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By P. Gordon

An isothermal jacket microcalorimeter, supplemented by metallographic, microhardness, and X-ray measurements has been used to study the isothermal annealing of high purity copper after room temperature tensile deformation. The amount of stored energy released during annealing has been measured as a function of deformation in the range 10.8 to 39.5 pct elongation. The data have shown the major heat effect to be associated with recrystallization and have allowed an analysis of the recrystal-lization kinetics and the calculation of activation energies of recrystallization. WHEN a metal is deformed plastically, some of the energy expended is dissipated as heat during the working process, while the remainder is stored within the metal in the form of lattice distortions and imperfections. During subsequent heating of the metal, the distortions and imperfections can be largely annealed out and the associated stored energy released as heat. It is apparent that measurements of the evolution of stored energy during such annealing may produce important information concerning the nature of the annealing mechanisms and the imperfections involved. Some excellent studies of this type have been made in the past, notably those of Taylor and Quinney,' Suzuki,2 Bever and Ticknor,3 Borelius, Berglund, and Sjöberg,4 and Clarebrough et al.5,6 None of this work, however, employed isothermal techniques, with the exception of the Borelius studies' in which only the early annealing stages were investigated. Since isothermal measurements, as compared with heating or cooling curve, have the merits that 1—they reveal the kinetics of a process more clearly, 2—the results obtained are more easily applied to theory, and 3—most fundamental investigations of annealing using techniques other than calorimetry have been carried out isothermally, it was considered important to apply calorimetry to the study of the isothermal annealing of metals. Accordingly, an isothermal jacket calorimeter of the Borelius type,' supplemented by metallographic, hardness, and X-ray measurements, has been used to study the annealing of high purity copper after room temperature tensile deformation. Experimental The microcalorimeter has been described fully elsewhere." Briefly, the specimen to be studied is placed in a constant temperature environment of virtually infinite heat capacity achieved, as shown in the drawing of Fig. 1, by means of a vapor thermostat. A high thermal resistance is provided between the sample and the environment and a sensitive differential thermopile (see Figs. 2 and 3) arranged with half its junctions in contact with, and thus at the constant temperature of, the environment, and the other half in contact with the sample. A reaction in the sample develops a small difference in temperature, AT, across the thermopile, which is followed by a recorder-galvanometer set-up as a function of time, t, and is converted to reaction heat per unit time, P, by the use of the equation AT P=a?T + b AT dt The constants, a and b, in Eq. 1 are determined by a simple calibration, making use of the Peltier heat developed by a small current run through the junction of a thermocouple located in an axial hole in the specimen (Fig. 2). In its present form, the limit of sensitivity of the calorimeter is a heat flow of 0.003 cal per hr. The copper used was the spectroscopically pure metal supplied by the American Smelting and Refining Co. in the form of 3/8 in. diam continuously cast rod, reported to be 99.999+ pct Cu. A small amount of the copper was available at the start of this work and is referred to hereafter as lot A. A second batch, lot B, was obtained later, most of the results described subsequently being for this lot. As will be seen, there is some indication that lot A was somewhat purer than lot B, but it is not known whether this difference was present in the as-received metal or arose during subsequent handling. The two lots of copper were remelted and cast into two 1½ in. diam ingots in vacuo, using high purity graphite crucibles and molds. The ingots were upset several times to break up the large cast grains, and then rolled and swaged to rods 0.391 in. in diameter, using several intermediate anneals with about 40 pct reduction in area between anneals. The penultimate anneal was 2 hr at 350°C. X-ray examination showed no marked general preferred orientation in the resulting rods. The grain structure typical of the two rods is shown in the micrograph of Fig. 4." It was found to be virtually im- possible to get an unambiguous measure of the absolute grain size in the two annealed rods because of the profusion of annealing twins and the lack of regularity of the grain boundaries. However, counts of the number of boundaries intersected per unit length along a random line on a polished section, making a correction for the proportion of boundaries (about half) estimated to be twin boundaries, gave a figure of about 0.015 mm for the average grain diameter. The grain size of the rod from lot A was about 5 pct smaller than that from lot B. The rods were cut into 1 ft long bars and these deformed in tension at room temperature to various total elongations in the range 10.8 to 39.5 pct. A strain rate of 1 pct per min was used. The deformed bars were then stored in a dry ice chest until such time as samples were to be cut from them. Five bars deformed as indicated in Table I were used for the subsequent tests. In all cases, all the calorimeter.

Jan 1, 1956

By J. M. Hodge, M. A. Orehoski

THE relationship between hardenability based on a 50 per cent martensite criterion, and that based on higher percentages of martensite in a number of low-alloy steels was discussed in a previous paper by the authors.1 It was found that the differences between the hardenability values based on the 50 per cent martensite and full martensite criterions increased as the hardenability increased and that, in the steels of higher hardenability, these differences were fairly large. Furthermore, it was found that these relationships could be expressed with reasonable accuracy as a function of the hardenability. The importance of the full martensite criterion of hardenability in relation to the attainment of the optimum mechanical properties of tempered martensite was emphasized in the earlier paper. The purpose of the present work is to study the effects of some of the individual alloying elements on hardenability, using three different percentages of martensite as criteria, and thereby to evaluate the role of these individual elements in the general hardenability relationships previously reported. EXPERIMENTAL PROCEDURE Induction-furnace heats weighing 17-lb., of the compositions given in Table I, were cast and forged into 1 ¼ in. round bars. All heats were killed with aluminum additions corresponding to 1 lb. per ton. The compositions were chosen to represent several series of steels, in which only one alloying element would vary and in which the nonmartensitic constituents on quenching would be predominantly bainitic. All bars were normalized from 1650°F. and tempered one hour at I 150°F. prior to the hardenability determinations. Hardenability values are based on metallographic examination of standard Jominy bars, quenched from 1600°F. (I hr. and 20 min. heating time). The general procedure was the same as outlined in detail in the previous paper; (I) that is, the distance from the quenched end of the bar to the point of 0.1 per cent transformation was first measured on the microscope and then the percentage of martensite was estimated at every 0.05 in. from the quenched end, and these percentage values plotted against the distance along the bar. In this case, samples 2 in. long were cut from the quenched end of the Jominy bars and 10 fields were examined and averaged at each distance. The conversion of Jominy distance to ideal diameter is based on a revised correlation curve (Fig. I). This curve is based on work carried out at the Research Department of the South Chicago Works, Carnegie-Illinois Steel Corporation, and represents a direct correlation between hardenability values as deter-

Jan 1, 1946

By Persifor Frazer

The following notes on the Whopper and adjoining mines in the Gunnison district of Colorado mere made in the spring of this year. The time chosen for the author to visit the region was, unfortunately, the most unfavorable of an exceptionably unfavorable year. About the middle of May all the hill slopes, which at this period of the pear are generally covered with pasture, were thickly covered with snow. The unusually large precipitation of this Tear caused loacal mountain torrents at every few hundred feet, which wore away the oft foothills into gulches, gouged great chasms out of the roads, and transformed miles of usually dry soil into dangerous quagmires. Travel was totally interrupted for weeks, except on horseback or afoot, and even then with great difficulty and some danger. The Whopper mine is situated on the Whopper Mountain, about two miles from the headwaters of Rock Creek, and on the right hank of that stream. The Whopper Creek flows into Rock Creek horn the east, and, by a precipitous descent, offers excellent facilities for its utilization as a source of power. This stream, which pours past the picturesque Whopper Cabin about thirty tons of water a minute, has a fall of 100 feet in 400 yards, and is said to be a stream of some size, even at the seasons of the year when drought prevails. The Whopper claim extends down the hill a distance of about 250 feet to its intersection with the Whopper Creek (on the other side of which is a small tunnel on its extension called the "Teller") and over the steep hill northwest to the limits of the claim about 1250 feet. The part of the mountain in which this mine is situated is remarkable for its splendid forest, the spruce, fir, and quaking asp covering the mountain-sides with a green growth of valuable timber. The distance from Gothic City to this mine is about eight miles along the valleys of East River and Rock Creek, and on the divide which separates them. The elevation of Gothic City is given from the engineer's notes as 9500 feet above sea-level, and the mean of several observations with a Beck watch-barometer made the elevation of Whopper Cabin (which is about fifteen feet above the floor of the Whopper upper tunnel) about 1260 feet above Skiles's Cabin in Gothic City. The record of this instrument must, how-

Jan 1, 1881

By Persifor Frazer

THE following notes on the Whopper and adjoining mines in the Gunnison district of Colorado were made in the spring of this year. The time chosen for the author to visit the region was, unfortunately, the most unfavorable of an exceptionably unfavorable year. About the middle of May all the hill slopes, which at this period of the year are generally covered with pasture, were thickly covered with snow. The unusually large precipitation of this year caused local mountain torrents at every few hundred feet, which wore away the soft foothills into gulches, gouged great chasms out of the roads, and transformed miles of usually dry soil into dangerous quagmires. Travel was totally interrupted for weeks, except on horseback or afoot, and even then with great difficulty and some danger. The Whopper mine is situated on the Whopper Mountain, about two miles from the headwaters of Rock Creek, and on the right bank of that stream. The Whopper Creek flows into Rock Creek from the east, and, by a precipitous descent, offers excellent facilities for its utilization as a source of power. This stream, which pours past the picturesque Whopper Cabin .about thirty tons of water a minute, has a fall of 100 feet in 400 yards, and is said to be a stream of some size, even at the seasons of the year when-drought prevails. The Whopper claim extends down the bill a distance of about 250 feet to its intersection with the Whopper Creek (on the other side of which is a small tunnel on its extension called the "Teller ") and over the steep hill northwest to the limits of the claim about 1250 feet. The part of the mountain in which this mine is situated is remarkable for its splendid forest, the spruce, fir, and quaking asp covering the mountain-sides with a green growth of valuable timber. The distance from Gothic City to this mine is about eight miles along the valleys of East River and Rock Creek, and on the divide which separates them. The elevation of Gothic City is given from the engineer's notes as 9500 feet above sea-level, and the mean of several observations with a Beck watch-barometer made the elevation of Whopper Cabin (which is about fifteen feet above the floor of the Whopper upper tunnel) about 1250 feet above Skiles's Cabin in Gothic City. The record of this instrument must, how-

Jan 1, 1881

By Daniel D. Pollock

The il'lott and Jones theory of thermoelectricity predicts that the absolute thermoelectric power of alloys of transition and noble metals should be a maximum when the concentration of the noble metal is approximately 55 to 60 at. pct. An examination of the emf of a series of relatively pure alloys of copper and nickel shows that the predicted maximum occurs at about 57 at. pct Cu. This excellent agreement with the theory is considered to substantiate the Mott and Jones theory of thermoelectricity for binary alloys of transition elements. This theory is extended to show that the emf behavior of dilute, ternary copper-nickel base alloys, which contain approsimately 60 pct Cu and 40 pct Ni, may be described in terms of a scattering mechanism. The scattering effect of a third element is demonstrated to be a function of its valence and its period in the periodic table. Small amounts of solute elements have additive scattering effects upon the emf of the Cu-Ni base. The Mott and Jones equation is modified to include this scattering parameter. This adaptation accurately describes the thermoelectric behavior of ternary and quaternary CLL-Ni base alloys. An empirical form of the modified Mott and Jones equation is derived which permits the calculation of thermoelectric power with an average error of less than 0.4 pct at 500 "C. CONSTANTAN has long been used as a thermocouple element. Its approximate composition varies from 50 pct Cu, 50 pct Ni to 65 pct Cu, 35 pct Ni. Small amounts of manganese, iron, and other elements have been used to modify the composition in order that the resultant emf vs platinum conforms to nationally accepted table. Adjustments of this type are made on a purely empirical basis. Constantan was originally made in Germany and was imported into this country for thermoelectric and electrical resistance purposes. During World War I, the supply of this material became seriously depleted. The work of Bash4 was done in this period in order to develop a satisfactory substitute for the imported material. Bash's empirical work on Cu-Ni alloys is still the basis for all commercial constantans made in this country. No reexamination of the electrical properties of this system has been made, despite the fact that it is now well known that Bash's alloys contained impurities which strongly affected their thermoelectric behavior.

Jan 1, 1962

By Frederic E. Carter

There have been many attempts to prove that platinum was known to the ancients, but since no traces of the metal have been found in the relics of early times, it must be concluded that it was not known to them. As far as records go, it was actually first discovered in the 16th century in a Spanish mine on the Pinto River in South America; from which source it received its name of Platina del Pinto (little silver from the Pinto). It was more or less of a rarity and was a subject of interest to a few chemists only, until the year 1822 when the metal was first discovered in Russia. In 1819 there were noticed in the washings of the gold sands of the southern part of the Ural Mountains, grains of a heavy white substance, but it was not until three years later that this substance was found to contain platinum. While at first the amounts of platinum brought from the Urals were meager, prospecting soon disclosed rich deposits extending over a considerable area, and nuggets from 10 to 20 lb. were by no means rare. This discovery assured to chemists an ample supply of platinum for their crucibles, etc. The ore is now found in various parts of the world but the richest deposits are still found in the Ural Mountains. The platinum of commerce is obtained entirely from alluvial deposits at depths varying from 6 to 40 ft. The sand and gravel of former river beds are subjected to a series of screenings and washings to effect the separation of the ore. Actually, probably all gold-bearing gravel beds of the world contain platinum, and it is more than likely that large quantities of platinum ore have been thrown away with the black sand washings from gold placer deposits. This is especially true of the alluvial deposits of the Pacific Coast in California and Oregon. Platinum ore is usually found in the form of rounded or flattened grains of "sand," and occasionally in irregular lumps of the size of peas. Large nuggets are very rare. The ore has a metallic luster and is distinguished by its steel gray color, but shows light gray streak when rubbed on a hard white surface; it has a high specific gravity, 16 to 19; is infusible in the hottest blast furnaces, and insoluble in any single acid. Platinum ore is a complex body consisting of the metal in combination with varying proportions of the other members of the platinum group; iridium,

By AIME AIME

THE organization of the Board of Directors was effected Tuesday afternoon in ' executive session. Messrs. Bassett,. Buehler, Cates, Daveler, Eavenson, Eilers, Elliott, Evans, Guess, Lovejoy, Moulton, Rickard, Tally, Turner,, Wraith and Wright being pres¬ent. Messrs. Tally, Bassett, Rickard, Mathews and Cates were chosen to form the Executive Committe with Mr. Tally as Chairman, and Messrs. Krumb, Guess and Moulton for the Finance Committee with Mr. Krumb as chairman. Karl Eilers was reelected as Treasurer and H. Foster Bain as Secretary, after which the Directors adjourned for the usual dinner reported elsewhere. At the open session of the Board, at which in addition Messrs. Allen and McAuliffe were present, the work of organization was continued with appointments to committees as listed herewith. Various actions of the Executive and Finance Committees were confirmed, the budget for 1931 formally approved, the meeting dates for the year adopted, 34 new Members and Associates, 13 Junior Members and 31 Student Associates admitted by election and transfer and 29 resignations accepted.

Jan 1, 1931

By J. R. Low, M. Gensamer

During the course of an investigation into the drawability of automobile-body sheet steel, it became apparent that certain advantages would be possessed by a deep-drawing steel with a very low yield strength, but almost normal tensile strength, provided a reduction in yield strength could be accomplished without sacrifice of ductility and fine grain size. It would also be desirable to have this steel free from strainaging; that is, free from the tendency for the yield point to return after it had been eliminated by straining. It was known that wet hydrogen treatment acted to eliminate aging, but as carried out by other investigators, at relatively high temperatures, this treatment resulted in grain coarsening. It has been established by some of the experiments reported in this paper that all of these objectives can be accomplished by treatment in wet hydrogen at a low temperature, in the neighborhood of 720°C. The time of treatment is relatively short (about 3 hr. to completion with 20-gauge sheet) if the water content of the hydrogen atmosphere is made fairly high, say almost 30 per cent by volume. At this temperature, the grain size remains fine in the time required. After this treatment sheet reduced the usual amount by cold-rolling has a grain size of about A.S.T.M. No. 7. The yield point is completely eliminated, and the yield strength is reduced to a very low value, in the neighborhood of 15,000 lb. per sq. in. The stress-strain curve departs gradually from the straight-line elastic part after the fashion of nonferrous deep-drawing alloys. This elimination of the yield point is accompanied by a very low indentation hardness; for example, 32 Rockwell B or even lower. There is no aging as measured by increase in the yield strength upon aging at room temperature or for 3 hr. at 200°C., after stretching about 10 per cent in tension. Tensile strength is only slightly less than the box-annealed sheet, seldom dropping much below 40,000 lb. per sq. in. Elongation is practically unchanged, or increased slightly. The term yield point, as here used, refers to the phenomenon of heterogeneous deformation occurring at a substantially constant load, observed principally in annealed low-carbon steels. If such a steel is loaded in tension, the load increases steadily with elastic strain, suddenly falls, fluctuates slightly about some constant value for a time and then begins to rise again as deformation proceeds. The maximum initial load before the sudden drop is generally called the "upper yield point"; the value of the load where deformation proceeds at a

Jan 1, 1943

By R. A. Burmeister, P. E. Greene

Two methods for the synthesis and growth of single crystals of B6 P are described: a solution-growth process employing nickel as the solvent, and a vapor-growth process employing BBr3 and pH3 as the reac-tants. Relevant portions of the Ni-B-P phase diagram have been examined and liquidus data are presented for an isobaric section at an equivalent P2 pressure of 3.8 Torr, and an isothertnal section at 1300°C. Solution-growth techniques are described and the purity and crystalline perfection of the resulting material is discussed. Epitaxial growth of BeP on &P substrates has been obtained using the vapor-phase system. Evidence is presented which supports the assignment of the stoichioknetry B6P to boron sub-plwsphide. THE B-P system differs from other III-V systems in that it contains two distinct compounds. The existence of the monophosphide (BP) has been known for some time,' whereas the subphosphide (B6P) was reported only recently.' Both of these compounds are large bandgap semiconductors (Eg = 2.0 ev for BP~ and 3.3 ev for B6P4), and are therefore of interest for optoelectronic applications. The crystal structure of B6P is quite different from those of most semiconductors, being derived from that of a-rhombohedral boron by the incorporation of the two phosphorus atoms in the intericosahedral sites of the a-boron unit cell?76 B6P also exhibits a number of unusual characteristics, including a high degree of chemical inertness, hardness, and high-temperature stability. No information concerning other physical properties is available in the literature. The present study is part of a broader investigation of the preparation and properties of B6P. This paper considers methods of growing single crystals of B6P of suitable size and quality for physical-property measurements. A detailed discussion of the electrical and optical properties of B6P will be given elsewhere.' GENERAL CONSIDERATIONS The method first used to synthesize B6P was the disproportionation of BP' according to the reaction The equilibrium P2 pressures corresponding to this reaction were also determined .'" It is therefore possible, in principle, to apply several of the reactions reported for the synthesis of BP to the synthesis of B6P merely by selecting lower phosphorus pressures or higher temperatures, in accordance with the equilibrium data. Other techniques for the direct synthesis of microcry stalline B8P have also been reported.1°

Jan 1, 1968

By H. S. Bell

IT SEEMS unnecessary to dwell upon the advantages of the modern pipe still as compared with the older type of distillation equipment used by oil refiners. The relatively low installation cost, coupled with remarkable operating efficiencies of pipe stills, precludes the consideration of other types except in rare instances where some peculiarity of product or plant may have an influence. The question of the actual heat required to distil petroleum is quite involved. We have extensive data on the latent heats of the various hydrocarbons under different conditions of pressure. We also have information regarding the specific heats of various oils and the effect of temperature thereon. Because of the complexity of petroleum and of each fraction, it seems impossible to theoretically analyze the partial-pressure effect of the great number of hydrocarbons upon one another during distillation. If a distillation curve and percentage analysis of any crude or product are available, it is possible to construct a curve with ordinates representing per cent. distilled and B. t. u. per pound or per gallon, or other desired unit. To do so the crude is split into fractions, of 5 or 10 per cent. The boiling point and gravity of each fraction being determined, it is possible to evaluate the heat required. As each fraction is removed, the residue must be raised to a higher temperature and latent heat supplied for the successive fraction. As the calculations progress, the latent heats decrease while the specific heats increase. Such a curve is illustrated by Fig. 1 for a typical 39.9 B° North Texas crude.

Jan 1, 1928

By M. M. Rao, P. G. Winchell, R. J. Russell

A detailed analysis has been used to correlate the avalable thermodynami c da In on iron-ric11 Fe-Ni (41loys in the body-centered a, and the face-centered y phases. The inp ut injovrt~ation required by the a am lysis consists of tile heat of the a, to y transformation at 1123°K, the heat of mixing of y at 1123°K, tile specific heats of both a, and y (decomposed into Debye, electronic, and magnelic contributions), and the positional and magnetic entropies of both a, and y. PYLrrzary oirt.bul of the analysis is the free energy of each phase as a Junction of temperature and composition. FOr Fe-Ni alloys the adjustment of twenty-one parunletevs allows the accurate reproduction of enthalpy data for both phases, the heat of mixing- for y, the a/y equilibrinm compositions in the Fe-Ni phase diagram, and the usually accepted enthalpy and entropy of a and y iron. Also obtaitzed are fuirly accurate reproductions of electronic specific heat coefficients predicted from electron- to-atom ratio interpolations and To temperatuves eslimanted from transformation studies. Also considered in the calculation are the elastic constants, Curie temperatures, saturation magnlelizalion values, and indications of short- range order. The measnred activity coefficient of iron in anstetnite could not be accurately matched. The major source of uncertainty in the model is thought to be the magnetic contribution to the entropy of austenite. Calcrclations were extended to Fe-ni-C alloys using available carbon-acliuity data. The free energy of transformation from martensile to r at fixed composition was obtained as a function of nickel and carbon contetzt, and binary thetal-carbon phase diagrams Were estimaled as a function of nickel contenl. We needed thermodynamic information for Fe-Ni and Fe-Ni-C alloys at temperatures between 400" and 800°K in order to interpret the results of several phase-transformation studies. The most recent theoretical analysis of the thermodynamics of Fe-Nialloysl was based on a lumped-parameter, regular-solution model and used the Fe-Ni phase diagram available at that time.' Because significant difficulties were encountered in attempting to extend this analysis to Fe-Ni-C alloys, and because more experimental data has become available recently, we decided to attempt a new correlation. The analysis used here allows the extrapolation of measured and calculated thermodynamic values to lower temperatures and the extension of the thermodynamic analysis to Fe-Ni-C alloys. The structure of this correlation consists of expressions containing a total of twenty-one adjustable parameters. The forms of these expressions are discussed in the next section; however, a less formal summary is presented now to provide a physical overview of the model and to indicate its connections to prior work. Primary input information for this correlation is described below. The measured values of the specific heat of iron3 and its analysis475 and theoretical estimates of the specific heat of y* iron at low tempera- loys at 1123°K has been measured by solution calori-metry.7 The enthalpies of both a, and y have been measured most recently by Scheil and Saftig,B who used a dry-ice calorimeter. These data are used to formulate expressions for the heat of mixing of y and the heat of transformation of a, to y both at 1123°K. The a and y solubility limits in the Fe-Ni phase diagram have been redetermined recently9 by methods which assure a close approach to equilibrium. The a to y transformation can occur without change in nickel content or free energy at a temperature called TO; TO temperatures for various nickel contents have been estimated from transformation studies. The computed free-energy functions are adjusted by means of the parameters to fit both the phase diagram and the TO temperatures. Primary emphasis is placed on the phase diagram fit. Iron activities have been measured in Fe-Ni austenite10 between 973" and 1173°K. These activity data, which cannot be fitted accurately with our model, indicate that iron is substantially ideal in iron-rich austenite. Secondary, but helpful, information for the present correlation is provided by neutron diffraction and saturation magnetization measurements on both body-centered and face-centered Fe-Ni alloys."-'3 These results were interpreted11 in terms of composition-insensitive, localized magnetic moments on both iron

Jan 1, 1968

By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph',' to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox' make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952

By Donald Barton

THIS paper outlines a time-saving graphical method of calculation for application to the interpretation of observations with the Eötvös torsion balance. Preliminary to the treatment of this short cut method which has been found practicable, the principal formu-las by which the student of interpretation can calculate the gradient and differential curvature produced by different types of bodies in different types of situa-tions are presented and discussed. It is necessary to split most geologic bodies into a series of simpler ones for which not too complicated formulas are avail-able. The gradient and differential curvature effects are calculated for each of the simple bodies and then summed to the total effect for the whole body. The calculations are considerable in number and, though more tedious than difficult, should be' entrusted to an experienced calculator. Considerable facility in qualitative interpretation can be acquired by the geophysicist from experience and from a thorough study of the types of gradient and differential curvature anomalies produced by the dif-ferent types of possible structural situations. How-ever, semi-quantitative calculations' of the probable structure bring out many relations that are not evident in a simple inspection of torsion balance results ; it throws out as impossible or improbable certain of the alternative structural possibilities that may seem equally probable under simple inspection of the results; it will determine more accurately the position of the crest of the structure; and reduce considerably the un-certainty in the interpretation and it is necessary to intelligent interpretations. The calculation of such cross-sections consists of a trial-and-error calculation of a body that will give gradient and differential curvature effects as closely as possible the same as those observed. From his knowledge of the gradient and differential curvature produced by different types of bodies, the geophysicist sketches a tentative cross-section of the structure as indicated-to him-by the observed results of the torsion balance survey, and the calculator then splits the struc-ture into blocks, and calculates the gradient and differ-ential curvature block by block. If, as rather usual, the calculated .gradient and differential curvature pro-files diverge considerably from, the respective observed ones, it is necessary to add and subtract blocks from the cross-section until a close agreement is obtained .between the calculated and observed profiles. The com-plete calculations have to be gone through for each block that is added or subtracted.

Jan 9, 1928

By Stephen Taber

A vein may be defined as an aggregation of mineral matter, more or less tabular or lenticular in form, which was deposited from solution and is of later origin than the inclosing rock. This definition differs from the one found in many text-books in that no assumption is made as to the origin of the space occupied by the vein or the manner in which the mineral matter was deposited. In the present paper the writer purposes to discuss the mechanics of vein formation, and does not wish to begin by begging the question. The origin of ore deposits has been diligently investigated in recent years, but, while much has been written concerning the chemistry of the process, the physical side of the question has received less attention. The source of the ore minerals; the chemical composition of ore-bearing solutions; the relative importance of magmatic and meteoric waters as agents of concentration; and the causes of mineral precipitation have all been discussed at length. On the other hand, little has been written concerning the mechanics of vein formation, and the theories given in text-books today are essentially the same as those developed by the early Cornish and Saxon miners. Early investigators often regarded both veins and dikes as igneous in origin, but today the theory that vein minerals have been deposited from solutions, either liquid or gaseous, is firmly established. The latter view is supported by the fact that many vein-forming minerals are not found in unaltered igneous rocks; by evidence obtained in the laboratory regarding the solubility of minerals; by the presence of many ore minerals in hot-spring waters; by the occurrence of some veins in regions consisting exclusively of unaltered sedimentary rocks; by evidence as to the temperature at which some minerals are formed; and by the absence of mineral segregation due to difference in specific gravity. There is still, however, much difference of opinion as to whether certain tabular-shaped masses should be classed as veins or as dikes. Some of the earlier investigators have also advocated the theory that veins are contemporaneous in origin with the inclosing rock, while others have believed the vein minerals to represent a recrystallization or transforma-

Jan 1, 1920

By C. Y. Garber

INTEREST in the sink-float plant operated by the Bunker Hill and Sullivan Mining and Concentrating Co. at Kellogg, Idaho, has recently been largely confined to the preparation and reconditioning of the galena medium. The ease and simplicity of these operations in a concentrating mill producing a flotation lead concentrate has occasioned enough comment to possibly justify a brief description. The subject is treated from an operator's viewpoint only; no effort is made to discuss it in a theoretical or technical manner. PLANT AT BUNKER HILL The sink-float plant was first operated in December 1941. It was built for the purpose of quickly increasing mill capacity with a minimum of equipment. It is the Huntington-Heberlein sink and float process using galena medium and is operated under license from the Sink and Float Corporation, New York city. Lead-zinc ore from the Bunker Hill mine is crushed to pass a I ¼ in. screen and is then washed and separated on vibrating screens having 4 ½ -mm. round-hole punched plates. The screen undersize, amounting to 33 per cent of the mill feed, is dewatered and sent to the ball-mill feed bins. The screen oversize goes to the sink-float plant, where 50 per cent of the oversize, or 33 per cent of the mill feed, is float, which is washed free of medium and disposed of as a tailing. The remaining 33 per cent is sink, which, after washing, is crushed to pass ½ in. and joins the undersize in the ball-mill feed bins. The normal plant capacity is 1700 tons per 24 hr. About 1.7 per cent of the total lead and 3.3 per cent of the total zinc in the feed is lost with the sink-float tailings (Table I). [ ] More complete descriptions of the H. H. process and Bunker Hill sink-float plant are given in several recent articles, listed at the end of the paper. PREPARATION OF MEDIUM AT BUNKER HILL New medium is made intermittently as needed, usually 12 hr. in each 6 days. A small portion of the current mill flotation concentrate is diverted from the lead cleaner cells to a I-in. vertical sand pump and pumped to a two-cell 36-in. Agitair flotation machine, where NaCn and ZnSO4 are added and the grade of concentrate is improved as shown in Table 2. Tailing from this operation is returned by gravity

Jan 1, 1946

The following is an incomplete list of members and guests who called at Institute headquarters during the period Nov. 10, 1918 to Dec. 10, 1918. Arthur C. Adair, Camp Meade, Md. L. S. Mitchell, Montreal, Canada. Arthur K. Adams, Camp Humphreys, Va. T. E. Mitchell, San Francisco, Cal. Toner Antisell, Chevy Chase, Md. H. Mortimer-Lamb, Montreal, Canada. V. W. Aubel, New Castle, Pa. Edmund Newton, A. C. Black, El Paso, Tex. Paul T. Norton, Jr., Columbus Ohio. 0. F. Brinton, Baxter Spgs., Kans. Elmer W. Pehrson, San José, Cal. C. S. Corbett, Minneapolis, Minn. Joseph E. Pogue, Washington, D. C. W. M. Corse, Mansfield, Ohio. T. C. Roberts, E. Orange, N. J. G. C. Crossley, Toms River, N. J. D. R. Semmes, Richmond, Va. H. S. Emlaw, Grand Haven, Mich. H. L. Slosson, Jr., San Francisco, Cal. Rudolph Emmel, Boston, Mass. W. H. Staver, S. G. Garrett, U. S. N. R. F. A. L. Sweetser, Boston, Mass. Lt. Francis Geib, Denver, Colo. Lt. H. B. Taylor, Kansas City, Mo. Wm. E. Hubbard, Wichita Falls, Tex. Kirby Thomas, New York. Arthur Iddings, Wichita Falls, Tex. Benj. F. Tibby, Salt Lake City, U. Zay Jeffries, Cleveland, Ohio. J. L. Towne, Whitepine, Colo. S. J. Kidder, Mogollon, N. M. Chas. W. Tubby, St. Paul, Minn. Lt.-Col. W. H. Lanagan (Engrs.). A. G. Waite, Brookline, Mass. Major W. F. Lewis (Engrs.). Timothy D. Walsh, Denver, Colo. 0. M. Lewyn, Thomas Warner, Phoenix, Ariz. A. McClintock, DeKalb June., N. Y. J. P. B. Webster, London, England. Major Donald G. Miller, N. M. E. W. Westervelt, Los Angeles, Cal. C. E. LeN. Arnold, formerly with the Inspiration Cons. Copper Co. at Inspiration, Ariz., has accepted a position with the Consolidated Arizona Smelting Co. at Mayer, Ariz.

Jan 1, 1919

By A. H. Tousley, C. L. Vickers

The author presents a history of the development of the Port of Long Beach from its beginning in 1905 to the present construction of a new bulk loading facility. In describing this new facility, emphasis is placed on such aspects as rail car and truck handling, gravity yard, rotary car dumping, bottom dumping, car dumping equipment, feeding and conveying, ship-loader-stockpiler, stockpiling and reclaim, dust control, and construction problems. Development of the Port of Long Beach, Calif. (see Fig. I), began in 1905. In that year private Long Beach interests acquired 800 acres of marshland in the Inner Harbor area and initiated a program of channel dredging and land reclamation. Efforts to establish a municipal port began a short time later and culminated in the opening of Pier 1 in 1911. An event of even greater significance to the port future also occurred in 1911. This was the tideland grant enactment by the state legislature that conveyed to the city of Long Beach all of the state's rights in the tidelands located within the city boundaries. The grant stipulated that all revenue produced from the tidelands be used for the development of navigation, commerce, and fisheries. During the next 15 years up to 1926, the port's commercial growth was steady, although relatively slow. During this period, several fundamental steps in the development of a major harbor were accomplished. These included the creation of the Board of Harbor Commissioners in 1917, the dredging of the Inner Harbor and entrance channel to accommodate deep draft vessels, and the correction of a serious silting problem through construction of the Los Angeles River Flood Control Channel. These efforts bore fruit during the ensuing 10 years in the establishment of more than $30,000,000 worth of industrial plants and private marine terminals in the Inner Harbor. Commerce over municipal wharves also increased more rapidly, and it became necessary to start the development of the harbor in a seaward direction. In 1936, oil was discovered in the harbor area, and the first Harbor Dept. well was brought in 2 years later. It soon became evident that the city of Long Beach would receive substantial revenue that, under the terms of the state grant of 1911, must be used in the development of the port. It was further realized that to properly guide and coordinate such development, a long range comprehensive plan was essential. The Board of Harbor Commissions contracted with G. F. Nicholson and J. F. Collins, consulting engineers, for the preparation of such a report that was completed in 1940. The Nicholson-Collins report proposed the development of an East Basin, between the entrance channel and the Los Angeles River, and a West Basin in the area now occupied by the Long Beach Naval Shipyard. Twenty full-size berths were to be provided in the East Basin and more than fifty berths in the West Basin. The report recommended extensive modern terminal facilities for handling waterborne cargo. Attention was given to improvement of the street and highway system to give better vehicular access and to avoid congestion within the port. To a large extent the recommendations of the Nicholson-Collins report were followed in the subsequent development of the East Basin. This development was greatly accelerated by World War 11, with its need for increased oil production and additional shipping facilities. The wartime and immediate postwar construction was largely concentrated on Pier A, with the development of Piers B, C and D following in more recent years. An important factor in the planning of these piers was their dual function as oil drilling sites and cargo piers. The Navy's acquisition of the West Basin area made it necessary to depart from the Nicholson-Collins plan and find other areas for future expansion. At the present time only one Inner Harbor Port-owned area having protected deep water frontage remains undeveloped. This is the property fronting on Channel 2 in the Inner Harbor acquired in December 1957, from Pacific Dock and Terminal Co. The growth of the port has been in a southerly direction since the construction of the Long Beach Naval Shipyard in the West Basin area. Recent extension of Piers F, G and J into the ocean follows typical port construction methods developed during the expansion of the Middle Harbor during the last 20 years.

Jan 1, 1963

By M. Kashiwada

The zinc leach residues are introduced into waelz kiln to fume volatile metals and before the end of 1967, the waelz-fume containing zinc, lead, cadmium and indium was directly recycled back to the leaching process for the production of electrolytic slab zinc. However, since 1968, we have been recovering with success those valuable metals contained in the fume separately instead of direct leaching. According to the improved process, the waelz-fume, after being mixed with chloridizing agents, is fed into the rotary kiln to be roasted, wherein most of lead and cadmium content is collected as fume and most of zinc remains in the calcine. Zinc calcine thus obtained, containing 70 to 75 per cent zinc and, less than 1.0 per cent lead is sent to zinc plant for further recovery and the fume containing 40 to 50 per cent lead and 3 to 6 per cent cadmium is further processed to recover lead, cadmium and indium. The advantage of this process can be secured to the utmost when it is combined with the following subsequent treatments. (a) Blast furnace smelting of non-magnetic waelz slag to recover copper, silver and gold as matte. (b) Gallium recovering process from magnetic waelz slag. (c) Soda process of lead bearing cake produced after removing cadmium and indium from the said fume. Thus the extractions of zinc, lead and cadmium from leach residues account for 87 per cent, 72 per cent and 85 per cent respectively.

Jan 1, 1970

By H. Biloni, B. Chalmers

Metallographic studies of the segregation of solute in and near the surfaces of chill-cast alloys have shown that, under sufficiently severe conditions, nucleation on the cold mold surface is followed by the formation of a disc of solid of the same composition as the liquid. This disc is surrounded by two concentric rings in which the concentration first decreases and then increases. The discs and rings are surrounded by a region in which arms of low solute concentration separate regions of high concentration. These arms start at the periphery of the outer ring and are initially radial; they make a gradual curved transition from the radial direction to a crystallographic direction. A normal dendritic substrcture is established beyond the position at which the arms have become crystallographically aligned. When the cooling is less severe, the disc becomes less irregular in shape and has a concentration minimum at the center. The term "Predendritic" is proposed for these transitions. A qualitative explanation is outlined for the phenomena observed at the surface and in the equiaxed region of the ingots. It is well-established1-' that the normal mode of solidification for alloys under most conditions is dendritic. A characteristic of dendritic solidification is the growth of rods or plates in specific crys-tallographic directions. The remaining liquid solidifies later, usually with a higher concentration of solute than the original liquid. Very little is known, however, about the transition from a crystal nucleus until the dendritic pattern is established. It is clear that there must be a transition because the nucleus is much smaller than the characteristic spacings found in the "steady-state" structure. And it also seems clear that the initial conditions must be important since the undercooling existing during the nucleation of the grains has a remarkable influence upon the grain size4 and the segregation pattern. The present paper reports a study of the micro-segregation in regions where crystals have nucleated, and the conclusions that can be drawn regarding the early stages of growth, in connection with the details of the solidification process. Aluminum of 99.993 purity, A1-Cu alloys containing 0.5 to 20 wt pct Cu, and Pb-Sn alloys with 5 wt pct Sn were cast and examined metallographically at the as-cast surface, close to the surface, and in the interior after casting. The alloys were cast from controlled temperatures against surfaces at different temperatures ranging from room temperature to approximately the liquidus temperature of the alloy. The surfaces were, in various experiments, graphite, stainless steel, copper, and aluminum. The methods used for metallographic examination were as follows. 1) The Nomarski phase contrast interferometer6 was used to obtain information on the topography of the as-cast surface. 2) The distribution of any solute present in A1 99.993 pct and copper in the A1-Cu alloys was studied by the anodic film technique originated by Lacombe and Mouflard7 and previously applied in the study of the solidification of aluminum by Biloni.8 The electropolished surface of the specimen is anodized under controlled conditions so that the thickness of the oxide film and therefore the interference colors under white light are sensitive to the local composition. This technique was applied to the as-cast surfaces and to metallographically prepared surfaces from the interior. 3) If in Al-Cu alloys, the surface is anodically oxidized for several minutes, instead of seconds as in the color-film technique, the copper segregation is outlined by a different level with respect to the matrix. This method is less sensitive but complementary to that for the color films. 4) The distribution of copper revealed and mapped by the metallographic techniques was confirmed by electron probe. 5) In samples with high concentration of copper, evidence for the copper distribution could be seen optically after electropolishing.

Jan 1, 1965

By A. Schild

The effect of heating a producing well on the rate of oil recovery has been analyzed in the simple case of a well producing oil by a radial drive and in the steady state. Differences of production rates with and without borehole heating have been calculated and plotted; these measure some of the benefits of the thermal recovery process. A striking feature is that the production increase tends rapidly to a constant value for large production rates. Some concrete examples, including a rough comparison with field data. are discussed. Heating requirements have been calculated and plotted on the assumption that the heaters used are 100 per cent efficient. Heating has been thought of as applying only to low volume wells producing heavy oils. However, the calculations suggest that the thermal process considered might be profitable even for some wells producing large quantities of light oil, especially in unconsolidated formations where fracturing is not possible. In the case of wells producing other fluids with the oil or of wells producing partly or wholly by gravity drainage, the theory developed does not apply in detail. It can be expected, however, that any general qualitative be-havior will remain valid. Under normal temperature conditions, high viscosity emulsions sometimes form around the wellbore, lowering the permeability in the vicinity of the well and impeding the production of oil. Borehole heating often prevents such emulsification. This important effect is not easily amenable to mathematical analysis and has not been included in the theory presented here. It should therefore be kept in mind that the benefits due to borehole heating may in fact exceed the values given by the following calculations. INTRODUCTION The recovery of viscous, low gravity oils can often be stimulated by applying heat to the production zone. The higher temperature lowers the viscosity of the oil, increasing its mobility, and therefore its rate of production. One thermal method of recovery 1,2,3,4. consists in operating a heater inside a producing well and, at the same time, producing oil from the well. In this paper a simple theoretical model is analyzed to study the effect of such heating on the recovery of oil. The reservoir mechanics of the process is the only aspect of the problem which is considered here. The details of the heating system are ignored, and it is simply assumed that the heater raises the temperature in the immediate vicinity of the producing well to a pre-assigned temperature T w. Although heating requirements are calculated, these refer only to the heat supplied to the formation and to the oil being produced; they do not include heat losses due to the inefficiency of the heater. A short outline of the theory follows: The heat supplied to the producing well flows out into the formation by means of thermal conduction. At the same time, the flow of oil carries heat by convection from the formation towards the producing well. After sufficient time has elapsed, a steady-state is reached where the temperature, the velocity of the oil, etc., no longer vary with time but are functions of position only. In the steady state the temperature decays like an inverse power from the high value Tw at the wellbore to the original reservoir temperature T. at some distance away from the well. The effect of the high temperature and low oil viscosity near the producing well is the same as if the oil were produced at reservoir temperature To but through a producing well of a larger radius. From this point of view, the energy and money being expended to provide heat

Jan 1, 1958