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By S. G. Epstein

Electromigration has been measured in dilute liquid alloys of lead in antimony and antimony in lead. In these alloys antimony migrates with the electron current; lead migrates in the opposite direction. These results, which contradict the mass criterion, were predicted by the electron drag model for electromigration in liquid alloys. The existing experimental data are shown to correlate with the difference in electrical resistivities of the alloy components. FOR many years investigators have attempted to relate observed electromigration phenomena in liquid alloys to the physical properties of the alloy components. The most successful correlation was found by Angus et' al.,1 who in 1959 proposed an empirical criterion for predicting the relative direction of motion of the components of a liquid alloy in an electric field: the component with the smallest atomic mass concentrates at the cathode. While this criterion is obeyed in nearly all the alloy systems which had been investigated, the physical basis for such an effect was not understood. It was also disturbing that the mass criterion predicted the wrong sign for the Haeffner effect; observations with pure liquid metals revealed that in every instance the lighter isotope was transported to the anode.2 Klemm3 explained these isotopic separations by suggesting that the lighter isotopes were more mobile and more easily carried to the anode with the electron stream. Additionally, several deviations from the mass criterion have been found in liquid alloys, notably involving transition metals such as chromium, nickel, palladium, and zirconium, which migrate to the anode in liquid bismuth.4'5 Recently, a model has been proposed6 in which electromigration in liquid alloys is attributed primarily to the interaction between the electron stream and the metal ions. In essence, this model predicts that the component with the greater electron-ion scattering cross section will be preferentially transported to the anode, displacing the other component to the cathode. The electrical resistivity of each pure component at its melting point is taken as the measure of its scattering cross section. This model was developed from the results of systematic studies with various solutes in liquid mercury,7'8 bismuth,9 and sodium.10 In every alloy, the component with the greater resistivity has centrates at the anode. Coincidentally, in every instance the component with the greater resistivity has also the greater mass, apparently satisfying the mass criterion. In order to differentiate between electron-ion coupling and atomic mass as the relevant physical prop- erty influencing electromigration, measurements were made with Pb-Sb alloys. Lead has an atomic mass nearly twice that of antimony, but lead has an electrical resistivity of 91 microhm-cm while antimony has a value of 113.5 microhm-cm at their respective melting points. The mass criterion predicts that in an alloy of the two antimony will concentrate at the cathode; the electron drag model predicts that antimony will concentrate at the anode. EXPERIMENTAL To conclusively determine the relative motion of lead and antimony in each other, solute electromigration was measured in dilute liquid alloys of antimony in lead and lead in antimony. Both starting materials were 99.999+ pct pure. The measurements were made with the same capillary-reservoir technique previously used for measuring electromigration in liquid bismuth alloys.11 Several changes in the experimental apparatus were necessary, however, to accommodate liquid antimony, which has a higher melting point than bismuth. The modified apparatus is depicted in Fig. 1. In each experiment four quartz capillaries were filled with the molten alloy. A direct current was passed through two of the capillaries; the electrode in one of these capillaries was made the cathode, and the electrode in the other was made the anode. The remaining two capillaries sampled the alloy in the reser-

Jan 1, 1969

By R. F. Lynch, J. D. Wood

The Al-1.0 pct Mg alloy 565 7 was studied using optical microscopy and electron microprobe X-ray analysis. Constituent particles were found to exist inter-dendritically in the as-cast material in a region of precipitate free a -aluminum. Five phases besides a fine precipitate and a-Al were identified in the cast structure: Fel3, Fe2Al7, Mg2Al3, CUMgAl2, and Cu2FeAl7. Thermal treatments conducted for 100 hr at 1180°, 1130°, 1080°, 1030°, 980°, and 880° F revealed a general dissolution and spheroidization of the in-terdendritic constituent network observed in the cast structure. The principal constituents present in the thermally treated structures were FeAl3 and Fe2Al7 with the relative amount of Fe2A17 to FeAl3 increasing with a decrease in the treatment temperature. The phases Present in the wrought structure were identical to those observed after the thermal treatments, with the constituent particles strung out in the direction of rolling. ALLOY 5657 is a nonheat-treatable commercial purity Al-1.0 pct Mg alloy utilized extensively because of its bright finishing characteristics. This investigation was conducted to determine the constituents present in 5657 alloy, and to study the effect of extended thermal treatments on morphology. Numerous studies have been carried out to establish the equilibrium diagrams for various aluminum systems,1-3 with phase identification based on X-ray analysis, morphology, and the etching response of relatively large particles. Phragmen4 conducted a study of the phases in aluminum eutectic systems and compiled a "corrected" table of etching responses, drawing on his work plus that of Schrader,5 Keller and Wilcox,6 and Mondolfo.7 A review of the original work of Keller and Wilcox, and Mondolfo, which was concerned with the constituents found in commercial alloys, reveals that in numerous cases their etching responses differ from those reported by Phragmen and from each other. These inconsistencies may occur because a specific constituent will react to a given etch in a varying manner depending upon its size, the elements dissolved in the phase, the other constituents surrounding a phase, and the solute content of the matrix. Work with a commercial orientation was conducted on alloys 2024 and 3003 by Sperry8,9 and on alloy 3003 by Barker,10 where the relationship between the phase diagram and the nonequilibrium structure of an alloy was examined. Backerud11 investigated the A1-Fe binary system and found that at high cooling rates the equilibrium eutectic reaction forming a-A1 and FeA13 is replaced by another lower temperature eutectic reaction forming a-A1 and metastable FeAl6, a constituent first identified by Hollingsworth et al.12 Most of the above mentioned studies were conducted on materials having a significantly greater alloy content than 5657 alloy, where the relatively small size and sparse distribution of second phase particles hinders the process of identifying constituents. EXPERIMENTAL PROCEDURE Material with a composition as given in Table I was examined in the as-direct chill cast, hot rolled and cold rolled conditions, and after thermal treatment of the cast structure. Thermal treatments were terminated by a water quench. Microscopic examination was conducted under various lighting conditions following the application of standard etchants as specified in Table 11. A semi-quantitative electron microprobe X-ray analysis was conducted for Al, Mg, Fe, Cu, Si, Zn, and Ti. RESULTS AND DISCUSSION Microstructure of the As-Cast Material. Particles of second phase material were found to exist inter-dendritically, principally in regions of precipitate free a-Al, as illustrated in Fig. 1. Adjacent to the ingot edge was a region of inverse segregation, resulting in an increased amount of second phase material containing large sized particles which aided in phase identification. Phase Identification. Cast Structure. Five phases besides a-Al and a fine precipitate were identified using optical microscopy and electron microprobe X-ray analysis, as presented in Tables II and III, respectively. FeA13 and Fe2A17 are often found with Fe2A17 forming a sheath around the core of FeAl3, resulting from an incomplete peritectoid reaction. These phases have a nearly identical appearance under white light, although they are easily differentiated under crossed polarizers, as characteristically illustrated in Figs. 2(a) and 2(b), respectively. Microprobe analysis con-

Jan 1, 1970

In the Texas Panhandle 277 oil wells and 60 gas wells were completed during 1942, as compared with 647 oil and 52 gas wells completed in 1941. Fourteen dry holes were drilled in the Texas Panhandle in 1942, of which five were wildcats, resulting in four failures and one gas-field discovery in Sherman County; the latter being Hazy-Herrington-Marsh No. I Bivins completed for 5,600,000 cu. it. ol gas from 2989 to 3226 feet. During the year 1942 the Texas Panhandle produced, by counties, the following quantities of oil:

Jan 1, 1943

In the Texas Panhandle 277 oil wells and 60 gas wells were completed during 1942, as compared with 647 oil and 52 gas wells completed in 1941. Fourteen dry holes were drilled in the Texas Panhandle in 1942, of which five were wildcats, resulting in four failures and one gas-field discovery in Sherman County; the latter being Hazy-Herrington-Marsh No. I Bivins completed for 5,600,000 cu. it. ol gas from 2989 to 3226 feet. During the year 1942 the Texas Panhandle produced, by counties, the following quantities of oil:

Jan 1, 1943

By James E. York

THE honor so fairly earned and so incompletely and tardily paid to Henry Cort, the inventor of the puddling-furnace and the, rolling-mill, has been fully set forth by Mr. Charles H. Morgan,1 and needs no further emphasis here. In view of the importance of the rolling-mill in the treatment of iron and steel, the paucity of information concerning it is surprising. With the exception of a hook, written about 35 years ago, by Peter Bitter von Tunner, an Honorary Member of this Institute, and of desultory articles on simple sections, which have appeared in technical journals, I know of no pub¬lication attempting to treat this subject, although volumes have been written on the scientific theory and technical manipulations involved in other branches of the iron- and steel-industry. This strange anomaly may be due to the fact that roll-turning cannot be called a scientific business. It does not ordinarily come within the range of an educated engineer; yet it cannot be performed by an ordinary mechanic. It demands some of the qualifications of an engineer, in designing, and those of a mechanic, in execution. The men who have followed this trade have controlled the training of their successors. In many cases the technical knowledge required bas been handed down from father to son, and there has been a motive of private interest to prevent its public dissemination. Moreover, the statement of the various principles involved in the process would require, besides manual experience, a degree of scientific knowledge which roll-turners do not usually possess; and, finally, any book on the subject, in order to possess real, practical value, would have to be so fully illustrated as to make it very costly to publish. Regarding my own experience, I may say that I served a six-

May 1, 1906

By AIME AIME

To accompanying photograph of the plant of the Beattie Gold Miner Limited, at Duparquet,. Quebec, is taken from the east and shows the open-pit from which the ore is taken during the summer. The buildings on the level ground above the open-pit are the change rooms, steel shop hoist building, compressor building, machine shop, warehouse, carpenter shop, and oil house. The main five-compartment shaft is shown west of the hoist building. The crusher plant adjoins the headframe and a long conveyor transports the fine ore

Jan 1, 1936

By H. Q. Golder

With the development of open-pit mines of ever increasing depth, the stability of the pit slopes in soil and rock is of growing economic importance. How is it, considering the newness of the problem that we know anything at all about the stability of man-made slopes? How much do we know and how did it all begin? We can make a reasonable estimate of the stability of a slope in soil, but we know as yet woefully little about slopes in rock because the problem is much more complex. It is only with the development of the capacity of the computer to handle wearisome calculations that any but the simplest of stability problems in rock have become possible of solution. But what we do know is a guide of immense value in the design of slopes in rock. But remember that the computer is a great elevator; it takes everyone's feet off the ground! So our study began with soils and what is now known as "Soil Mechanics", which is a translation of the German term "Bodenmechanik". It is a pity that the title of Terzaghi's book "Erdbaumechanik" was not used instead. But here the task of the translator is difficult because English lacks the facility of German to string together several words and make a new one whose meaning is unequivocal. Thus, we have the three German words 'Erde' 'Bau' and 'Mechanik'. 'Erde' means "earth" in almost all the English senses including "soil". 'Bau' and 'bauen' convey the meaning of building and construction, and 'Mechanik' means "mechanics" which includes statics and dynamics and the 'mechanics of materials', etc. So that a correct translation of the German is a phrase like "the mechanics of construction with, in or on, earth or soil." However we are stuck with 'Soil Mechanics' and that is where it all began. Now this study or subject did not begin with 'Terzaghi' although his contribution to the subject is unquestionably greater than that of any other single person. Every scientific discipline has its 'classical problem' and that of soil mechanics is 'the earth pressure problem' and it began in the 17th century. In fact, it probably began before this with the introduction of gunpowder to Western Europe in about the 15th century, but the first known reference to the problem was by Vauban, a distinguished French military engineer who lived from 1633 to 1707 and who gave rules for the dimensions of retaining walls from 6 to 80 ft. in height. The soil properties were not mentioned by Vauban probably because the rules were intended to be applied to fortifications only, but Poncelet (1840) claimed that Vauban's rules were based on a theory, and not simply on military and practical

Jan 1, 1972

By H. W. McCue

In 1944, in the Texas Panhandle, 245 oil wells were drilled with a total daily initial production of 32,886 bbl., representing an average initial production of 134 bbl, per well. This was an increase over 1943 of 121 wells drilled, and an increased initial production of 13,861 barrels. On Dec. 31, 1944, the field was operating on an allowable of 113,567 bbl. per day, but actually was producing 85,539 bbl. per day from the 5901 oil wells. The tota1 production for the year was 33,439,436 bbl., bringing the cumulative total to 5.04,537,048 barrels. Gas Sixty-three gas wells with a combined open flow of 992 million cu. ft., were drilled during 1944. This was an increase of seven wells over 1943, but a drop of 216 million cu. ft. in initial open flow. The

Jan 1, 1945

By John Fritz

MEMBERS of the American engineering societies who were in London and Paris during the last days of. June and early July were present at many interesting gatherings. The official delegates of the Founder societies were the specially honored guests of the foreign engineering societies, but other American engineers took part in the meetings. The members of the delegation were: Arthur S. Dwight, Charles F. Rand, William Kelly, representing A. I. M. E.; Ambrose Swasey (general chairman of deputation), Ira N. Hollis, Jesse M. Smith, representing A. S. M. E.; F. B. Jewett, A. E. Kennelly, G. O. Squier, representing A. I. E. E.; Charles T. Main, Robert A. Cummings, John R. Freeman, D. C. Henny, representing A. S. C. E.

Jan 1, 1921

By A. E. Bibb, J. R. Fascia

Single-crystal wafers of zirconium have been exposed to 680°F neutral water. The single crystals were of known orientation and weight-gain data as a function of crystal orientation were obtained. These data show that all the crystal faces studied obeyed a cubic rate law out to the time of transition whereupon the crystals corroded at an approximately linear rate. The time to transition varied from 114 days for (1074) crystals to about 325 days for the (2130) faces. The epitaxial relationship be-tween metal and monoclinic oxide was found to be (0001) H (111) and [1120] 11 [101]. A black tight adherent oxide layer was formed on the crystals in the pretransition range. This black oxide was found to be monocrystalline. The white corrosion product produced after transition was found to be polycrys-talline but highly oriented. X-ray line-broadening studies found that the black oxide was a highly strained structure whereas the white oxide was relatively strain-free. These results indicate a strain-induced re crystallization or fragmentation accompanies the change from protective black oxide to nonprotective white oxide. ZIRCONIUM alloys have been used quite extensively in high-temperature aqueous environments. Alloy additions can be made to commercial sponge zirconium which enhance the corrosion resistance of the zirconium in both water and steam media, which raise the tolerance limit for certain impurities detrimental to corrosion resistance, and which reduce the amount of free hydrogen pickup during corrosion. The development of the corrosion-resistant zirconium alloys has been a long and tedious job involving trial and error methods. This technique has been necessary because of a lack of fundamental data and hence understanding of the corrosion mechanisms. The objective of the work described herein was to provide some fundamental data with respect to the aqueous corrosion of zirconium crystals as a function of the orientation of the exposed surfaces. Hg. The zirconium chunk was then cooled to below the transformation temperature (862°C) and reheated to 1200°C for 8 hr. The ultimate size of the zirconium grains increased with the number of cycles. Rapid or even furnace cooling through the transformation temperature produces a considerable amount of substructure which was intolerable in corrosion experiments as it would be in the study of any crystallographically dependent property. It was found that a high-temperature a-phase anneal for approximately 4 days reduced the substructure below the limits detectable by visual or X-ray means. Crystals so produced were carefully cut from the massive zirconium chunk and oriented by standard back-reflection Laue techniques. The crystals were then mounted in a goniometer head and, by using the three degrees of freedom available, slices on the order of 0.015 to 0.020 in. were cut parallel to any desired crystal plane. These slices were then carefully polished on both sides to produce smooth flat faces, pickled to remove about 0.002 in. per face, annealed for 1/2 hr at '750°C in a vacuum of approximately 10"5 mm Hg, flash pickled, and checked for orientation. The pickling solution was 45-45-10 vol pct HN0,-H20-HF and continuous agitation was provided to eliminate pitting of the slices. Any slice that was not within 2 deg of the desired orientation was discarded, and any evidence of substructure as indicated by the Laue spots was also grounds for discarding the sample. Thin slices were used for the corrosion tests because weight gain per area data could be obtained with only a minimum area exposed to the corrosive media that was not of the desired orientation. The thin single-crystal slices were of irregular shape and as a result the areas were determined by placing a crystal inside an inscribed square of known area, enlarging a picture of this assembly about X5, and tracing both the enlarged square and crystal with a planimeter. The zirconium used to produce these single crystals was crystal-bar grade, a typical analysis of which is given in Table I. An oxygen analysis on prepared crystals gave a concentration of 205 ppm. The hydrogen concentrations are believed to be less than 15 ppm due to the dynamic vacuum anneal given each crystal. Typical nitrogen values for zirconium treated in this manner are about 10 to 20 ppm. RESULTS AND DISCUSSION Single-crystal wafers have been exposed to de-oxygenated, deionized water in static autoclaves.

Jan 1, 1964

By H. W. McCue, Henry Rogatz

Oil.—In the Texas Panhandle, during the year of 1941, 647 oil wells were drilled with a total daily initial production of 133,435 bb1.—that is, 145 more oil wells than in the previous year, with a decrease in total daily production of 5752 bbl. On Dec. 31, 1941, a daily allowable of 116,766 bbl., which was an increase of 27 per cent over 1940, was assigned to the field to be produced from 5182 wells. The total amount of oil produced for the year was 27,904,846 bbl., making a cumulative total of 404,657,324 bbl. during the past 20 years. Gas.—During the year, 52 gas wells were drilled, having a combined open flow of 2.62 billion cu. ft. per day—that is, 40 less than the number of wells drilled in 1940, with an increase in the open flow of 217,100,000 cu. ft. per day. The gas

Jan 1, 1942

By Henry Rogatz, H. W. McCue

Oil.—In the Texas Panhandle, during the year of 1941, 647 oil wells were drilled with a total daily initial production of 133,435 bb1.—that is, 145 more oil wells than in the previous year, with a decrease in total daily production of 5752 bbl. On Dec. 31, 1941, a daily allowable of 116,766 bbl., which was an increase of 27 per cent over 1940, was assigned to the field to be produced from 5182 wells. The total amount of oil produced for the year was 27,904,846 bbl., making a cumulative total of 404,657,324 bbl. during the past 20 years. Gas.—During the year, 52 gas wells were drilled, having a combined open flow of 2.62 billion cu. ft. per day—that is, 40 less than the number of wells drilled in 1940, with an increase in the open flow of 217,100,000 cu. ft. per day. The gas

Jan 1, 1942

By Rex O. McLellan

The formation of a monovacancy in a metal is simulated in an elastic model by the displacement of the surface of a small spherical cavity in a large elastic continuum. The application of linear elasticity to this distortion results in a well- known formula for the energy and an expression for the concomitant entropy change due both to the shear strain in the continuum and also to the dilation of the solid resulting from the boundary conditions at the surface of the solid. Elastic data (the sliear modulus and its temperature coelficient) are used to calculate the entropy and energy of formation for many metals. Despite the simplicity of the assumptions involved, the agreement between the calculated entropies and energies and experimental values is remarkably good. In recent years there has been a large increase in measurements of the absolute concentration of mono-vacancies in metals as a function of temperature. Hence new data for both the energy and the noncon-figurational entropy of formation of monovacancies has become available. Recent measurements&apos; of the anomalous (non-Arrhenius) self-diffusion in many bcc metals has also focused interest on the prediction of the thermodynamic parameters of mono- and multi-vacancies in those metals for which no data are available. Damask and Dienes&apos; have discussed the various theoretical calculations of the energy of formation EL, of a monovacancy. These include simple models involving the breaking of atomic bonds on moving atoms from the interior of a crystal to the surface, models combining elastic calculations with surface-energy terms and detailed quantum mechanical calculations. The simler models give the correct order of magnitude of &, but tend to overestimate it by a factor of about two. The quantum mechanical calculations4"7 have been carried out for the noble and alkali metals with generally reasonably good agreement with the available Ef data. The calculation of entropy of formation Sfv14 lnvolves a fundamental calculation of the perturbation of the phonon spectrum caused by the creation of a vacancy. Huntington, Shirn. and wajda8 have given an approximate evaluation of sJV by considering an Einstein model for the localized vibrations in the immediate neighborhood of the defect and then using elastic theory to calculate the entropy associated with the shear stress field in the distorted crystal (as originally proposed by Zenerg). They also included a term due to the dilation of the crystal. They obtained a value of 1.47k for copper, in good agreement with the experimental value (1.50k). However, Nardelli and Tetta- manzi1° have recently shown that neglecting the coupling between atoms (Einstein Model) may lead to a serious error so the agreement may be somewhat fortuitous. In this work simple linear elastic theory is used to calculate the entropy and energy of formation of mono-vacancies. Despite the simplicity of some of the assumptions involved, the agreement with the available experimental data is remarkable. However. the reasonable degree of success in the application of linear elastic calculations to the excess entropy of a solute atom in a dilute solid solution1&apos; indicates that the application of elastic theory to vacancies. where the interaction of different atomic species is not involved, may not be inappropriate. THE ELASTIC MODEL The metal is assumed to be a spherical elastic continuum. A small spherical cavity of volume V = 4i;v:&apos;/3 is cut from the center. removed. and dissolved rever-sibly in the bulk of the material. TO a good approximation no net atomic bonds are broken and the material does not undergo a volume change although the externally measured volume of the body would increase by V. The radius of the sphere of metal is much larger than r Next a negative pressure is applied to the cavity causing its surface to be displaced inward by an amount simulating the relaxation of the lattice around a monovacancy. In this model the energy and entropy accompanying the distortion are taken as 4, and <. As a first approximation the equation of state for the solid is taken as: r = ro(i + *~D LiJ where K is the bulk modulus. P the hydrostatic pressure. Vo the volume of the material at 0°K and zero pressure. and d+/dT = 30. where 0 is the linear thermal expansion coefficient. The variation of entropy with hydrostatic pressure is given by the Maxwell equation: These equations give the entropy change resulting from increasing the hydrostatic pressure from 0 to P as: and since • we have: This is the entropy arising from the dilation resulting

Jan 1, 1970

By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

By W. Spencer Reid

ALTHOUGH there have been some developments during the last five years which have had far- reaching and important bearing on lead smelting, it cannot be said that any basic principles of pyrometal-lurgy have been discovered. Eighteen or twenty years ago the Dwight & Lloyd sintering machine was intro-duced and literally turned the roasting end of lead smelting upside down. There has been nothing com-parable to the advent of the sintering machine during recent years. Actual blast-furnace practice today is slightly, if any, better than it was five years ago ; although immeas-urably better than it was twenty to thirty years ago. Some tell us that as far as cleanness of slags is con-cerned, it is no better today than in the days of the old Romans. The metallurgist of a generation ago did very good work, considering the equipment he had available. It is true he was working with the cream of the ores, the clean oxides and carbonates and the low-zinc sul-fides. He was troubled very little with high zinc and selected his type of slag according to preference of -some authority such as Eilers, Iles, Raht, Hahn, etc. As these free-smelting ores were depleted the complex ores were encountered, and the metallurgist gradually discovered that he had to forget the old type slags and run a slag according to the percentage of zinc on the charge. I believe it is now universally agreed that SiO2 and CaO must be lowered and FeO raised in a slag as the ZnO increases. The ratio of these variations is practically uniform and can be relied upon over wide fluctuations of the determining element, zinc. These "bastard" slags, as they are sometimes inappropriately designated, are actually in daily use, and the metallurgist of today has been forced to adopt certain standards, as a guide to successful operation. These slags practically refute the old Eilers&apos; theory that all good slags are chemical combinations of SiO2 with FeO and MnO, and CaO and MgO. Eilers&apos; and the other type-slag theories were based upon the assumption that a good slag must con-form to a definite formula, such as 3 (FeO)2 SiO2 + 2 (CaO)2 SiO2 or 2 (FeO)2 SiO2 + 2 (CaO)2 SiO2 which respectively figure 31.3 and 36 per cent SiO2. The SiO2 was supposed to remain constant even with the entrance of impurities such as Zn and A1,0? into the slag. The increasing amount of impurities, espe-cially Zn, soon discredited the theory, for in actual practice the slag failed to run freely.

Jan 1, 1927

By R. G. Garlick, H. B. Probst

Tungsten single-crystal specimens of various orientations were deformed in tension at room temperature. Slip traces indicated both (112)(111) and (110) (111) slip; however, about 10 pct plastic dejormation was required bejore these traces could he seen. Resolzled shear-stress considerations indicated that at least some of the particular systems observed were not those on which slip initiated hut were secondary systems. This is highly probable, considering the high plastic strains involved. Analysis of the stress data with respect to possible slip systems indicated that slip must have been initiated at stresses below the proportional-limit stresses measured. ALTHOUGH there is general agreement that slip deformation in fcc and hep metals takes place on the plane of close packing and in the direction of close packing, there is no such agreement for slip in bcc metals. It is generally agreed that the close-packed direction (111) is the slip direction, but investigations have led to conflicting descriptions of the slip plane. As Hoke and Maddin1 point out, there are essentially four points of view. 1) Deformation in bcc metals is composite shear on (112) and (110) planes or on nonparallel (110) planes, and any apparent slip on other planes can be accounted for completely by slip on these planes. Chen and Maddin have reported this to be the possible case for molybdenum." 2) Slip occurs in the (111) direction and is limited to {110), {112), and (123) planes (the three closest packed planes of the lattice). 3) Slip occurs in a (111) direction, but not necessarily on planes of close packing (banal slip). 4) Slip occurs in those directions and on those planes for which ß, the ratio of Burgers vector to interplanar spacing, is a minimum. The slip systems of the bcc metal tungsten have never been fully determined, although several investigators have reported pertinent results.3"7 The present work was initiated to determine the active slip systems in tungsten at room temperature, the critical resolved shear stresses associ- ated with these systems, and the orientation dependency of operative systems. These features of tungsten deformation at room temperature have never been reported in the literature. The authors find this somewhat surprising, particularly in view of the availability of tungsten single crystals since the advent of electron-beam zone-melting techniques and the widespread interest in refractory metals. It would seem apparent that such work has been attempted but the results have not been reported, possibly due to the conflict with deformation theory. The results of the present work conflict with any straightforward description of deformation based on the proposed explanations of slip in bcc metals. Although these conflicts have not been resolved, a presentation of the problem seems in order and should be of value to others working in this field. MATERIALS AND PROCEDURE Single-crystal tungsten rods of 1/8-in. diameter were grown from undoped commercial rod by one-pass electron-beam zone melting in apparatus previously described by witzke.8 Representative analyses of the rod before and after melting are given in Table I. There was no detectable zoning of impurities during melting. Buttonhead tensile specimens, as shown in Fig. 1, were machined from single crystals. Two flats 90 deg apart were ground in the gage length of each specimen. These flat surfaces facilitated the analysis of slip traces. No attempt was made to position these flats with respect to the crystal orientation. The worked surface layer of the machined specimens was removed by electrolytic polishing in a NaOH solution. Tensile-axis orientations were determined by standard Laue back-reflection techniques. The sharpness of the Laue spots indicated that the crystals were free of strain.

Jan 1, 1964

A New Microscopy and Its Pntentialities. By Charles S. Barrett. (Metals Technology, .April 1945) Physical Metallurgy Fundamental Principles Involved in Segregation in Alloy Castings. By R. M. Brick. (Metals Technology, Sept. 1944) A Stud) of Age-hardening Using the Electron Microscope and Formvar Replicas. By D. Harker and MI J. MurphyI (Metals Technology, June 1945) Standards for Identifying Complex Twin Relationships in Cubic Crystals. By C. G. Dunn. (Metals Technology, April 1945) Orientation Changes during Recrystallization in Silicon Ferrite. By C. G. Dunn (Metals Technology, April 1945) The Orientation Texture at the Surfacr of Cast RIetals. By Gerald Edmunds. (Metals Technology, Jan. 1945) (With discussion) Internal Friction of Single Crystals of Brass, Copper and Aluminum. By George H. Found. (Metals Technology, June 1945) (With discussion) Recrystallization of Aluminum in Terms of the Rate of Nucleation and the Kate of Growth. By W. A. Anderson and R. F. Mehl (Metals Technology, Feb. 1945) (With discussion) Copper and Copper-rich Alloys Textures, Anisotropy and Earing Behavior of Brass. By F. H. Wilson and R. ill. Brick. (Metals Technology, June 1945) (With discussion) Phantom Laminations in Brass. By Daniel R. Hull, H. F. Silliman and John R. Freeman, Jr. (Metals Technology, Jan. 19451 (With discussion) Corrosion of Yellow Brass Pipes in Domestic Hot-water Systems—a Metallographic Study. By E. P. Polushkin and Henry L. Shuldener. (Metals Technology, Oct. 1944) (With discussion) The .Alpha Solid Solution Field of the Copper-manganese-zinc system. By R. S. Dean, J. R. Long, T. R. Graham and .%. H. Robersori. (Metals Technology, June 1945) A White High-manganese Brass. Ry K. S. Dean, J. R. Long, T. R. Graham and C. W. Matthews. (Melds Technology, June 1945) Magnesium Alloys Oxidation Inhibitors in Core-sand Mixtures for Magnesium Castings. By O. Jay Myers. (Metals Technology, Feb. 1945) (With discussion) Grain Size and Properties of Sand-cast Magnesium Alloys. By R. S. Dusk and C. R. Phillips. (Metals Technology, Feb. 1945) (With discussion) Rater Quenching of &apos;Some Typical Magnesium Casting Alloys. By R. S. Busk and R. E. Anderson (With discussion)

Jan 1, 1945

By S. W. Parr

FRom a study of sulfur with reference to its specific combination in coal, published as University of Illinois Bulletin No. 111, 1919, it is now possible to determine the various forms of this constituent with a good degree of accuracy. This fact suggests two questions: (1) Are the same analytic methods applicable to coke? (2) Is there any correlation between the forms of sulfur as it occurs in coal and the residual sulfur found in the finished coke? The answer to the second question might be helpful in answering a still further question as to what chemical route the sulfur travels during the carbonization process. While the special studies along these several lines are by no means complete, a few preliminary statements are herewith presented. They may, at least, prove suggestive of further possibilities from a continuation of research along these lines. There is no reason, chemically, why the analytic methods devised for coal should not apply to coke and a fair amount of experience in connection with such use affords confirmation of this statement. The procedure in the case of coal may be briefly outlined as follows: Combinations of sulfur as sulfate, or sulfides other than FeS2, are readily dissolved without disturbing either the pyrite sulfur or the sulfur that is in organic combination by means of dilute hydrochloric acid— 1 part of concentrated HC1 to 10 parts of water or approximately 3 per cent. acid. Digestion at 60" C. for 24 hr. insures the complete removal of the sulfur thus combined. In freshly mined coal the amount of such sulfur is very small; weathering processes, however, may very materially increase the amount of sulfate present. Sulfur in the form of iron pyrites, or marcasite, may be quantitatively removed without oxidation of the organic sulfur as follows: A dilute solution of nitric: acid is prepared having 1 part of concentrated HNO3 to 3 parts of water or with an approximate specific gravity of 1.12. The coal sample, ground to 100 mesh, is digested with this solution at room temperature for 3 or 4 days, filtered and evaporated to dryness, taken up with water, and acidified with hydrochloric acid. It is now ready for precipitation with barium chloride in the usual manner. If sulfate is present in the original sample to an appreciable amount, it should be removed by the procedure outlined above. It is not necessary here to give the methods for determining the two

Jan 1, 1920

AS I told you in the chapter on salts, saltpeter is a mixture composed of many substances extracted with fire- and water from arid and manurial soils, from that growth which exudes from new walls or from that loosened soil that is found in tombs or uninhabited caves where the rain cannot enter. It is my belief that it is engendered in these soils from an airy moisture that is drunk in and absorbed by the earthy dryness. Considering its effects, I do not know how to decide and say exactly what the nature of saltpeter is. The learned and very wise physicians find it salty and with a subtle sharpness both in taste and in their medical experiments. Considering its strong biting qualities, they decide to say that it is of a hot and dry nature; on the other hand when they see that it is engendered from the air and that when touched by fire it becomes inflammable and vaporous, and rises with a fearful impetus when mixed in powder for military guns, it manifestly shows itself to be of a hot and moist airy nature. And then when they see that it is shining and transparent with whiteness and is fusible in every fire in a manner corresponding to a thing of a watery nature, and since it. is heavy, it seems that it can be said to be watery in nature. To this is added the experience of touch and of the great cooling action which it has on water in summertime when wine is to be cooled, and since it crushes and breaks with but little pressure, it might be thought to be earthy in nature; especially when it is seen to change into a hard, white stone when burned with an equal amount of sulphur. Thus it seems that every one of the elemental qualities is predominant in it. Now the ancients called this, or a similar thing, nitrum. [150] Pliny, in Book XXXI of his Natural History, has said that it was a thing not much different from salt, that doctors do not seem to have yet known its nature, that it is found in various places, and that the best is found in Macedonia. But among the moderns and especially in our regions, it is not known today what it is that Pliny and other writers refer -to, since according to the aforesaid Pliny and other ancient writers it is a natural mineral. Some say that in place of, the natural kind the artificial will serve for the same medicinal purposes, since it has the same nature and is perhaps more powerful.

Jan 1, 1942

By T. S. Plaskett

A striated structure perpendicular to the growth axis was observed by the copper-decoration tech-nique in dislocation-free, .float-zoned silicon crystals. The striations, which were spaced about 100 p apart, fitted the relationship d = f/u , where d is the spacing, f is the growth rate, and u is the crystal rotation rate. Each stria was resolved into an UNDOPED silicon crystals pulled from quartz crucibles by the Czochralski technique usually exhibit a striated structure perpendicular to the growth axis.&apos;-&apos; This structure has been attributed to oxygen segregation, with the oxygen being introduced from the quartz crucible. If the crucible is rotated, the level of oxygen contamination has been reported as high as 10° atoms per cu cm.10 These striations are similar to solute striations commonly observed in doped Czochralski-grown crystals. The periodic nature of the striations is caused by a periodic variation in the growth rate",12 which is attributed mainly to thermal gradients in the melt.13 A finer striated structure14 attributed to constitutional supercooling is sometimes observed between the coarse striae. The oxygen striations have been observed by infrared transmission techniques,&apos; by the copper-decoration technique,&apos; by X-ray diffraction microscopy,6-8 and by 9 p absorption measurements3 on crystals pulled from the melt both with and without dislocations. In this investigation float-zoned dislocation-free crystals were examined by the copper-decoration technique. The level of oxygen for float-zone material is less than 1016 atoms per cu cm the lower limit of detection by 9 p absorption measurement. EXPERIMENTAL TECHNIQUE The crystals were grown by the float-zone process with the rf heating coil outside of the quartz envelope containing the silicon. All float zoning was done under an atmosphere of purified helium. The Dash technique15 was used to grow the crystal dislocation-free. This involves growing the crystal initially with a diameter between 2 and 3 mm and at array of starlike precipitates of copper. The strucLure was not .found at the surface tor a depth of about 1.5 mm, or in a region of similar width ahead of a dislocation network. The structure is postulated to consist of vacancy clusterings or dislocation loops. very rapid rates, about 20 mm per min, for a distance of about 3 cm. The diameter of the crystal is then increased to the diameter of the source of silicon, which in this case was about 19 mm. Because of the arrangement of the apparatus, the zone was passed downward rather than upward, contrary to the standard float-zoning practice. Also, the source was rotated rather than the seed. ziegler17 has made dislocation-free crystals by a similar technique but has passed the zone upwards. The starting material was zone-refined and had a p-type resistivity of 150 ohm-cm. The major impurity was boron; the total impurity excluding the boron was reported by the supplier (Dow-Corning) to be typically less than 2 x 1013 atoms per cu cm. The crystals were examined by the Dash copper-decoration technique18&apos;19—a method in which about 10" atoms per cu cm of copper are diffused at a temperature between 900" and 1000°C into silicon which is then quenched to room temperature. On quenching, the copper precipitates on crystalline defects which are then visible when viewed by transmission infrared microscopy. The photomicrographs shown were taken either of the infrared image tube screen or directly on infrared film. All sections prior to decorating were chemically polished and, for some sections, given a sirtlZ0 dislocation etch-pit examination. After decorating, the samples were mechanically polished. RESULTS A photomicrograph, taken in transmission of a decorated cross section, is shown in Fig. 1. The portion of the section shown is near the surface of the crystal. The entire cross section showed no dislocation etch pits after being given a Sirtl etch treatment. It is seen that the copper precipitated randomly. Each precipitate, as has been reported by others, was found to have a starlike structure.

Jan 1, 1965