Search Documents

By Kurt Stock

The war caused a demand for enormous quantities of high-grade zinc, which were not available and could not be produced from pure ores in sufficient amounts and in the time required. Redistillation of virgin spelter on a large scale was practiced to supply this demand; this paper gives a full description of the process used by the Oklahoma smelters of the Bartlesville Zinc Co. As the redistillation of zinc has become of historical interest only, having been superseded by the electrolytic process, it was deemed advisable to give expression to this phase of the metallurgy of zinc that, in the past, had never gone beyond laboratory experimentation. THE grades of spelter demanded by the consuming industries were not definitely established until the American Society for Testing Materials undertook to fix specifications, based on the varying percentages of the common impurities (lead, iron, and cadmium) as follows: TOTAL, NOT LEAD, IRON, CADMIUM, OVER. PER PER CENT. PER CENT. PER CENT. CENT. A. High grade 0.07 0.03 0.05 0.10 B. Intermediate 0.20 0.03 0.50 0.50 C. Brass special 0.75 0.04 0.75 1.20 D. Prime western 1.50 0.08 The question which grade was the best for certain purposes and why was left unanswered. The conservatism of the zinc-smelting industry and the unwillingness of the spelter-consuming industries to engage in research work prevented the full benefits being obtained that such standardization promised. The custom smelters, producing spelter in pigs or plates, found it impossible to adhere closely to the established limits on account of the variety of ores treated; and the smelters with long-established and known brands, or those manufacturing their metal into marketable products, like sheet zinc, did not have to abide by the newly established grades based on chemical percentages.

Jan 7, 1924

By Arnold S. Epstein

Tlze green electroluminescence occurring at liquid-nitvogen temperature in epitaxial gallium phosphide diodes is exarnined using the donor dopants silicon and sulfur. Zinc is used as the p-type diffusant. Two tt~ain peaks are found, namely til 0.56 and 0.535 p. The intensity of the gYeen peak occurring at 0.56 is found to oary as -4"' wlzere Jf is the forward current density and to first order appears to be dependent on the concet~tvation of ionized donovs. Tile vadintive lifetinze fov this process is -10-'sec. The intensity of the 0.56-p lu~ninescence is nt least several ovdevs of magnitude greate,, at liquid-nitvogen temperature than that noted jor the 0.538 radiation for current densities up to about 35 amp per sq cm. The variation oj- the intensity of. the 0.538-p peak with current density caries according to the donor dopant. With sulfur as the donor one has a J12 dependence, whereas when silicon is the donov a J1.5 dependence is noted. Tl~e above can be fitted to a In molecular process (in first order) such as a band to band recombination. The constant B fir band to band vecombination) is found from our experitt~etlt to be of the order of 2 CZI cm per sec, zcl~ereas for tlze impurity vecombination peak (0.56 p]) tile A cotzstor~t is of the order of. 7 x 10-' cu cm per sec. The structuve o/. the diodes at liquid-nitvog-en tett~peruture is oj tlze double injection type, and by carefi~lly selecting. the thickness of the structure one can regulate the onset of the 0.538-p radiation. The diode clzavaclevistics follow an I-Vx laiv where x is >1. Llregatiue resistance in these structures con be correlated with saturation of tlze 0.56- peak. ThE development of high-purity, large single crystals of epitaxially grown gallium phosphide is the ultimate aim of the studies to be reported. While a number of papers and reviews' have been presented on properties of gallium phosphide grown from gallium solution and from the melt, less attention has been paid to the properties of epitaxial gallium phosphide grown from the vapor. In the studies to be reported we have examined the effects of shallow donor impurities, primarily silicon and sulfur, at liquid-nitrogen temperature, on both the electrical and green electroluminescent properties of carefully characterized single-crystal epitaxial Gap. I) EXPERIMENTAL PROCEDURES A) Material Preparation and Properties. The samules used in this investigation were single-crystal n-type epitaxial gallium phosphide. he single crystals were synthesized from the elements by vapor transport and epitaxial deposition on single-crystal gallium arsenide substrates. Typical transport agents used were chlorides. The growth procedures are described in more detail in Ref. 2. The samples were grown in the (111) orientation and had thicknesses up to 480 . Following the growth, the GaAs substrate was removed from the epitaxial Gap by etching in nitric acid. The Hall effect and resistivity of these n-type samples were measured as a function of temperature and analyzed for impurity content and compared with spectroscopic emission analysis. The results are given in greater detail in Ref. 3 but a summary is noted in Table I. In Table I, AED denotes the donor ionization energy, Nd is the donor impurity concentration, lvA is the acceptor impurity concentration, NI is the total impurity concentration, Rip vs temperature is the measured Hall mobility-temperature relationship from liquid nitrogen to about 400"K, n(77"K) is the measured carrier concentration at liquid nitrogen, and R/p(77'~) is the measured Hall mobility at liquid nitrogen. Good agreement is noted between electrical and emission analysis for the major donor impurity, silicon, in the two materials where it is a major constituent. In the case of the two samples SC90-6 and AP138-3(111) B which were sulfur-doped the ionization energy found from the electrical data is in good agreement with that reported for sulfur.4 The acceptor impurities are not known, although from the presence of magnesium in the samples as indicated by emission analysis and its known role as an acceptor in GaP,4 magnesium could be present as an acceptor. Similarly, since silicon is known to be an amphoteric impurity4 it may also be present as an acceptor in the Gap.* The *A small band has been noted at 0.625 11 in samples SC90-6, SC76-4, and SC77-4, suggesting according to Ref. 5 that sillcon could be present as an acceptor In these samples since these authors have found this peak to represent a donor-silicon emission. presence of calcium deduced from emission analysis is not correlatable with the electrical analysis and its presence as an electrically active impurity should be questioned. B) Sample Preparation and Diode Fabrication. The original slices were of the order of 2 sq cm in area witi the (111)B face up. The material was cleaved and sectioned and the best pieces selected (i.e., those which visually appeared to have the least strain and defects). The samples were polished, lightly etched, and cleaned in trichloroethylene. Zinc was diffused in a closed tube at 800°C to form a p-n junction. Diodes were made from these samples. The depth of junction varied, but did not exceed 10 p depth. The back side of the slice was lapped back and a low-resistance n-type contact was formed (at 600°C in forming gas) to an Au-Mo tab with a hole in the middle for

Jan 1, 1968

By M. J. Marcinkowski, A. Szirmae, R. M. Fisher

Room -temperature hardness measurements obtained from single and polycrystalline samples of a 47.8 at, pet Cr-Fe alloy which were aged for various times al 500°C show a two-fold increase over that of the unaged alloy after annealing for 1000 hr. A detailed examination of the deformation markings in the neighborhood of the hardness imbressions reveals that twinning becomes an increasingly more important mode of deformation as aging proceeds. this observation is shown to be inconsistent with the Proposals that the transformation is eve of order-disorder On the other hand, the results are in agreement with previous observations of Fisher et al. of a coherent chromium-rich precipitate which forms in an iron-rich matrix as a result of a miscibility gap in this alloy system as proposed by Williams . Using the coherent precipitate hypotlzesis as a model, a detailed analysis of the various possible strengthening contributions to both the slip mid twinning stresses is made. In the case of' slip, lattice friction within the chromium-rich phase and the chemical energy associated with the interface between the two phases contribute about 60pet to the total strength. The contributions from coherency strains and modulus differences are thought to contribute the remaining 40 pet of the strength but are difficult to evaluate because of uncertainties regarding the flexibility of the dislocation line. All of the factors have nearly the same or else a smaller effect on the twinning stress in the aged alloy. Twinning is never observed in the unaged alloy because the twinning stress is much higher- than that for slip. With increased aging times, the various contributions to the total stress for both twinning and slip increase, but most of those for slip increase much more rapidly, so that, in the fully aged alloy, it surpasses the stress for twin propagation. When a twin is nucleated by the chance occurrence of an internal stress concentration during a test, the subsequent twin burst results in a low hardness reading. FeRNTIC Fe-Cr alloys from about 15 to 80 at. pet Cr content show considerable change in properties such as hardness, electrical resistivity, saturation magnetization, and so forth, after aging in the vicinity of 500°C.* The most marked change is a large increase in hardness accompanied by a sharp decrease in ductility, so the phenomenon has often been referred to as the 475°C (885°F) em-brittlement problem. Changes in microstructure are rather subtle and most investigators have not been able to observe any X-ray diffraction or metal-lographic changes during aging. There is little doubt that the phenomenon is inherent to the Fe-Cr binary system and is not directly related to the formation of a phase. Two distinct schools of thought have developed during the past decade concerning this problem. Masumoto, Saito, and sugiharal have concluded, from their own specific-heat measurements, that atomic ordering occurs in this temperature range. Pomey and Bastien2 have also attributed the changes in physical properties with aging in the neighborhood of 500°C to atomic ordering. In addition, Takeda and Nagai3 claimed to have found X-ray verification for superlattices corresponding to the compositions FesCr, FeCr, and FeCr3. However, all known attempts to observe superlattices in Fe-Cr alloys using neutron diffraction, which should be much more sensitive, have been unsuccessful. These have been reported by Shull et al.4 for 25 at. pet Cr, williams5 for 75 at. pet Cr, and Tisinai and samans6 for a 28.5 at. pet Cr. steel. The second and more prevalent opinion ascribes the 475°C embrittlement phenomenon to the formation of a coherent precipitate due to the occurrence of a miscibility gap in the Fe-Cr system below about 550°C. This latter concept was first indicated by the results of Fisher, Dulis, and Carroll,7 who were able to extract fine particles about 200Å in diameter from samples of 28.5 at. pet Cr steels aged from 1 to 3 years at 475°C. The extracted material was found to be nonmagnetic, to have a bee structure with a lattice parameter between that of iron and chromium, and to contain about 80 at. pet Cr. Williams and paxton8 and williams5 confirmed these results and first explicitly proposed the existence of a miscibility gap below the a region in the equilibrium diagram. Alloys aged within this gap

Jan 1, 1964

By J. K. Kerver, J. S. Osoba, J. G. Richardson, J. A. Hafford

A detailed study of a number of methods of relative permea-abilitv measurement has been made in a search for the tech-niqrle most suited to routine analysis of cores taken from reservoir rock. It has been found from tests run on the same samples of core material by a number of techniques that the Penn State, Hassler, Hafford, and dispersed feed techniques all yield results which are felt to be reliable. Conditions under which the faster single core dynamic technique may be used are described. Further work on the calculation of relative permeabilities to oil from data obtained by the gas drive method is needed before this latter rapid method can be utilized. Correlations between theoretical studies and experimental results have been obtained in studies of the boundary effect. pressure distribution in two-phase flow, and gas expansion effects. Previous conclusions that the effects of the outflow boundary could be made negligibly small have been substantiated. Results of experimentally determined oil and gas pressure distributions along a core sample during flow are presented. Further studies of the effects of rate of flow in the measurement of relative permeability-saturation relations have shown that results are independent of the rate of flow as long as the flow rate is below the point where inertial effects commence. An analysis of the effects of a severalfold expansion of gas along the flow path indicates that while saturation gradients are induced in the test sample, the errors caused by this phenomenon in relative permeability measurements are small. INTRODUCTION Many pages of literature have been devoted to pointing out the need for relative permeability-saturation relations in reservoir engineering. One of the most attractive ways of obtaining this information is by the analysis of samples of core material taken from the formation in question, and again literature has described man); methods for obtaining these data. It is the purpose of this paper to present the work that has been done in the study of some of these published methods together with some other methods that have been recently developed in this laboratory. Also, a study of some of the factors that influence the laburatory determination of relative permeability-saturation relations is presented. FACTORS WHICH AFFECT LABORATORY STUDY OF FLUID FLOW THROUGH RESERVOIR ROCK To determine relative permeability-saturation relations of samples of reservoir rock in the laboratory, it is important to know what factors affect these measurements in order that the magnitude of these effects can be ascertained and steps then can be taken to eliminate or, in some cases, to minimize them. The factors that have been investigated are the boundary effect, the effect of gas expansion. and the rate effect. Boundary Effect In laboratory experiments in which two immiscible fluids are flowed through a porous medium, there exists a discontinuity of capillary properties at the outflow face. This discontinuity exists became the fluids pass from a region of finite capillary pressure in the sample to a region of zero capillary pressure in an open receiving vessel. The capillary forces existing in the core caupe the rock to tend to retain

Jan 1, 1952

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By E. P. Jennings

Large deposits of titaniferous iron-ore occur at Caribou, an old silver-mining camp in Boulder county, Colo., 17 miles west by south of Boulder, and a few miles northwest of the tungsten-mines. Professor Regis Chauvenet1 published a part analysis of the ore many years ago, but gave no description of the wall-rock. Caribou hill, which contains both the silver-bearing veins and the iron-ore deposits, is a low dome of gabbro surrounded by the Archæan schists and gneisses of the Front range of the Rocky mountains, the peaks of which, a few miles west of Caribou, attain an elevation exceeding 12,000 ft. The gabbro stock is roughly elliptical in outline, with approximate diameters of 1 and 3 miles. The crest of the dome is 10,500 ft. above sea-level, and the town and ore-cleposits are 500 ft. lower. Outcrops of the iron-ore occur in the town and extend NW. for 2,000 ft., where they disappear under the swampy meadows of Caribou park. Portions of the deposit are covered by drift, but one continuous outcrop is 900 ft. long and from 200 to 250 ft. wide. A second deposit is 0.25 mile south of the town along the eastern slope of the hill. It is not as well defined as the north bed, but is approximately 1,000 ft. long and from 100 to 200 ft. wide. The easily disintegrated ore does not form prominent outcrops, but the outlines of the deposits are readily traced by the large amount of ore fragments that cover the ground. Trenches and pits sunk on the outcrop expose a roughly banded magnetic iron-ore, with pyroxene as the principal gangue-mineral. The Gabbro. This rock was classified in the field as a gabbro from the presence of pyroxene and striated feldspars, and for convenience the field-name will be retained.

Jan 1, 1913

INTRODUCTION Data available on prophyry copper occurrences in the Andean, Caribbean, Appalachian, and Cordilleran orogens may be categorized in a manner to suggest a hypothetical evolution for deposits that occur in the western hemisphere. A classification of de- posits is also suggested. A classification dependent on internal structure of a porphyry copper deposit would lead to two broad categories, breccia pipe and stockwork models. A classification of this type is examined herein but it is not universally accepted in the literature. Modeling based on igneous petrography as well as metasomatism attendant with the sulfide mineralization is more widely accepted by economic geologists whose evaluation of porphyry systems is influenced by the presence or absence of a phyllic zone. Lowell and Guilbert model deposits ordinarily include a phyllic zone, whereas those of the diorite model do not. Position of the phyllic zone in the alteration sequence is a significant ore guide. Should the phyllic zone be absent, dependence on alteration zoning to identify metallization is weakened. Presence or absence of the phyllic zone therefore is a significant parameter in the economic evaluation of a porphyry copper deposit (Hollister. et al., 1975). The Lowell and Guilbert (1970) model commonly includes a phyllic zone in quartz- bearing rocks. Parameters of both calc-alkalic and the quartz monzonite models mentioned elsewhere in this volume are sufficiently close to the Lowell and Guilbert (1970) model that it should be expanded to encompass them. The diorite model remains separate and distinct because deposits of this type are characterized by an absence of quartz in the pluton, commonly highly gold: copper ratios, low molybdenum content, and regular absence of sericite in the alteration zones. Therefore, for the benefit of those

Jan 1, 1978

By A. M. Gaudin

A great number of hypotheses has been advanced to explain the complex phenomena that are encountered in flotation. In the days of bulk-oil flotation, when a large quantity of oil was employed, it was observed that the oil-mineral aggregate floated above the ore-pulp because of its lesser density. With the advent of froth-flotation this phase of the theory had to be modified to take into account the presence of air bubbles. The reason why the mineral-bearing froth of today rises to the top of flotation cells is, of course, because the air-mineral aggregate, with whatever reagent may be associated with it, is lighter than the pulp. In an attempt to explain froth-flotation the fact has been emphasized that certain minerals are wetted and therefore remain in water; while others are not wetted and therefore become associated in preference with air. Such an "explanation" does not explain facts, it merely states them; for instance, it does not explain why minerals are wetted under some circumstances and not wetted under others. Going somewhat further, the wetting or nonwetting of minerals by water has been ascribed' to differences in the angles of contact between oil droplets and mineral surface at the surface of the minerals. This explanation, however, was abandoned when soluble flotation reagents came to replace the so-called "insoluble" reagents. Another theory, sponsored about 10 years ago by Ralston,² involves the effects of electric charges at the surface of the mineral particles and air bubbles. This theory, unfortunately, was not developed as fully as it seems desirable. The belief that adsorption phenomena might play a preponderant role in flotation3 has been rather widespread for the last 10 years. Unfor-

Jan 1, 1928

By Carl G. Hogberg

During recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. Principles 01 Iron Desulphurization in Furnace Although investigations of the blastfurnace process have not clearly revealed the detailed mechanism of iron desulphuri-zation within the furnace, they have been sufficiently extensive to permit a postula tion of the following general principles: 1. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurizatioil is relatively narrow, being confined to a vertical distance extending zapproximately from tuyere level to the iron-slag interface in the hearth.' 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.= Coke ash is released as the coke bums in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943

By Carl G. Hogberg

During recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. Principles 01 Iron Desulphurization in Furnace Although investigations of the blastfurnace process have not clearly revealed the detailed mechanism of iron desulphuri-zation within the furnace, they have been sufficiently extensive to permit a postula tion of the following general principles: 1. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurizatioil is relatively narrow, being confined to a vertical distance extending zapproximately from tuyere level to the iron-slag interface in the hearth.' 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.= Coke ash is released as the coke bums in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943

DISCUSSION, M. Cohen presiding A. H. Geisler and D. L. Martin (GeneTal Electric Research Laboratory, Schenectady, N. Y.)—We were rather interested to note the author's conclusion that the cubic to tetragonal transformation may be of the second order, for we have been able to show that the order-disorder transformation in an analogous alloy system is a first-order transformation with a discon-

Jan 1, 1952

By T. R. Scott

The acid pressure leaching of zinc-lead flotation concentrates from the McArthur River deposit, Northern Territory, Australia, has been studied in a three-stage, continuous, co-current system, using titanium reactors of 6 gal capacity. The starting pulp contained 2.7 lb solids per gal of synthetic spent electrolyte and the final liquors contained 120-125 gpl Zn. Parameters investigated included temperature (95-120°C), oxygen pressure (30-100 psi), acid addition (80-130% of theoretical), and leaching time (35-65 min per stage). Technical factors studied included mixing and pumping of feed, agitation, settling and washing and control mechanisms. The chemistry of liquor impurities, of scale formation in autoclaves and of lead jarosites in residues was studied in some detail. Results indicated that 90-93% zinc recovery could be obtained with a "low- acid" process, using 113°C and 70 psig with oxygen as the favored operating conditions. Residues contained 16-18% elemental sulphur and 15% lead, together with unreacted pyrite and gangue minerals. Pelletizing of residues was impracticable, and alternative suggestions for the recovery of lead, sulphur and silver are discussed. Preliminary estimates for plant and operating costs are given and enable some comparison to be made with conventional procedures.

Jan 1, 1973

By K. Huessener

In presenting the following data on combustion in the open hearth furnace and the advisability of automatic combusion control, the author finds himself much more severely handicapped by the lack of reliable test results than he had anticipated when he first undertook to write this paper. In order thoroughly to investigate how the results of an open-hearth furnace are influenced by combustion, one would have to draw up a large number of heat-balance sheets, as Kinney and McDermottl have given for one heat in their extremely able paper on "Open Hearth Efficiency,' presented before the American Iron and Steel Institute on October 27th,1 1922. Instead of covering only one heat, however, such heat-balance sheets would have to embrace a large number of heats, and not only for one kind of fuel, but for all the various fuels in customary use. Use of Radiation-protected Pyrometer Such tests necessitate extremely careful temperature readings, and here the first serious difficulty presents itself. Nearly all the temperature readings so far published have been taken with thermocouples for the lower ranges and with optical or radiation pyrometers for the higher ranges. This method of measuring reveals the temperature of the surrounding walls, or in the case of optical or radiation measurements, the temperature of that part of the opposing walls which has been focused by the instrument. The error in ascertaining the temperature of the gases entering or the waste gases leaving the checker chambers is probably not very large, as the flowing gases impart their temperature to the walls of the flues. On the other hand, the uptakes, where the preheat temperature of gas and air are usually measured, are under the influence of radiated heat from the port ends, and correct temperature readings can here be taken only by using a radiation-protected pyrometer of the aspirating type.

Jan 1, 1926

By J. Rourke, F. S. Minshall, E. G. Zukas, C. M. Fowler, O&apos

The Hugoniot curves were determined for Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si. The pressure of the transition increased as the silicon content of the alloy increased. Single crystals of 2.9 wt pct Si-Fe were also studied. The pressure of the transition was not dependent on crystallo-graphic orientation. All of the Neumann bands (mechanical twins) were attributable to (112) planes but not all of the {112} planes showed twin markings. A thorough study of the iron Hugoniot (the relationship between specific volume and pressure) under plane wave shock loading revealed a pressure transition at about 130 kbar shock pressure. The results of this investigation were reported by Bancroft, Peterson, and inshall1 in 1956. At the time of this discovery, it was felt that this was probably the a, to y transition normally found in iron and many of its alloys. Subsequently a number of iron alloy systems were surveyed in which the alloying element has a considerable effect on the normal a, to y transformation. The influence of carbon and nickel and/or chromium have already been reported.2,3 At the present time, there appears to be some doubt that this pressure transition is the usual a, to y transition In this study, Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si were chosen for several reasons. To the present, the transition has been found only in iron-base alloys which were originally in the a, phase (bcc). Secondly, the y loop at atmospheric pressure extends to only about 2.5 wt pct Si. If the transition were a, to y, then one might expect a rather drastic pressure effect for alloys containing more than 2.5 wt pct Si. Finally, single crystals of Fe-Si alloys large enough for shock loading studies are readily available thereby making it quite easy to determine the effect of crystal orientation on the transition pressure and on the twinning behavior of the alloy. EXPERIMENTAL PROCEDURE Fe-Si alloys containing up to 7 wt pct Si were produced by normal vacuum casting procedures. Single crystals of Fe-2.9 wt pct Si were purchased from Monocrystals Co., Cleveland, Ohio. The orientations of these crystals were determined and samples cut so that the shock wave would be parallel (to within 1.5 deg) to either the (loo), (Ill), or (112) principal orientations. Three distinct experimental testing techniques were used. First, the pin technique, described elsewhere,4 was used to determine the transition pressure for the polycrystalline alloys as well as for the (111) and (112) orientations of the 2.9 wt pct Si single crystals. Secondly, the recovery studies, described in detail in an earlier paper,2 were used for determining the effect of alloy composition and crystal orientation on the plastic II compression-plastic I rarefaction interaction zone for several specific shock pressures. Finally, measurements of pressures above the two-wave threshold were made on the polycrystalline alloys so that more complete Hugoniot curves could be constructed for this alloy system. The optical techniques described by Rice et al.5 were used to measure the shock and free surface velocities of the samples from which the Hugoniot data were obtained. This method is applicable only in the single wave region, since velocities are obtained from the measured total transit times of the disturbances through measured sample thicknesses.

Jan 1, 1963

President MRS THORNS E LLOYD 14 Green Hill Road Morristown, N J First Vice-President MRS A B PARSONS 52 Edgewood Road Scarsdale, N Y Second Vice-President MRS H A PROSSER 1001 Park Avenue New York, N Y Third Vice-President MRS HARRY J WOLF 3 Glenwood Avenue Littleneck, N Y Fourth Vice-President MRS MARK LAWRENCE REQUA 140 North Plymouth Blvd Los Angeles, Calif Fifth Vice-President MRS NEWELL G ALFORD 314 South Homewood Avenue Pittsburgh, Pa

Jan 1, 1952

By William G. Pariseau

The flexure of geologic strata, a phenomenon of interest to geologists and mining engineers alike, is examined as a sheet bending problem in Coulomb plasticity. Fonnulae for the distribution of stress, strain, and displacement increments; volume change; change in the length of the central surface; and power of dissipation, as well as for the neutral surface shift are given. Strains of any magnitude are considered. The analysis shows that deeply buried strata may bend and develop "tensile" cracks under generally compressive states of stress. It is also shown that bed separation and high capacity props are desirable in mechanized longwall mining, a result in keeping with operating experience. Although speculative at this time, the analysis provides a rational working hypothesis as regards the problem of strata flexure and control. | he purpose of this paper is to present an analysis of the flexure of geologic strata as a problem in the bending of a sheet of material failing in accordance with a Mohr-Coulomb criterion. The flexure of strata has an obvious academic interest to the geologist concerned with the mechanics of folding. It is of interest to the economic geologist as it relates to the structural control of certain types of ore deposits. It has an intimate association with mine subsidence phenomena, and is of concern to the mining engineer. Strata flexure is also the dominant feature of roof behavior about longwall workings. An improved understanding of strata flexure through a rational mechanical analysis thus appears desirable not only from the academic view but from the economic one as well. In the field, the most commonly observed feature of folding, subsidence, and longwall roof behavior is the permanent and therefore inelastic nature of the strata movement. Fig. 1 illustrates the physical disposition of strata in the vicinity of a longwall face. Inasmuch as most rocks (with the possible exception of certain evaporites) do not exhibit significant viscoelastic behavior, at least not over time spans of engineering interest, a plastic analysis is indicated. The analysis is meant to apply to strata whose deformation is dominantly that of bending such as might be expected in the remote roof about a longwall face.

Jan 1, 1970

By Cyril Wells, Robert F. Mehl

THE practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out 1,13 This importance ties chiefly, though by no means only, in the study of carburizing and in the study of reactions involved in the eutectoid inversion in steel The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in y-Fe and their mutual effects are measured with precision The present paper reports the results of meas¬urements of diffusion coefficients D of manganese in -y-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients [$] Data on the rate of diffusion of manganese in y-Fe have been reported by Fry2 and by Paschke and Hauttmann 3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq cm per sec at 960°, which will be shown to be incorrect by many orders of magnitude Paschke and Hauttmann gave a rough value of 9 6 X 10-8 sq cm per sec at 1400° Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon METHOD AND MATERIALS Method -The method employed is identical with that used earlier 5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded The diffusion anneals were performed in argon, except one (test 18) in which hydrogen was employed for purposes noted below The temperatures reported are accurate to about 3° and constant within I°C , the diffusion times are reported to the nearest half hour The specimens were furnace-cooled after the diffusion anneal at about 2° per min Layers, usually 0 004 in thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0 01 per cent Mn, the distances of these layers from the interface was measured to ±0 0002 in The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions e The D values calculated by these two methods do not differ appreciably 5 The Grube solution was used except in tests in which the effect of concentration upon D was greater than 50 per cent, in such cases the Matano method, which explicitly provides for the variation of D with concentration,1 is the more reliable In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer In 3 of the 30 tests, however, this is not justified, and the D values

Jan 1, 1941

By B. S. Hickman

Using primarily quantitative single crystal X-ray techniques studies have been made of the precipitation of the metastable w phase in alloys of titanium with Mo, Mn, Fe, Cr, and Nb. It is shown that, in agreement with earlier work on the Ti-V system, the composition of the w phase during aging approaches a constant; the value varies from one system to another in a systematic manner with the electron concentmtion. Results relevant to the mechanism of w precipitation during quenching and during aging are presented and discussed. Results are presented to confirm that the w phase is coherent and the nzorphology of the Necipitates is described and discussed. PRECIPITATION of the metastable w phase in alloys of titanium is of interest because of its severe embrittling effect and also because of the enhancement of the superconducting properties which accompanies precipitation.1 The general features of w phase precipitation have been discussed by cuillan and by Bagaratskii et d3 The work described in this paper forms part of a general study of w phase precipitation which was undertaken to elucidate various unknown or controversial features of the process, namely: i) What is the mechanism of formation of the phase ii) How does its composition, morphology, volume fraction, and particle size vary with the type and content of the alloying element and with the heat treatment conditions? iii) What is the relation between the w phase and the equilibrium a phase? In a previous paper4 the results of a detailed study of w phase in Ti-V alloys were presented. It was shown that: U During aging the composition of the w phase approached a saturation value of 13.5 to 14.0 at. pct V. ii) w precipitated as cube shaped particles and once precipitation was complete, particle coarsening did not occur. iii) a phase formed initially by direct conversion of w-phase precipitates. In this paper similar measurements are reported on Ti-Mo alloys and some more limited data given on the Ti-Cr, Ti-Fe, Ti-Mn, and Ti-Nb systems. The results i.1 the six systems are then compared. It has been shown previously by electron microscopy that the w precipitates as ellipsoids in both the Ti-Nb system,&apos; and in i-o.&apos; Blackburn and williamsz3 have reported the precipitates in Ti-Fe, Ti-Cr, and Ti-Mn are cubic, i.e., similar to the Ti-V system.476 EXPERIMENTAL METHODS 1) Specimen Preparation. Samples of the compositions shown in Table I were prepared by arc melting. High purity electron beam zone refined titanium (Materials Research Corporation Grade I—total impurity content =250 ppm) was used; the other source materials are given in the table. A commercial Ti-8 wt pct Mn alloy was used for studies of this system. After homogenization the materials were rolled or cut into strip approximately 1/4 in. by 2 in.; the strip was then heated at temperatures of 1200" to 1300°C for several hours by passage of a direct current through the strip in an ultra high vacuum system (<10-torr) and then quenched by admitting high purity helium and switching off the current. This treatment resulted in crystals up to 2 in. by 2 in. by A in., almost all of which had a [100] direction nearly perpendicular to the plane of the strip. The crystals were cut from the strip by spark machining and their composition checked by lattice parameter measurements supported by chemical analysis. 2) X-Ray Diffraction Methods. Lattice parameter measurements were made using a modification of the single crystal spectrometer described by ond. In this technique the crystal angles for reflection on either side of a highly collimated primary beam are measured. Generally the 400 CuK, or the 400 CuKp reflections of the bcc lattice were used. In the as-quenched crystals a precision of 1 in 105 was obtained, but due to line broadening the parameters in aged materials could only be measured to 1 in lo4. This accuracy was, however, quite adequate for the purposes of these experiments and enabled the composition of the p phase to be obtained to 10.1 pct in all systems except Ti-Nb where the lattice parameter change with composition is very small. The precipitation and growth of the w phase was examined using a single crystal goniometer attached to a Phillips diffractometer. The relative intensities and line shapes of b-phase and w-phase reflections

Jan 1, 1970

By J. Szekely, V. Stanek

Heat and gas flow interactions in nonisothermal packed beds were examined in the paper. A study was made of the response of the system to a step or pulse change in the inlet gas temperature, with a fixed value of the overall pressure drop across the bed. Under these conditions the heat flow and fluid flow transients are coupled because the convective heat transfer rate is alfected by the mass flow rate of the gas which, in turn, for a fixed pressure drop will depend on the temperature profile in the system. The Problem was stated in terms of differential equations, which were integrated numerically. The parameters used in the computation were so chosen to reflect the operation of the stack region of blast furnaces and sinterbeds. The computed results showed that the pressure drop-flou1 relationships and the rate of progress of the temperature fronts (waves) were strongly interrelated and were also markedly affected by variations in particle size and in void fraction. MANY metallurgical processes involve the contact of solid particles with a gas stream in a packed bed arrangement under nonisothermal conditions. Examples are shaft furnaces, regenerators, pebble heaters, and the sinter process. Although the heat and mass transfer aspects of packed bed processing have been extensively studied, the associated flow phenomena and in particular the effects of nonisothermality on the flow, have received little attention to date. :In fact, most of the previous workers considered the flow rate of the carrier gas time invariant and independent of the heat or mass transfer processSzekely and carr2 have shown that the pressure drop-flow relationships in nonisothermal packed beds may be strongly affected by the temperature profile within the system. These authors have devised a method for relating the pressure drop to flow for a given temperature profile. thus providing an extension of the Ergun equation to steady nonisothermal systems. Finally, in a recent paper willmot3 examined the response of regenerators to externally imposed changes in the gas flow rate. Both these investigations were somewhat specialized since, in general, neither the temperature distribution nor the gas flow rate may be regarded as truly independent variables, thus the heat transfer and the fluid flow problems have to be solved simultaneously. The work reported here is divided into two parts: in Part 1 the general formulation is given and a detailed discussion is presented of fixed bed systems. Part is devoted to systems in which a gas and particulate solids are contacted in a counter flow arrangement. FORMULATION Consider a nonisothermal fixed packed bed, extending from through which a gas is flowing. The problem is to develop a relationship between pressure drop and gas flow (with the gas flow being the dependent variable) and to evaluate the rate at which a change in the gas temperature, imposed at the inlet, travels through the system. Let us consider an infinitesimal section of the bed and establish differential heat, mass, and mechanical energy balances over this region. In addition, relationships are needed describing the temperature dependence of gas density (equation of state) and the temperature dependence of viscosity. These may be written as: where c, and are constants. It is noted that in this formulation we neglected any temperature gradients within the solid particles, thus assuming these to be either sufficiently small or of sufficiently high thermal conductivity to meet this condition. The justification and consequences of this assumption will be mentioned in the discussion.

Jan 1, 1970

By Alan Arias

On grinding in pure water, zirconium, tantalum, iron, and stainless-steel powders were extensively comminuted and simultaneously oxidized with hydrogen release, whereas nickel, copper, and silver powders did not react with water and their particle sizes increased. On grinding nickel, copper, and silver in water pressurized with oxygen, nickel and copper became extensively comminuted and were oxidized, whereas silver did not react with oxygen and its particle size increased. From these results and other considerations , it is hypothesized that for extensive comminution of ductile metals and alloys to occur on grinding they must react with the grinding media. UlTRAFINE metal and alloy powders are finding an ever-growing number of applications in metallurgy and in other fields.&apos; Of particular interest are ultrafine metal and alloy powders suitable for dispersion strengthening.2&apos;9 Various research programs on dispersion strengthening are being carried out and in some of these programs the ball-milling method is being used to produce dispersion-strengthened materials. This method usually involves the simultaneous grinding of metal or alloy and a dispersoid followed by consolidation of the resulting powder mixture. To obtain the ultrafine powders required for dispersion strengthening,&apos; grinding is carried out in many liquids, including aqueous and nonaqueous media, with or without grinding aids.4&apos;5 Nonaqueous liquids usually contain water as an impurity and some grinding aids may contain water of hydration.5 The water present may affect the grinding process. The writer has shown5 that. on ball milling chromium in water, the chromium is oxidized and hydrogen is released. It was surmised that the same reaction may occur on ball milling other metals and alloys in waterbearing liquids. Therefore, the investigation of ball milling in water was extended to metals and alloys other than chromium. In the course of the investigation, however, it became apparent that the data-to-gether with the results from a few additional experi-ments—could be used to postulate a comminution mechanism for ductile metals and alloys. A well-known comminution theory is that of smekal.7 According to this theory, comminution is possible because of the weakening effects of surface cracks and other imperfections in materials. This theory imposes a lower limit of about 1 µm for the ground particles. The beneficial effects of liquids and additives on the rate of grinding are well known.8 Mechanisms by which liquids and additives may aid in grinding were reviewed by Rose and Sullivan.&apos; One aspect of these effects is based on Rehbinder&apos;s theory of crack propagation in materials under stress.9 According to Reh-binder&apos;s theory, liquids or additives may promote the spread of cracks in stressed materials by lowering the surface tension at the crack tip. Rose and Sullivan surmise that the same mechanism may be operative during grinding, thereby facilitating comminution of the particles. In addition, Rose and Sullivan reviewed how additives may act as dispersants as a result of their being adsorbed on the surface of the particles being ground. This concept has been suggested by Quatinetz, Schafer, and smea15 to explain from their experiments the major role of additives that enabled them to grind metal down to 0.1 µm. Discussions of other comminution theories and additional sources of material on the subject will be found in Ref. 10. None of these previous suggestions and theories, however, can account for all phenomena encountered during ball milling of metals to submicron size in this and in a previous investigation by the author.6 The objectives of this investigation were to determine the behavior of metal powders during ball milling either in pure water or in oxygenated water and to gain an insight into the grinding mechanism. Zirconium, tantalum, iron, nickel, copper, and silver powders were ball-milled in pure water. These metals were selected because their oxides cover a wide range of free energies of formation. For comparison purposes, an alloy-type 430 stainless steel-was also ball-milled in pure water. The pressure of the hydrogen released during ball milling was monitored in order to determine the oxygen that combined with the metal or alloy. In order to obtain more information on the nature of the grinding process, nickel, copper, and silver powders were also ball-milled in oxygenated water (water pressurized with oxygen). The oxygen that reacted with the powders was determined from the pressure decrease in the mills. The powders resulting from ball milling in pure water and in oxygenated water were subjected to surface area, optical microscopy, and X-ray diffraction analyses. With these data, the oxygen calculated to be combined with the metals during ball milling, and comparison of the free energies of formation of the oxides of the milled powders with that of water, a comminution mechanism was postulated. MATERIALS, EQUIPMENT, AND PROCEDURES The materials used in this investigation were powdered metals, deaerated distilled water, high-purity helium, and commercial grade (99.5 pct purity) oxygen. The powdered metals used were zirconium, tantalum, iron, nickel, copper, and silver. A 16 pct Cr, ferritic stainless steel, type 430, was also used. The purities (or nominal compositions) and the surface areas of these metals and the alloy are given in Table I.

Jan 1, 1970