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By D. J. Hawthorn

The widespread interest shown during the past year in the study of subsurface pressures warrants brief reference to its early development. Though it is impossible to set an exact date when constructive thinking on the subject first began, nevertheless, evidence is available that thought was given to the problem as far back as 16 or 1.7 years ago. There is record in one of the foreign journals of actual subsurface tests made by crude methods in one of the Rumanian fields in 1918 and 1919.' These tests were performed in conjunction with studies made on wells produced by bailing and, incidentally, the final outcome of the work led to the development of the so-called "duplex bailer" which is reputed to have trebled volumetric bailing efficiency. From this time on to 1927 a few scattered bottom-hole pressure determinations were made with makeshift instruments of one form or another, but probably not until 1927 was any great amount of concerted effort directed to the subject. At this fall meeting of the Petroleum Division four years ago was presented one of the first papers2 to appear in this country written for the express intent of advocating the value and importance of subsurface pressure determinations. It is thought to have been the first to present direct data on subsurface pressures obtained through the use of a specially designed recording instrument. As might be expected, the instrument had its limitations, but reasonably accurate results were obtained and, to say the least, it constituted a progressive step in the right direction. During the period from 1927 to 1931, many noteworthy improvements were made in the design and perfection of subsurface pressure instruments suitable to meet all conditions. Because of the magnitude of this task much credit is due the men who pioneered this work. They should feel a keen sense of satisfaction in the thought that their efforts have paved the way for the continuation of this most valuable study. At the present time more than a dozen companies are operating subsurface pressure instruments in the Mid-Continent field. Engineers in

Jan 1, 1933

By Ralph Hultgren, Louis A. Carapella

When F. Heuslerl found in 1898 that certain alloys containing only copper, manganese, and tin were ferromagnetic, the discovery excited a great deal of interest and led to numerous investigations. It was early found that tin could be replaced by aluminum, arsenic, antimony, bismuth, or boron without destroying the ferromagnetic nature of the alloys.2 Copper may also be replaced by silver.% All these alloys have come to be known as "Heusler alloys." The aluminum alloys apparently were the most magnetic and have been most extensively investigated. However, no agreement has yet been reached as to the source of the ferromagnetism arising from these nonferromagnetic elements. Absence of reliable quantitative data makes speculation hazardous. The value of much of the earlier work was vitiated by lack of necessary precautions against contamination, and by lack of close control of heat-treatment. It was only recently established that in aluminum Heusler alloys4 the ferromagnetism arose from a single phase, an ordered body-centered-cubic structure. With modern methods of preparation, heat-treatment, and X-ray examination, it is possible to prepare these alloys without contamination, to heat-treat them intellgently, and to determine what phase or phases are present in the finished sample. In the present investigation, a series of pure alloys in the comparatively neglected copper-manganese-tin system have been prepared, which consist of a single, body-centered-cubic structure (the beta phase) and whose compositions vary within wide limits. The magnetic saturation values of these single-phase alloys have been quantitatively determined, so that considerable data on the effect of composition on the ferromagnetism have been made available. In the course of the investigation some information on the extent of the stability of the beta phase and the nature of phases in adjacent regions of the ternary diagram has been accumulated. Anomalies in earlier data. have been explained, and alloys have been prepared that are much more strongly magnetic than any previous Heusler alloys. Previous Work In the original work of F. Heuslerl and coworkers,2 a maximum magnetic saturation value of I = 107 was found at the composition Cu6Mn3Sn, while a value for CusMnAl of I = 443 was early measured. Ross and Gray5 found a second maximum at the composition Cu2MnSn, which was much more magnetic than Heusler's original alloy. F. Heusler6 hen reinvesti-gated the system, confirmed their results,

Jan 1, 1942

By Louis A. Carapella, Ralph Hultgren

When F. Heuslerl found in 1898 that certain alloys containing only copper, manganese, and tin were ferromagnetic, the discovery excited a great deal of interest and led to numerous investigations. It was early found that tin could be replaced by aluminum, arsenic, antimony, bismuth, or boron without destroying the ferromagnetic nature of the alloys.2 Copper may also be replaced by silver.% All these alloys have come to be known as "Heusler alloys." The aluminum alloys apparently were the most magnetic and have been most extensively investigated. However, no agreement has yet been reached as to the source of the ferromagnetism arising from these nonferromagnetic elements. Absence of reliable quantitative data makes speculation hazardous. The value of much of the earlier work was vitiated by lack of necessary precautions against contamination, and by lack of close control of heat-treatment. It was only recently established that in aluminum Heusler alloys4 the ferromagnetism arose from a single phase, an ordered body-centered-cubic structure. With modern methods of preparation, heat-treatment, and X-ray examination, it is possible to prepare these alloys without contamination, to heat-treat them intellgently, and to determine what phase or phases are present in the finished sample. In the present investigation, a series of pure alloys in the comparatively neglected copper-manganese-tin system have been prepared, which consist of a single, body-centered-cubic structure (the beta phase) and whose compositions vary within wide limits. The magnetic saturation values of these single-phase alloys have been quantitatively determined, so that considerable data on the effect of composition on the ferromagnetism have been made available. In the course of the investigation some information on the extent of the stability of the beta phase and the nature of phases in adjacent regions of the ternary diagram has been accumulated. Anomalies in earlier data. have been explained, and alloys have been prepared that are much more strongly magnetic than any previous Heusler alloys. Previous Work In the original work of F. Heuslerl and coworkers,2 a maximum magnetic saturation value of I = 107 was found at the composition Cu6Mn3Sn, while a value for CusMnAl of I = 443 was early measured. Ross and Gray5 found a second maximum at the composition Cu2MnSn, which was much more magnetic than Heusler's original alloy. F. Heusler6 hen reinvesti-gated the system, confirmed their results,

Jan 1, 1942

By R. E. Reed-Hill, W. H. Hartt

High-purity magnesium single crystals, oriented with basal plane parallel to stress axis, were deformed in tension at room temperature so as to form second-order (1011)- (1012) twins. Investigation by optical and replica electron microscopy revealed that these twins can support very large internal strains approaching 1000 pct and that fracture follows as a direct consequence of these strains. At low strains the basal plane within (10i1)- (10i2) twins rotates with increasing deformation until it becomes approximately parallel to the twin boundaries. This rotation is not consistent with deformation by basal slip in the double twin, but may be rationalized in terms of nonbasal slip. Observations also indicate that basal slip in the primary (1011) twin, prior to second-order twinning, may contribute to this rotation. Deformation markings that are difficult to interpret in terms of slip on previously observed systems were noted in the twin bands. A possible means of rationalizing these markings is to relate them to grain boundary shear. The fracture associated with these twins is thought to initiate by formation of voids at the twin boundaries. These grow into microcracks, with ultimate fracture occurring by tearing of the interconnecting regions. THE significance of deformation and fracture along second-order (10i1)-(10i2) twins in polycrystalline magnesium1-' and many magnesium alloys4 was discussed in a previous paper.5 It was noted that this double twinning mode effectively controls the room-temperature deformation and fracture of magnesium single crystals, oriented with the basal plane parallel to the tensile axis. Reed-Hill and Robertson6 observed that, although these crystals may fracture at a macroscopic strain of less than 1 pct, shear strains up to 1000 pct could occur within (1011)- (10i2) twin bands. They concluded that the fracture was "ductile" and resulted from concentrating the deformation into a very small volume. The present research was undertaken to obtain a better understanding of the deformation and fracture associated with these twins. EXPERIMENTAL TECHNIQUES The experimental procedure involved straining high-purity magnesium single crystals in tension at room temperature. Specimens were oriented so that the applied stress direction was within 2 deg of the [1010] crystal axis. The specimen cross section was rectangular with faces closely parallel to (1210) and (0002). The specimen preparation and testing procedures have been described in detail elsewhere.5 Second-order (1011)- (1072) twins nucleated during straining were studied using optical and replica electron microscopy techniques. For the latter, cellulose acetate-carbon double replicas were employed. Observations were made on the (1210) crystal surface, which is the plane of shear for twins of this type. In addition to the single crystals, some investigations were carried out on longitudinal polycrystalline specimens. These were obtained from high-purity magnesium plate with a texture in which the basal planes of the grains tended to be nearly parallel to the specimen axis. All. polycrystalline specimens were annealed prior to testing in order to produce a coarse grain structure, permitting Laue back-reflection X-ray photographs to be obtained from grains of interest. EXPERIMENTAL RESULTS a) Deformation Within ( 101 l )-( 1072) Twins. Fig. 1 is an optical micrograph demonstrating the extent of the plastic deformation that can occur in (1011)-(10i2) twin bands. Notice at the lower left corner of the photograph the large displacement of the dark band (a polishing step) where it crosses the twins. The shear strain in the twin band at this position was computed to be 700 pct, using the ratio of step width to twin thickness. It was previously shown5 that (1011)- (1012) twin bands are often composed of small, separate twins aligned close to the macroscopic habit plane. Fig. 2 is an electron micrograph from near the upper end of the twin band in Fig. 1. This illustrates that the twin habit often does not coincide exactly with the macroscopic band habit, but may be inclined at a slightly smaller angle to the matrix basal plane. Figs. 3 through 6 are electron micrographs of the twin band in Fig. 2 illustrating successive steps in the development of deformation inside the band. A twin band such

Jan 1, 1969

By Henry S. Mackay

The interesting paper recently submitted by Messrs. Tobelmann and Potter1 shows that chemical problems have developed which are of great interest in this new and important branch of metallurgy. Those who realize what a process of this kind really involves will agree that it deserves a better name than '(leaching process." The word leaching conveys the idea that the copper is simply leached out of the ore with acid and then precipitated on iron; the chemistry of such a process would be of little interest. As, however, during the first year's operation of this plant 24,400,532 lb. (11,067,837 kg.) or about two-thirds of the produce, was electrolytic copper, while 7,992,033 lb., or about one-third, was cement copper, it would seem more appropriate to term the process electrochemical. It further appears, from the particulars given, that efforts have been made to have the entire production in the form of electrolytic copper. This could be done if the chemistry of the problem were kept in balance, so that it would not be necessary to discard any solutions that carried copper and acid of commercial value. A process, such as that under consideration, in which the copper is precipitated from solution by electrolysis, the solvent being at the same time regenerated, is one that requires special chemical and electrochemical knowledge and experience if all the copper in solution that has been extracted from the ore is to be successfully and economically produced as electrolytic copper. The object of this paper is to discuss, from the practical and theoretical standpoints, the chemical and electrochemical problems involved in the working of a process of this kind, and which must be solved to keep it in chemical and electrochemical equilibrium. In such a process, if the chemical balance is maintained, a solution can be used alternately as a solvent for the copper in the ore and as an electrolyte of high efficiency for the precipitation of the copper. To maintain the chemical equilibrium and so attain this result, the process must be so controlled that the solu-

Jan 1, 1921

By Ellis Clark

The greater portion of the brown ore in the vicinity of Easton, along the north slope of the Lehigh Mountain or Durham range of hills, is obtained from mines instead of from open cuts or quarries, as is the case in the ore-beds in the western part of Northampton County, in Lehigh County, and in Berks County. The reasons for this method of procedure are various, and the principal causes of the shaft and regular mine system of working being adopted instead of the open air cuts, are: First, the large amount of stripping that would be necessary, as the richer and more valuable portions of the ore do not appear to be found as near the surface as those in other portions of the Kittatinny valley; second, the occurrence of the ore in regular beds, interstratified with the clay, and, to a less extent, in pockets or erratic deposits, as is the case in the mines of Lehigh County; and third, on account of many of the mines being situated at the immediate base of the Lehigh Mountain, where the surface water would be in such large quantities as to be with difficulty handled, and where the subsequent caving in of the sides of the open cut would be almost certain to expose the gneiss rock, which is water-bearing, the large quantities of water coming from which would probably drown out the ore-bed. Shafts, and a regular system of gangways and mining are therefore required by the configuration of the surface, the depth of the deposits and their geological structure. The ordinary size of the shafts is about four feet square, but where an extensive plant of pumping machinery is required the size may be increased to eight feet by six, with two compartments for the hoisting and pump-shaft respectively. A man-way, consisting of ladders with rests at intervals of twenty or thirty feet, is comprised in the pump-shaft, the wire rope being used for purposes of ascent and descent only in exceptional cases, on account of accidents which

Jan 1, 1879

By Walter B. M. Davidson

Phosphorus is one of the elements having the widest distribu tion, and phosphoric acid plays an important part in the composition of the crust of the earth. It is allied in various chemical combina- tions with many bases, of which lime, alumina and iron are the most common. It is difficult to state in what chemical combination phosphoric acid predominates in the crust of the earth, for while phosphate of lime, as the mineral which is sought for and found in deposits of economic value is the most familiar, it is probable that the phosphates of alumina and iron are the most usual forms in which phosphoric acid exists in all soils not essentially calcareous. It has been shown by thousands of analyses that all fertile soils contain from a trace to 0.5 per cent. of phosphoric acid. All limestones, dolomites and chalks contain it in proportions which, though usually small, are large enough to make careful analysis necessary in the selection of limestone as flux for iron-smelting. It is generally Trenton limestones that are found best for this purpose, the more recent strata being more phosphatic. In some places phosphoric acid replaces carbonic acid, and the limestone or chalk becomes phos phatic to a large degree, or sometimes pure phosphate of lime. The waters of the ocean, from very early periods, have contained phosphoric acid. Different analyses show varying contents; it is asserted that some portions of the Gulf Stream are more phos phatic than the surrounding waters of the Atlantic. Many springs, usually from limestone regions, contain soluble phosphates in vary ing quantities. I think it safe to assert that phosphorus is nearly the most widely and evenly distributed element on the surface of the earth, and probably the most subdivided. This can be readily understood when the important part which phosphoric acid plays and has played in the vital cosmos is taken into consideration. Phosphorus was on the earth in gaseous, liquid or solid form before the dawn of life, and since then all animal and vegetable creation have combined with the

Jan 1, 1893

By W. B. Triplett, H. I. Aaronson, G. M. Andes

THE morphology and mechanism of the proeutectoid a and the eutectoid reactions have been recently investigated in some detail in an iodide-base Ti—7.22 pct Cr alloy.' These studies have now been extended to an iodide-base Ti—10.8 pct Cr alloy in order to evaluate the effects of composition on the proeutectoid and eutectoid transformations in titanium-chromium alloys. The alloy used in this investigation had the following composition: 10.8 Cr, 0.0327 0, 0.011 N, 0.0063 H, and 0.011 pct C. Specimens of this alloy were heat treated in evacuated and internally get-tered Vycor capsules. The specimens were solu-

Jan 1, 1959

By R. E. Hurst, D. E. Ramsey, J. M. Moore

The "frac" method of well stimulation has been applied successfully to all producing formations in the Permian Basin area. During the five years since its development, many changes and improvements have been made in treating materials. procedures, and equipie11t. A number of fluid carrying agents, having different physica1 and chemical properties, have been developed to meet variorus well requirements. The current trend is toward larger gallonage treatments, employing higher injection rates. The use of "down-the-casing" techniques has greatly reduced high surface working pressures, attributable to friction losses resulting from injection throrugh tubing. Petrographic studies of various Permian Basin formations, coordinated with laboratory and well log data, have been found a valuable guide in planning frac treat111o1t.s. A knowledge of the extent (and orientation of naturally occurring fractures and planes of weakness in the formation, aid in predicting the ultimate drainage pattern resulting from the frac treatment. INTRODUCTION The South Permian Basin covers an area in Wcst Texas and New Mexico about onc-half the size of the state of Texas, This vast region has been called the "Permian Basin" for so long that the term will he used here. It includes an area south of the Matador Arch. approximately 250 miles wide and 300 miles long. Structural features of importance within the basin are the Northwest Shelf, Eastern Platform, Midland Basin, Central Basin Platform, and Delaware Basin. The principal producing formations include sand, limestone and dolo-mite, with lesser amounts of shale, anhydrite. chert. and various silicates. All of the producing formations in the Permian Basin have responded to some type of frac treatment. Essentially, a frac treatment may be defined as the injection, into a formation. of a fluid carrying agent containing a particulated solid (usually sand), for the purpose of increasing production. The application of this method of well stimulation to many differing Permian Basin reservoirs has necessitated numerous changes and improvements in carrying agents, solids, service equipment. well equipment. and treating techniques. CARRYING AGENTS A number of different types of fluid carrying agents have been developed since the introduction of the frac method of well stimulation. These agents have different physical and chemical properties, and in many cases the extent of production increase derived from the frac treatment depends on the choice of fluid carrier. Unfortunately, due to many different systems of nomenclature used in the oil field, these differences are not always recognized by the oil Operator. In general, carving agents may he divided into the following broad classi-

Jan 1, 1956

By P. A. Larssen, P. R. Gage, R. W. Bartlett

The kinetics of formation of intermediate sili-cide compounds from MoSi2/Mo and WSi2/W couples were studied using a cylindrical sample configuration. Concentration profiles of the constituent metals were deter mined from electron-microprobe analysis of cross-sectioned samples after isotlzernzal diffusion annealing. These data also yielded hand widths of phases. Growth of intermediate phases depends on diffusionin them and obeys a parabolic rate law. The rates of formation of the intermediate phases decrease in the order Mo5Si3 > W5Si3 > Mo3Si. Crowth rates. for the isomorphous phases Mo5Si3 and W5Si3 had the same activation energy. 43 kcal per mole. SILICIDE coatings employed to protect refractory metals from high-temperature oxidation are usually formed by a diffusion process requiring concurrent transfer of silicon to the refractory metal surface. For a simple binary system and a coating thickness of one or two mils, the coatings on molybdenum and tungsten are primarily the disilicides WSi2 and MoSi2, respectively. During use of the coated re- fractory-metal system at high temperatures, in the absence of the silicon source, further diffusion causes growth of lower silicide compounds and depletion of the disilicides. Recent investigations have shown that the lower silicides are less effective than the disilicides in forming a glassy oxide film which impedes oxidation.' Consequently, failure of coatings at high temperatures may coincide with complete conversion of the disilicide phase. The purpose of this part of the study is to investigate the growth kinetics of the intermediate compounds in the W-Si and Mo-Si systems. There are three intermetallic compounds in the Mo-Si system: MoSi2 with a tetragonal structure

Jan 1, 1964

By Paul J. Sirkegian

A detail of the guide rollers is shown on Fig. I; and Fig. 2 shows a photograph of a guide roller that has been in service for several months on the haul-back cable. The former practice of supporting and guiding the haul-back cable on slusher hoists at Kimberly was accomplished by using the conventional type of snatch-block pulley, but it was found that an excessive amount of cable whipping and unreasonable wear on both rope and pulley resulted from this type of cable support. The guide, which is wholly made in the Corporation's shops, consists of two vertical and one horizontal roll assembled in a frame that is lagged to the cap timber in a slusher drift. In some slusher drifts more than one guide-roller assembly is used, depending upon the length of the drift. The installations usually are placed at 30-ft. intervals. We have found by actual experience that these rollers have increased the life of the haul-back cable approximately 200 per cent, as compared with the usage of the conventional sheave-block pulley. Cable Care The underground rigging crew and the slusher operators are trained in rope splicing. No cable clamps or knots are permitted on slusher cables and all cable "eyes" are spliced. The standard practice has been to use preformed cables of ?-in. diameter for haulage and ½-in. diameter for the haul back. The preformed cables have proved to be important factors for safety in use and speed in making splices. No external lubrication is used on the cables. It has been found that dry ropes have about 400 per cent longer life than those that were lubricated under these operating conditions. An accurate record is kept of all cable life and the tonnage moved by the slushers in each working place, and if the rope wear is excessive in any particular working place, an investigation is made to determine the reason. Wire-rope Sling for Snatch-block Anchor The rope sling is shown by Figs. 3 and 4. These slings support the snatch-block pulley for the haul-back rope. The standard practice at Kimberly is to use a roller-bearing snatch-block pulley 10 in. in diameter. The snatch-block housings are equipped with a clevis attachment in preference to swivel hooks, as it has been found that the more rigid clevis keeps the cable in better alignment. The snatch blocks are hung from the cable sling, which is wrapped around the posts of the drift sets as shown on Fig. 3. This method of anchoring the pulley provides better anchorage and flexibility than those of the rigid or spring-mounted types. When the slusher-drift headings are being advanced, the snatch blocks are hung from a "gin" pole ahead of the last set of timbers' An employee is assigned on each production shift to take care of the lubrication of all slusher hoists that are being used and he is provided with tools for minor repairs.

Jan 1, 1946

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Extensive solid solubilities of CdTe (zincblende-type struckre) and InTe (B37 type) in each of the rock salt-type compounds, PbTe and SnTe, have been observed. Partial phase diagrams have been determined by thermal analysis and X-ray metallography. The limiting mol fraction. X,, of the solute in the rock salt-type a phase and the corresponding eutectic temperatures, T,, are: (PbTe)l-x(CdTe)x: X,- 0.2, T, =866°C; (PbTe),-,(lnTe),: X, - 0.35, T, = 646"C; (SnTe),-,(CdTe),:X,- 0.11, T, = 784 "C; (SnTe),-,(lnTe),: X,-0.53, T, = 630°C. The lattice parameters of the a phase decrease linearly with X, even in (PbTe),-,(CdTe),, where a, (CdTe) = 6.481A > %(PbTe) = 6.459A. This is taken as proof that the cadmium atom enters an octahedral interstice of the tellurium atom sublattice; i.e., the formation of the a phase entails the direct replacement of lead by cadmium. The a, us X curve extrapolates to 6.16A at X = 1, in agreement with the value predicted for an ionic crystal of CdTe; it is also consistent with the reported lattice parameter It is well-established that the compositions of intrinsic semiconducting and semimetallic compounds conform to normal valence rules.1"5 The apparent exceptions can be explained by taking account of anion-anion covalences, as in CdSb, or of multiple cation valences, as in In Te.'This empirical generalization is the basis of the chemical approach to semiconductors2 by which the properties of an intrinsic semiconductor are rationalized in terms of the ionic-covalent bonds necessary to saturate the valence-electron complement of the anion sublattice. A fundamental shortcoming of this approach is its disregard of long-range crystal interactions. It cannot, accordingly, deal with the phenomenon of charge conduction except through the use of ad hoc postulates. As an example, a crystal of CdTe would, in the valence-bond picture: be described in terms of electron pairs, each with the same discrete energy, localized between every cadmium and tellurium atom. This is, of course, contrary to the Pauli of the high-pressure rock-salt form of CdTe, corrected for decompression from 36 kbar. The free energy of formation of the a phase of pure CdTe at room temperature is calculated from the phase diagram to be +10 kcal per g-atom, in accmd with the value calculated from the transformation pressure. The standard enthalpy is +13 kcal per g-atom, and the standard entropy is +9 eu. The latter value implies the formation of extra classical particles, such as vacancies, interstitials, or nondegenerate charge carriers, but these alternatives are not consistent with the semiconducting properties and the densities of the a phase. The extrapolated values of the lattice parameters of (PbTe),-,(lnTe), and Spectively, for the rock salt-type modification of InTe. The corresponding interatomic separation is intermediate between monovalent and trivalent indium. The qualitative implications of the results are considered from the viewpoints of both valence-band theory and energy-band theory. principle, and is corrected by methods of molecular-orbital theory in which bonds are replaced by bands of molecular orbitals whose energies, E, depend upon a crystal-momentum vector, k.7 Each band is derived from a linear combination of atomic orbitals with two electrons required to saturate each molecular orbital in the band. In a crystal of N atoms containing z atoms in its primitive unit cell, there are 2 N/z states per band which lie in a region of k space bound by the Brillouin zone. In an intrinsic semiconductor, the bands can be grouped into valence bands which are normally filled and conduction bands which are normally empty. If the highest valence band and the lowest conduction band overlap anywhere within the Brillouin zone, the material is rendered semimetallic. The quantity defines the effective mass, m*, of an electron in a conduction band (or of a hole, i.e., an electron deficiency, in the valence band) and leads directly to the concept of charge mobility through the relation \x = et/m*, where e is the electron charge and t is the lattice relaxation time.

Jan 1, 1964

By J. D. Irving

In the summer of 1899 there appeared in the Black Hills Mining Review† a short note announcing the discovery of certain deposits of wolframite in the vicinity of Lead City and Yellow creek, Lawrence co., South Dakota.

Jan 1, 1902

By P. T. Chiang

Chemical etching methods for the simultaneous revealing of the tellurium or selenium Phase and the chalcogenide grain boundaries of the alloy systems are given. A tellurium eutectic was found Present in zone-melted ingots. Similarly, a selenium monotectic was present in ingots. In general, the second phase (tellurium or seleniumn) occubies three different sites; viz., along the chalcogenide grain boundaries, as inclusions within the chalcogenide grain, and on the undersurface of the ingot. The detection limit for the tellurium phase is about 1 u in width. THERMOELECTRIC materials based on Group V (bismuth, antimony) and Group VI (selenium, tellurium) elements have aroused considerable interest in recent years in the practical application of thermoelectric cooling. In many cases, a small amount of excess tellurium (or selenium) was added to the material to optimize its thermoelectric properties. Then the question immediately arises as to the number of phases present in the resultant alloy. In the binary systems of Bi-Te, Sb-Te, and Bi-Se, the congruent melting compositions have been reported to be non-stoichiometric and are represented by Bi~Te respectively. It is to beexpected and known that Bi2Te3 and SbzTe3 crystallize from the melt with an excess of bismuth and antimony in the lattice and that tellurium forms a eutectic.~' The same could be assumed to take place in the pseudo binary systems of (Bi,Sb)zTe3 and Bi2(Se,Te)3 as well as in the system studiedby puotinen5 and other workers. Likewise, BiaSe3 crystallizes from the melt with an excess of bismuth in the lattice and selenium forms a monotectic.~ Therefore, in practice, alloys solidified from the melt often contain a second phase (tellurium or selenium) in one region or another of the solid mass even without the addition of excess tellurium (or selenium). ~u~~recht' studied the thermoelectric properties of (Bi,Sb)2Te3 alloys with excess tellurium and simultaneous additions of selenium. He mentioned that the materials show two phases because of the considerable excess of tellurium or selenium. However, he did not report as to how the tellurium or selenium phase was identified. It is generally believed that the presence of an excessive amount of tellurium or selenium phase in the alloy would adversely affect its thermoelectric properties and its uniformity. Consequently, there is a need for a simple method for the identification of the tellurium and selenium phase. The quantity of the second phase present is usually too small to be detected either by chemical analysis or by normal X-ray techniques. This investigation was therefore carried out, first, to devise a simple metallographic method for the identification of the tellurium or selenium phase coexisting with the chalcogenides and, second, to determine the distribution and specific location of the tellurium or selenium phase in the ingots. EXPERIMENTAL PROCEDURE The starting materials used for the alloy preparations were 99.999 pct pure bismuth, antimony, and tellurium and 99.997 pct pure selenium. The bismuth and antimony were obtained from Consolidated Mining and Smelting Co. of Canada Ltd., while the selenium and tellurium were obtained from Canadian Copper Refiners Ltd. The tellurium was purified further in the laboratory by zone refining. The elements were pulverized in a stainless-steel pestle and mortar. The amounts for the desired composition were weighed out each time on an analytical balance to make up a 100-g sample. Then the sample was introduced into a Vycor ampule (19 by 150 mm), pumped down to a vacuum of 10"5 Torr for 15 min, and sealed off. The ampule was then heated in a horizontal resistance furnace at 800" to 900°C for about 20 hr. During this period the assembly was rocked back and forth several times to ensure good mixing. At the end of the heating period, the ampule was quenched in cold water and then transferred to the zone-melting apparatus described in a previous publications to grow large-size aligned polycrystals. The background and ring-heater temperatures were adjusted to make the freezing solid-liquid interface slightly convex to the liquid. The recorded temperature gradient in the vicinity of the freezing solid-liquid interface was around 15°C per cm. The ampule was moved horizontally at a speed varying from 0.4 to 2 cm per hr so that the ring heater would cover the whole ingot length from end to end. A single zone-melting pass was used for the Bi-Te, Sb-Te, and Bi-Sb-Te ingots. Two passes in the forward and reverse directions were carried out for the Bi-Se and Bi-Se-Te ingots. Six passes in the forward and reverse directions were performed for the Bi-Sb-Se-Te ingot. The zone-melted ingots were found to contain several large crystals, with their basal planes (0001) approximately parallel to the growth axis. Samples of bismuth and antimony tellurides coated with a layer of tellurium, and bismuth selenide coated with a layer of selenium, were prepared for comparison in phase identification. These coatings were made by dropping a piece of the zone-melted ingot into some molten tellurium or selenium under argon atmosphere and allowing them to cool slowly to room temperature. The metallographic specimens were prepared by

Jan 1, 1969

By J. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies. THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.'-" This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications. Geology The geology of the Picher mining field is similar to that of the entire Tri-State district because the sedimentary horizons that are found here are found throughout the district, and the ore bodies in the respective horizons have similar characteristics. The beds that contain the ore bodies in the Picher field are illustrated and described in fig. 2. The five unconformities found in the mines of the Picher field are indicated on the geologic section, fig. 2. The unconformity shown at the base of Meramec (B bed) is relatively unimportant since B bed was mostly eroded from the area of the Picher field before the Chester beds were deposited. B bed has been observed in the cuttings from only a few churn drill holes. The Pennsylvanian (Cherokee shale) formation is the top horizon found in the Picher mining field. It has been eroded from the southeastern part of the field, but because of the regional dip of the sedimentary beds to the west, it attains thicknesses of 100 ft to 200 ft along the west edge of the field. It is 200 ft to 300 ft thick in the Miami trough. It was deposited on the Boone limestone surface, which contained relatively few shallow erosion channels and very few depressions. Subsequent to the deposition of the shale, solution of limestone from underlying limestone horizons by circulating solutions caused the overlying beds, including the Cherokee shale, to slump into the larger openings formed by the solution and removal of the limestone. Chert The origin of the chert in the Tri-State district has been a controversial subject among geologists. Tarr7 advocated a syngenetic origin for the chert, postulating that it formed from colloidal silica deposited in the Mississippian seas. Leith, Dake and Leighton' argued in favor of silicification of erosion

Jan 1, 1951

By J. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies. THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.'-" This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications. Geology The geology of the Picher mining field is similar to that of the entire Tri-State district because the sedimentary horizons that are found here are found throughout the district, and the ore bodies in the respective horizons have similar characteristics. The beds that contain the ore bodies in the Picher field are illustrated and described in fig. 2. The five unconformities found in the mines of the Picher field are indicated on the geologic section, fig. 2. The unconformity shown at the base of Meramec (B bed) is relatively unimportant since B bed was mostly eroded from the area of the Picher field before the Chester beds were deposited. B bed has been observed in the cuttings from only a few churn drill holes. The Pennsylvanian (Cherokee shale) formation is the top horizon found in the Picher mining field. It has been eroded from the southeastern part of the field, but because of the regional dip of the sedimentary beds to the west, it attains thicknesses of 100 ft to 200 ft along the west edge of the field. It is 200 ft to 300 ft thick in the Miami trough. It was deposited on the Boone limestone surface, which contained relatively few shallow erosion channels and very few depressions. Subsequent to the deposition of the shale, solution of limestone from underlying limestone horizons by circulating solutions caused the overlying beds, including the Cherokee shale, to slump into the larger openings formed by the solution and removal of the limestone. Chert The origin of the chert in the Tri-State district has been a controversial subject among geologists. Tarr7 advocated a syngenetic origin for the chert, postulating that it formed from colloidal silica deposited in the Mississippian seas. Leith, Dake and Leighton' argued in favor of silicification of erosion

Jan 1, 1951

By C. Laird, C. E. Feltner

IN previous workif2 we have shown that the steady state cyclic stress response of pure copper tested in the low cycle fatigue range was determined only by the plastic strain amplitude and the test temperature. hus, copper, at any given temperature, has a unique cyclic stress-strain curve independent of prior history. Cu-7.5 wt pct Al, however, showed a stress response for a given plastic strain amplitude and temperature which depended sensitively on prior history. From this work we predicted that all wavy slip mode materials, typified by copper, would have a unique cyclic stress-strain curve; whereas all planar slip mode materials, typified by Cu-7.5 pct Al, would not. This prediction has now been tested for a number of materials of widely varying crystal structure and slip character. Wavy slip mode materials studied include: Fe. Al, Cd, disordered FeCo-V, and Cu-3 pct Co (quenched and aged). Planar slip mode materials investigated include: Fe-3 pct Si, ordered FeCo-V, disordered Ni3Mn, ordered Ni3Mn, and Zn. The treatment and properties of these materials are listed in Table I. Cyclic stress-strain curves were determined by controlled plastic strain tests (see Ref. 1 for details) at room temperature for all materials in both the initially annealed and cold worked conditions. The results obtained for iron and Fe-3 pct Si are typical of wavy and planar slip mode materials, respectively. The cyclic stress-strain curves for these materials are shown in Fig. 1 and it can be seen that iron has a unique cyclic stress strain curve while Fe-3 pct Si does not. Aluminum, Cu-3 pct Co, and disordered FeCo-V showed a behavior like that for iron, while Ni3Mn in both the disordered and ordered condition behaved in the same manner as Fe-3 pct Si. These results therefore support the general conclusion drawn in Refs. 1 and 2 that. for wavy slip mode materials, a cyclic mechanical equation of slate it =t.(hcp, i. T) is approximated in which the satura-

Jan 1, 1970

By A. Dubé, G. Letendre, C. E. Beaulieu

An experimental study has been made of the time dependence of internal .friction and modulus of rigidity in- freshly quenched steels at room temperature. The effects of frequency, composition, and various thermal treatments are given. The kinetic 1aws observed cannot be fully explained by the so-called first stage of tempering and the transformation of retained austenite. It is suggested that the observed phenomena are due to the progressive immobilization of dislocations introduced by the martensitic transformation. It is generally agreed that the conversion of tetraginal martensite into cubic ferrite and ce-mentite occurs in three stages which at moderate rates of heating take place in the following temperature ranges:'-3 a) The first stage involves mainly a partial loss of tetragonality of martensite and the formation of ?-carbide between 95" and 175oC. b) The second stage consists of the decomposition of retained austenite between 230 and 290' C. c) The third stage covers the formation of ce-mentite between 290o and 400' C. The kinetic laws of these heterogeneous reactions have also been the subject of isothermal studies. Thus, Roberts, Averbach. and cohen3 report a very low reaction rate with a eutectoid steel at room temperature. For example, less than 10 pet of the contraction associated with the first stage is observed after 50 hr at room temperature. Hollonlon, Jaffe, and Buffum4 show that under the same conditions less than 10 pet of the tetragonality is lost. These results have led to the belief that martensite is a relatively stable phase at room temperature. On the other hand, it is well known that important structural changes occur in martensitic steels during the first few minutes at room temperature after quenching. This pretempering has at least two important consequences. In the first place, freshly quenched steels have a tendency to crack at room temperature, a fact which leads to the necessity of tempering as soon as possible after the quench. Another important consequence of pretempering a steel for short periods of time at room temperature is the stabilization of the retained austenite. Thus, as shown by Cohen,5 a very pronounced stabilization is effected with holding periods of 30 min at room temperature. Since these two effects are apparently not caused by the heterogeneous reactions mentioned above, they must be related to the rearrangement of structural defects within the martensite and retained austenite. According to the modern theory of dislocations, the shears required to effect the austenite-marten-site transformation may be realized through the motion of dislocations at the austenite-martensite interface and within the martensite plates.6 In this way, a martensitic transformation closely resembles a plastic deformation. In cold-worked solids, high concentrations of dislocations are left immediately after the plastic deformation and it seems reasonable to assume that appreciable densities of dislocations should also appear in the wake of a martensitic transformation. A considerable part of the high hardness of martensite would then originate in the obstruction of dislocations in analogy

Jan 1, 1961

By A. Eilers

ALTHOUGH the process to which I refer in this paper has been in successful operation for nearly five years, during which time it has been introduced, superseding all other processes having in view the same end, in almost every lead refinery in the country, no description of it, giving economical data, has ever appeared in print, nor has the process been known in its details to any considerable number of engineers beside those conducting it at their works. A discussion of this subject at the present time becomes especially interesting in view of a late publication in the Prussian ministerial organ for Mining and Metallurgy, by Dr. Wedding, in which the method of treating the zinc-silver-lead alloy by distillation, as finally settled upon at Tarnowitz, is very minutely and fully described. It is the more interesting, because in that article reference is made to the American method in an unfavorable light, while, at the same time, it is clear from the article itself, that the most important details of the process, besides the one that it is conducted in black-lead retorts, were not at all understood. In publishing herewith the details of our American method, one of my objects is to invite comparisons between our simple and direct process and the elaborate one at Tarnowitz. In extracting the silver from work-lead by means of zinc, it is always the intention, in this country, to obtain a zinc-crust so rich in silver that the rich lead resulting from subsequent distillation

Jan 1, 1875

By O. P. Arora, M. Metzger, G. R. Ramagopal

Single-phase aluminum containing 0.0001 to 0.06 pct Cu was studied in strong acid, mainly through observations of hydrogen evolution. The strong influence of copper was exerted almost entirely through the imposition after a certain delay time of an auto-catalytic localized-corrosiott reaction. Additions of cupric ion to the acid produced lower accelerations. The significance of the quantity and distribution of copper was discussed, and the implications for intergranular corrosion and neutral chloride pitting were indicated. AN investigation of intergranular corrosion in single-phase high purity aluminum exposed to hydrochloric acid indicated the copper content of the metal to have an influence on corrosion at lower levels than previously suspected.&apos; The work reported here was a closer examination of the action of copper but dealt with general corrosion to gain the advantage of having a continuous measure of corrosion through the volume of hydrogen evolved, the reduction of hydrogen ion to hydrogen gas being the principal or only cathode reaction in strong hydrochloric acid. Previous work on the hydrochloric acid corrosion of aluminum was sometimes insufficiently structure-conscious and the need for care in evaluating it arises from the low solubility of the iron impurity,&apos; and of some alloying elements, and the known or possible presence in many of the compositions studied of second phases leading to greatly increased corrosion rates.3 These increases are attributed to the presence of low hydrogen-overvoltage cathodes provided by the second phase.3&apos;4 For the present single-phase work, a few studies which used high-purity base material and small copper additions5-&apos; provide the essential information most unambiguously. The corrosion rate was shown to be increased markedly by the introduction into the acid of small quantities of the ions of copper (and of certain other metals) which cement on the aluminum and provide cathodes of low overvoltage.5 When there was sufficient copper in the aluminum, the same result was produced during the course of corrosion leading to a rate which increased with time as the reaction was stimulated by one of its products (autocatalytic reaction). In 2N (7pct) HC1, an accelerating rate was observed at 0.1 pct Cu but not at 0.01 pct.5,7 The present work dealt with corrosion rate and morphology and their correlation with the quantity and distribution of copper catalyst for copper contents from 0.0001 to 0.06 pct. PROCEDURE A lot of high-purity aluminum containing 0.0021 pct Cu, 0.001 pct Fe and 0.003 pct Si (Alloy A) was alloyed with copper to yield aluminum containing 0.014 pct Cu (B) and 0.06 pct Cu (C). Later it was found necessary to include the lower copper Alloy K which contained 0.0001 pct Cu, 0.0004 pct Fe and 0.0004 pct Si. The upper limit for any other element can be confidently estimated as 0.0005 pct. No element other than copper appears to be present in quantities sufficient to have an effect on general corrosion as great as the observed effect of the copper in A, B, and C. The only other heavy metal detected by spectrographic examination was silver (< 0.0001 pct). The acid was made up from a selected lot of 37 1/2 pct CP hydrochloric acid containing 0.1 ppm heavy metals (mainly Pb), 0.05 ppm Fe, and < 0.008 ppm As and from water distilled from 1 megohm-cm demineralized water and believed to have contained negligible quantities of heavy metals influencing corrosion. Acid strength was adjusted to within 0.05 pct HCl of the stated value by using precision specific gravity measurements. Test blanks 10 by 41 mm were sheared from 1.65-mm cold-rolled sheet. Edges were finished by filing. The blanks were annealed in air at 645°C for 24 hr in alundum boats and rapidly water quenched. The anneal is thought to have produced a substantially homogeneous solid solution—for iron, copper, or silicon, for example, the annealing temperature was 200°C or more above the solvus-and the quench is considered to have preserved the high-temperature structure except for the condensation of lattice vacancies into dislocation loops.&apos; The 0.06 pct Cu alloy did not appear unstable in respect to slow precipitation reactions at room temperature since two pairs of tests failed to show significant differences between specimens heat treated 3 1/2 years earlier and specimens heat treated 1 or 2 days before.

Jan 1, 1962