above 700°C. The features consisted of parallel rows of elongated or circular shapes (500 to 1000A diam) lying along the direction of the wire axis and were identified as internal voids by diffraction contrast experiments. In recrystallized doped PM rod, larger voids were observed and were identified by precision dark field analysis to be cubic in shape and bounded by (100) planes. In marked contrast with both the doped PM materials, recrystallized undoped PM rod exhibited only very occasional and randomly arranged voids. Furthermore, no voids were observed in either material after electron beam melting. The high concentration of voids in the doped PM materials is attributed primarily to vaporization of doping additions or their pvoducts situated at the original grain boundaries , whereas the few voids in undoped material are considered to be traces of microporosity which were not eliminated during sintering. A tentative mechanism is suggested for the dezlelopment of the voids in relation to the processing sequences (sintering and working) and to the subsequent annealing. In recent years, a characteristic substructural feature consisting of rows of small elongated or circular regions of light contrast lying along the direction of working has been seen in thin foil electron microscopy studies of annealed sheet, wire, and rod tungsten. These features were present in the published micrographs of sheet by Weissmann et al.1 and of wire by Meieran and Thomas2, although the authors did not draw attention to them. Wronski and Fourdeux3 observed similar features in sintered rod tungsten (it was not specified whether or not the material was doped*) and interpreted them on the basis of their ap- particles, based on extraction replica evidence from the fracture surface of the initial hot-rolled slab material from which the sheet was prepared. No diffraction contrast experiments on the features were reported in any of these studies. The present investigation was undertaken with the primary objectives of: a) identifying the nature of these substructural features in tungsten by electron diffraction contrast experiments, since the contrast for voids can be expected to differ from that for crystalline or glassy particles, and b) elucidating the origin of the features and their development. For the latter purpose, doped and undoped powder metallurgy tungsten was obtained as rod and wire to represent different stages of reduction during final processing. These materials were examined both in the as-processed condition and after annealing to successively higher temperatures. In addition, the same doped and undoped materials were examined after vacuum melting in rod form. I) MATERIALS AND PROCEDURE Doped powder metallurgy (PM) tungsten wire (commercial purity 99.9 pct W) was obtained in the as-drawn and surface ground condition (0.030 in. diam "ground seal rod"). Doped and undoped tungsten rod (0.075 in. diam) representing an earlier stage of final processing was obtained from the same commercial source (Refractory Metals Division, General Electric Co.). Lengths of both the doped and undoped rod materials were single-pass melted in an electron-beam zone refiner to examine the effect of vacuum melting on the substructure. Annealing was carried out in a tungsten crucible in a tantalum strip resistance furnace under a vacuum of l0-15 mm Hg. Longitudinal sections of the wire and rod materials were examined by light and electron microscopy. The preparation of thin foils suitable for electron transmission from 0.030 in. diam tungsten wire and the rod specimens was carried out by means of a high-precision microjet technique developed to provide lack of jet stability and precise control of the area thinned. The method is described in detail elsewhere.' The foils were examined in a JEM 6A electron microscope using a goniometer stage (±20 deg tilt, 360 deg rotation) and operated at 100 kV. To minimize contamination problems a 200 µ condenser aperture was used in conjunction with a useful beam current of 50 µA. II) RESULTS AND DISCUSSION A) Diffraction Contrast Analysis. In order to determine the optimum conditions for the development of the substructural feature, a series of isochronal 30 min annealing experiments were carried out on specimens of the doped PM tungsten wire. The transmission electron microscopy analysis showed that the as-drawn wire, Fig. 1(a), consists of 'fibers' whose long axis is closely parallel to the wire axis of (110). The fiber width averages some 0.5 µ. Dense disloca-

Jan 1, 1969

By William A. Vogely

Mining employment in the United States declined from 986,000 employees in 1948 to about 600,000 employees today. This has occurred even though the Index of Physical Volume of Mineral Production (1957-59=100) has increased from 88 to 111 and the value of mineral production measured in constant(1957-59) dollars has increased from $14.7 billion to approximately $19.3 billion. Average unit mine value has increased 24% as compared with a 34% increase in prices in general. Apparent consumption has increased more than domestic production, indicating an increased dependence on imports. The mineral economy presents a complex pattern of development factors in the post-war period. This article presents a technique by which the various forces that have been acting on the market for a mineral commodity may be sorted out and by which the extent of the impact of technological change in use as well as the technological change in production can be measured. If one is interested in delineating fully and completely the impact of technological change upon the mining industries, it is not sufficient to describe the increase in productivity reflected by the above employment and production figures. What is reflected there is only the effect of technological change in the production function of the commodities under concern. These effects are obviously very substantial and have major implications for labor, capital and supplying industries. However, they are not the only effects of technological change and, in fact, may be relatively minor when the impact which arises because of changing technology in the using or consuming industries is considered.

Jan 4, 1965

By R. A. Vandermeer, J. C. Ogle

Two distinct types of depth-dependent variations in texture have been observed in niobium cold-rolled various amounts up to 99.5 pct reduction in thickness. These nonuniformities are thought to be the results of nonhomogeneous plastic dewmation during rolling. The first type is characterized by a zone at intermediate depths that tends to lack certain strong orientations which are present in the surface and center layers of the rolled stock. This type of texture modification seemed to be associuted with "high" body rolling and may be related to the shape of the zone of deformation in rolling. The second type of texture inhomogeneity found involved the formation of a unique texture in the surface layers of heavily rolled strip. High fiiction forces between work piece and rolls appear to be needed to generate and maintain this texture. We believe that this unique surface texture results from a shear mode of deformation in the surface layers. THE evolution of texture in both the surface and center regions of cold-rolled niobium as a function of increasing deformation from 43 to 99.5 pct reduction in thickness was reported in a previous paper.' It was noted that for strips rolled between 95 and 98 pct reduction a distinctly different texture appeared in the surface layers which was unlike the center texture. Certain other layer to layer textural variations were also detected during the experimental phase of that work but were not described in the paper. Surface textures have been reported previously for the bcc materials iron and Steel2-4 and are well known in the fcc metals.5 It is usually stated that these are shear textures which arise under conditions of high friction between specimen and rolls. Work by Mayer-Rosa and Haessner5 n niobium rolled under conditions presumed to be high roll friction gave no indication, however, of a surface texture in that material. This is indeed puzzling in view of our results.' Thus we undertook additional experiments designed to study the stability of the surface texture for certain rolling variables. The variables investigated were the presence or absence of lubrication, amount of reduction per pass, and reverse vs unidirectional rolling. It is the purpose of the present paper to describe the kinds of depth-dependent textural inhomogeneities that we have observed in rolled niobium as well as to present the results of our recent experiments on the stability of the surface texture. Possible explanations for the depth-dependent texture variations will be discussed in terms of nonhomogeneous plastic deformation during rolling. EXPERIMENTAL Specimens cut from the niobium rolled to different reductions in the previous study1 were examined at various layer levels throughout the strip thickness for textural inhomogeneity. The specimen surfaces were either etched or machine ground and etched to remove material to a specific depth. Textures were determined by means of the Schulz X-ray reflection pole figure method with a Siemens texture goniometer and Cum X radiation. Since the important intensity peaks of the textures in niobium are usually located on the normal direction (N.D.) to rolling direction (R.D.) radius of the (110) pole figures, it was sufficient in many cases to scan only along this radius. At selected depths or where additional information was required the entire (110) pole figure was also obtained. In studying the stability and formation of the surface texture, experiments were conducted on 0.400-in.-thick, fine-grained, randomly oriented niobium specimens extracted from the same starting stock as that used in the earlier study.' Two of these specimens were rolled at room temperature to a total reduction of 96.4 pct. One was rolled between cleaned and degreased rolls with no lubrication. The other was lubricated between passes with Welch Duo Seal vacuum pump oil. The rolling schedules of each were kept as nearly identical as possible. Drafts were of the order of 0.006 to 0.012 in. per pass. Other experiments consisted of rolling specimens at constant fractional reduction per pass, i.e., (ta- tb)/ta equals a constant where ta and tb are the entrance and exit thickness of the rolled stock, rather than at a constant draft, i.e., ta- tb equals a constant. Ten specimens were rolled at room temperature on a two-high, motor-driven rolling mill with 8-in.-diam rolls. These specimens were rolled to thicknesses of between 0.041 and 0.073 in. (82 to 90 pct total reduction) at approximately constant reductions per pass ranging from 9 to 45 pct. Kerosene was used as a lubricant. Half of the specimens were always rolled in the same direction while the other half were reversed end to end at each pass. The texture in the surface regions was determined with the X-ray technique described above. RESULTS The textural inhomogeneities noted in niobium rolled from fine-grained, randomly oriented stock 1.5 in. long by 0.75 in. wide by 0.40 in. thick can be classified into two types. The first may be discussed with the aid of Figs. 1 to 3. Fig. 1 is a three-dimensional plot of the X-ray intensity in units of times random vs f , the angle from the N.D. to any point along the N.D. to R.D. radius of the (110) pole figure, and depth, given as percent of the thickness (?t/to X 100, where at is the thickness of material removed and to is the as-rolled

Jan 1, 1970