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By F. H. Vitovec, D. W. Hoeppner

Pusk-pull fatigue tests were conducted on copper tricrystals of 99.988 pct purity to ascertain the role of grain boundaries in the initiation and propagation of fatigue cracks. Significant differences in behavior were found for specimens which possessed different transverse-boundary misorientation. In speciwens with low boundary angles cracks initiated within the transverse boundary, while higher angles led to transcrystalline fatigue failure. It is suggested that at low angular misorientation moving dislocations may interact with dislocations of the boundary or dislocations present in adjacent pains on favorably oriented glide planes, thus initiating a fatigue crack. MANY fatigue studies have been concerned with fatigue-crack initiation within grains and the mechanism causing initiation and propagation1-3 Although the initiation of fatigue cracks in or near grain boundaries of pure metals has been observed and reported in the literature, the mechanism of this phenomenon has received little attention.4"11 EXPERIMENTAL PROGRAM Testing Procedure. To investigate the role of grain boundaries regarding initiation and propagation of fatigue cracks, copper tricrystals were tested in push-pull. Axial-stress tests were used to avoid the stress gradients introduced by stressing of some other nature. Copper was selected as the most suitable test material since extensive work has been done on the formation of fatigue-induced slip in copper. Tricrystal specimens were used to provide a grain boundary geometry with one boundary transverse to the principal stress axis and one or more boundaries nearly coincident with the direction of maximum resolved shear stress. The boundary energy and the slip characteristics in the vicinity of the transverse boundary depend on the relative orientations of grains across the boundary. Testing was done at room temperature, at a frequency of 700 cpm, in an atmosphere of either air or argon. It is known that the incidence of grain boundary cracking increases with increasing temperature and decreasing frequency.4 The fatigue machine applied a uniaxial tension-compression load to the specimen by a flat spring which was actuated by an adjustable eccentric. Use was made of an adjustable head and a load cell which had strain gages mounted at 120-deg intervals around its periphery, thus providing a means for eliminating any detectable superimposed bending moment. A clip gage was mounted between the gripping heads to record the cyclic strain amplitude applied to the specimen. Each specimen's hysteresis characteristics were recorded by supplying the load and strain signals to an oscilloscope. Microstructural changes were observed and recorded with an optical microscope which was mounted on the fatigue machine. Immediately prior to insertion in the machine, each specimen was chemically polished. Extreme care was exercised while inserting the specimen in the test machine to avoid either bending the specimen or introducing a mean load. Each specimen was stressed in the tensile direction first and subsequently the load was reversed. Specimen Preparation. Tricrystal fatigue specimens of 99.988 pct Cu were grown from the melt using a modified Bridgman technique. Ingots about 1 in. high were grown to the configuration shown in Fig. 1. Upon sectioning the resultant ingot, several specimens were provided with an identical shape and grain boundary orientation. Except for plane sectioning and final polishing, this method eliminated machining the specimens. The apparatus used for growing the tricrystals is shown in Fig. 2. A spectrographically pure graphite mold, Fig. 3, was inserted in a vycor tube which was mounted on a vertical zone-refining table. Prior to insertion in the tube the mold was assembled as follows. The insert and graphite rods were fixed in position in the mold. The copper was then placed in the mold and the entire mold assembly was positioned in the vycor tube, Fig. 2. At this point the tube was sealed, evacuated, purged with helium gas, and finally placed under a slightly positive helium pressure. The heating coil was then adjusted to melt the copper charge, after which it was raised at a speed of 4 in. per hr. It is also possible to use

Jan 1, 1964

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

By W. C. Winegard, J. R. Carruthers, A. Plumtree, L. R. Morris

The unidirectional solidification of dendrites containing central twin planes was studied in A1-Ti alloys. Once nucleated, the twinned dendrites are a Twore ejficient form for solute redistribution and therefore grow in preference to the normal columnar dendvites. Comparison of these twinned dendrites to adjacent colunmar dendrites by means of decanting experinzents and electron-probe rnicvoarmlysis indicates that these special dendrites grow with less undercooling than normal dendrites. These findings are further supported by the effect of forced convection on the dendrite morphologies. COMMERCIAL semicontinuous cast ingots of most aluminum alloys frequently exhibit large grains which appear to be composed of hundreds of parallel, continuous, thin lamellae. This structure has been termed "basaltic",' "fiederkristall", or, commonly, "feathery grain". The lamellae are 'about 100 p thick, several inches long, and each lamella contains a central (111) coherent twin boundary. The feathery grain has been reported to have a (112) direction2 and a (110) direction4 in the twin plane parallel to the casting direction, in contrast with the usual columnar structure where a (100) direction predominates. Aust et uZ.~ proposed that the twin boundaries were growth twins nucleated by stacking faults on the octahedral planes. chalmers6 has suggested that feathery grain may grow by a re-entrant edge mechanism, as proposed by wagner7 for twinned dendritic growth in germanium. Cahn et ~1.~ have concluded that the occurrence of feathery grain is evidence of some form of lateral layer growth rather than the atomically continuous growth normally observed in metals. The postulates by Chalmers and Cahn would seem to be contradicted by the work of Nakao~"' who showed that feathery grain only occurs when growth rates are high and the aluminum contains some solute. Specifically, Nakao found that in order to obtain feathery grain, in small castings solidified unidirec-tionally upward, the rate of growth must be above 2.4 cm per min and a critical solute concentration must be present. Below this solute concentration the grain structure was totally columnar. The critical solute concentration was found to be approximately: 0.04 wt pct Ti, 2 wt pct Cu or Mg, and 8 wt pct Zn. As pointed out by Chalmers it is not obvious why a twin-plane re-entrant edge mechanism would occur in aluminum which is thought to have a diffuse solid-liquid interface. The present experiments were undertaken to determine the growth mechanisms in- volved and to study the solute segregation in more detail. EXPERIMENTAL PROCEDURES Alloys ranging in composition from 0.05 to 0.23 wt pct Ti* were prepared from 99.9 pct pure Ti and 99.993 pct pure Al. Two-hundred-gram samples of A1-Ti binary alloys were solidified unidirectionally and vertically upward from a water-cooled copper base, in a heated insulated mold. The 1-in.-diam, 6-in.-length mold was made of Marinite (manufactured by Johns-Manville Co.). The mold was attached to a 24-in. pivoted arm such that by dropping a weight the mold was rotated 180 deg, throwing the liquid metal from the solid. In this way, the solid-liquid interface was revealed by decanting. A sketch of the decanting mold is shown in Fig. 1. The alloy was poured into the mold at temperatures ranging from 680" to 750°C, partially solidified by water cooling from the base, and decanted after a measured time interval. Growth rates for each metal-pouring temperature were calculated from solidification-time vs length solidified curves. Temperature gradients in the melt were measured using four No. 34 gage thermocouples which protruded into the mold cavity. Grain orientations were determined by X-ray diffraction using Laue back-reflection techniques. Grain substructures were examined metallographically, using polarized light, by applying a thin epitaxial anodic film to polished sections after the method of Hone and pearson." Titanium micro segregation was measured by electron-probe microanalysis using a NORELCO AMR/~ with a mica crystal and proportional-flow counter. Several of the cast samples exhibited feathery and columnar dendrites growing in the same direction and

Jan 1, 1967

By Robert C. Freas

Lime, the versatile chemical is, generally speaking, a calcined or burned form of limestone commonly known as quicklime, calcium oxide or, when water is added, calcium hydroxide or slaked lime. Almost 40 different lime products are available, a fact which has contributed to the rather loose use of the term lime as well as to confusion and misunderstanding. The term is frequently, albeit erroneously, used to denote almost any kind of calcareous material or finely ground form of limestone or dolomite. Lime is made from high calcium or high magnesium limestone, generally having a minimum of 97% combined carbonate content. Normally, high calcium lime has less than 5% MgO. When the lime is produced from a high magnesium limestone, the product is referred to as dolomitic lime. Calcination/Hydration Calcination, or the production of lime, has its origins in the earliest days of alchemy, with the general reaction class having been identified in an Arabic text printed in 1000 AD. It was much later, however, in the mid-1700s to the mid-1800s before this basic reaction became understood from scientific perspective. The pro- duction of lime has been so basic and simple that its underlying scientific principles have over the years received only intermittent investigation. Rather, much of the thought and inquiry has been directed toward the development of kilns. Thus, it has only been in the last 25 to 30 years that lime has received any concentrated scientific investigation relative to the thermodynamics and kinetics of the calcination and hydration reactions. Particular emphasis has been focused upon energy consumption and fuel efficiency. Calcination refers to a broad class of reactions, of which the limeflimestone reaction is just one, wherein a substance is heated to less than its melting point, resulting is a weight gain or weight loss. In the calcination of limestone to produce lime, the basic chemical reaction is as follows: [ ] While there is nearly universal agreement bout the equilibrium conditions related to the limestone/lime reaction above, there have been numerous and varied calcination models developed for the reaction. Recent investigations have resulted in the development of the model shown in [Fig. 1]. From this model it can be seen that calcination is a function of both temperature and CO, pressure. It does not, however, provide any indication of the rate at which the reaction takes place. Calcination is strongly time variant with different limestones. In a very broad sense this relates to the fact that the calcination reaction starts on the exterior surface of the limestone and then proceeds toward the center. As the calcination reaction takes place, the CO2 released at the interface must make its way through the lime to the exterior surface. Since calcination is limited by gas diffusion to the surface of the partially calcined limestone, the natural impurities in the stone, differences in crystallinity, grain boundary chemistry, density variations, and imperfections in the atomic lattice all play a significant role in calcination rate. Therefore, the suitability of a given limestone as a source material for lime production can be determined only after completion of adequate burn tests designed to evaluate the various limiting factors. When a coal-fired kiln system is considered, the entire process of calcination is made even more complex by the introduction of additional chemical constituents into the calcination environment. The reader is referred to the references for a more detailed description of the complete calcination reaction and the differences inherent between differing kiln systems. In the foregoing discussion it was noted that CO2 is released during the reaction. This release results in a 44% weight loss during the complete calcination of a high calcium limestone, or a 48% weight loss for a highly dolomitic limestone. The trade term for this weight percent loss is loss on ignition, or LOI. This weight loss is frequently used as a measure of the completeness of calcination. Because the calcination reaction is chemically reversible, quicklime or burned lime is frequently referred to a being highly reactive, or unstable. The more stable form of lime, hydrated lime, is commonly preferred and generally specified by the user. Hydrated lime is obtained by adding water to quicklime to produce a dry, fine powder. Quicklime's affinity for moisture is then satisfied, although it still retains a strong affinity for CO2.

Jan 1, 1994

By P. B. Baxendell

The performance of a water-drive reservoir having a gas cap depends primarily on the movement of the gar-oil and oil-water contacts. The movement of the contacts during production depends in turn on fluid withdrawals and how the reservoir pressure changes as fluids are produced from the reservoir; that is, on how effectively the aquifer maintains pressure by replacing withdrawals. inasmuch as pressure changes, fluid withdrawals, contact positions, and produced gas-oil and oil-water ratios are interdependent, the analysis and prediction of the performance of a reservoir produced in a given way must take into account this interdependence throughout depletion. This paper presents an analysis which, within the limitations of the assumptions made, yields an engineering approach to predicting future performance based on reservoir pressure and production history. The most significant assumption is the method of extrapolation of future gas-oil and water-oil ratios. The extrapolation procedure smoothly increases both ratios to preselected values as the remaining oil column undergoes a specified decrease in thickness. This preselection is made on the busis of previous field experience in depletion of similar reservoirs under similar conditions. For computing future performance a vdumebic balance L combined with the differential equation defining pressure distribution in the aquifer to obtain positions of water-oil and gas-oil contacts. From these positions are extrapolated produced water-oil and gas-oil ratios. Reservoir performance can be investigated when oil production rates are dependent upon various factors including the performance of the reservoir itself. Examples of practical application of the procedure are included. INTRODUCTION To predict performance of water-drive reservoirs with gas caps and thin oil columns, it is necessary to describe the motions of the fluids within the reservoir during the entire production period to depletion. These motions depend on the pressure changes and on the withdrawal of oil, gas and water. Production of oil from the oil zone primarily causes water to move in to take its place; production of gas from the cap tends to cause oil to migrate into its place. In addition, the volumes of oil and gas remaining in the reservoir depend on changes in the pressure, since a decrease in pressure causes fluid expansion, gas liberation and oil shrinkage. A method of relating the future pressure to total withdrawals is used to describe the motions of fluids within the reservoir under conditions arising in possible modes of production. The analysis is based on two relationships and will reduce the problem to one amenable to digital computation. The first of these concerns the dependence of the pressure distribution in the entire aquifer furnishing the water drive upon the total reservoir withdrawals. This dependence is dictated by the permeability distribution and the extent of the aquifer; at present, such information is most readily obtained from the performance history by means of the resistancecapacitance reservoir analyzer. The second relation involves withdrawals, pressure in the reservoir, and movement of oil, gas, and water within the reservoir. The analysis is subject to certain simplifying assumptions that are necessary to permit solution of the problem. A comparison of the methods of this paper with those presently practiced is pertinent. One method of analysis is to use the reservoir analyzer to predict reservoir behavior based on aquifer characteristics determined from production history. Inasmuch as the total withdrawal rate depends upon the gas-oil and water-oil ratios, which depend in turn upon, among other things, the positions of the gas-oil and water-oil contacts, these ratios must be assumed in advance. In this paper these ratios are, instead, related to the computed positions of gas-oil and water-oil contacts. Thus, our method can be applied to problems in which the oil production rate is limited by produced gas-oil ratio, or to problems in which it is desired to determine the variable gas injection rate that will maintain the gas-oil or water-oil contact stationary. These problems cannot be worked satisfactorily on the analyzer. Another method presently used is based on a paper by Hurst.' Since his procedure is dependent upon using the solution of the heat flow equation, which requires constant permeability within the aquifer, and our procedure recognizes variations of permeability in

By K. R. Evans

The yield and fracture characteristics of a Ti-8 pct A1 alloy have been examined at room temperature as a function of exposure temperatures to 1700°F. Em-brittlenzent of the alloy is observed to occur following exposures below 1280°F, the critical temperature for formation of ordered Ti3Al particles. Presence of Ti3Al particles results in an increase in the yield and flout stresses which, for a given exposure time, are a maximum at the critical temperature. Embrittlement is attributed to the occurrence of plastically induced fracture controlled by the increase inflow stress. This interpretation is compatible with the decreasing ductility and increasing crack popagation rates observed with increasing exposure time below the critical temperature. Slip line observations and measurements of the gain size dependence of the yield stress indicate that the slip character of the alloy is not influenced by exposure treatments below the critical temperature. ThE potential usefulness of Ti-A1 alloys in structural applications has prompted considerable interest in studies of their microstructure and mechanical characteristics. The relatively recent surge of interest in the system and at the same time its complexities are indicated by the fact that despite numerous recent efforts14 there has not even been general agreement upon a phase diagram for the system. However, most of the Ti-A1 alloys of commercial interest range in aluminum content from 5.0 to 8.5 wt pct where most investigators achowledge the existence of the ordered Ti41 phase. Goldak and parrs confirmed the existence of Ti41 from X-ray diffraction analysis of the stoichiometric composition while Blackburn6 has determined its presence in commercial Ti-8 pct A1 alloys by electron diffraction analysis and dark field transmission microscopy. The embrittlement of Ti-8 pct A1 alloys was initially reported by Crossley and carew7 who showed that aging in the temperature range of 750" to 1110°F resulted in extreme brittleness. This behavior was later confirmed and correlated by Soltiss to the presence of long-range order in the commercial Ti-8 pct Al-1 pct Mo-1 pct V alloy (Ti-8-1-1) which exhibited anomalous creep and yield strength behavior at 950°F. This investigation was designed to study the mechanical characteristics of a binary Ti-8 pct A1 alloy in order to further examine the nature of the embrittlement behavior reported for the alloy system. EXPERIMENTAL PROCEDURE A Ti-8 pct A1 binary alloy was obtained from the Wah Chang Co. in the form of 0.050 in. sheet. The chemical composition of the alloy is given in Table I. Heat-treatment of the alloy was conducted in evacuated vycor capsules for the tensile sDecimens (1.25 bv 0.25 in. gage section) and in evacuated stainless steel jackets for the crack growth-rate panels. All specimens were annealed at 1700°F for 24 hr and water quenched before an exposure at elevated temperatures. Tensile testing was conducted at room temperature in an Instron testing machine equipped with a pushbutton control for instantaneous control of the cross-head motion. In this manner the change in stress, Aa, accompanying an increase in strain-rate by a factor of 10 was measured immediately after yielding. The crack growth-rate panels used were 3 by 18 in. with a precrack 0.33 in. long cut into the center of the panel. The panels were cycled at a maximum gross stress of 40,000 psi at a maximum to minimum tension stress ratio of 20. Cycling of the specimens was continued until the crack propagated the width of the panels. The crack length was intermittently measured during slow crack growth. EXPERIMENTAL RESULTS Correlation of Embrittlement to the Critical Temperature for Ordering. Blackburn6 has found that the critical temperature, T,, for the formation of Ti41 in a Ti-8 pct A1 alloy with an interstitial content on the order of that given in Table I is approximately 1245°F. The relationship between the ductility of the binary alloy used in this investigation and T, was estimated from tensile tests on specimens which were exposed for 24 hr at various temperatures followed

Jan 1, 1970

A simulation program has been developed tc predict the airflow distribution and thermal environment in multi-level narrow lode Cornish =n mines. Because of the approximate equality between fan power and natural ventilation _rergy a true thermodynamic mesh balance using mass flow rather than volume flow rate was required. Compressibility is allowed for by calculating mesh corrections on a mass flow of dry air basis. In this context, and within the confines of any steady state model, both the steady flow energy and pressure equations are satisfied with equal validity. The mesh balance includes natural ventilation energy, frictional losses, moisture lift work, water droplet energy and fan energy.

Jan 1, 1988

Develop technology for preparing thick corrosion-resistant coatings and electroforms of iron-chromium-nickel alloys. Approach To reduce the United States' dependence upon foreign sources for supplies of strategic and critical metals such as chromium, cobalt, and nickel, new technology must be devised to conserve these valuable commodities. One approach being investigated by the Bureau of Mines is the use of a modified-aqueous-electrodeposition method to prepare thick (-25 µm), complex alloy coatings (e.g., stainless steel composition) with properties similar to the commercial alloys. An alloy coating on a low-alloy steel or carbon steel substrate would require significantly less strategic and critical metals than those contained in an equivalent mass of the commercial alloy. Coatings applied to appropriate mandrel materials make possible the preparation of intricately-shaped alloy electroforms (near-net-shape parts). As a result, the loss of valuable metals associated with machining finished products would be minimized.

Jan 1, 1986

By MCA Woolsey

(Butte. Meeting, August, 1913.). IN metallurgical circles it is known widely, but somewhat vaguely, that the ease of: reduction of metallic oxides depends largely on the way they have been prepared. It is likewise known that different forms of carbon have different and greatly varying reducing powers. It is the purpose of this paper to show somewhat more definitely and scientifically these facts. Some years ago the writer published an account of pyrometric determinations of the reduction- temperature of zinc oxides variously prepared and of several kinds.1 In said paper it was shown that the temperature it which zinc oxide evolves zinc according to the equation Zn0. +' C = Zn + CO depends upon the ;nature of:., the.' two reacting bodies. The determinations bad a range of accuracy of from 2° to. 6° C.,whereas differences were found to. amount to an extreme. of 90° C. :.86 the differences are real ones and must have, definite cause. The equation of boiling water, (H20)4 = 4 (H2O) has a fixed temperature for equilibrium of 100° C. at 760 mm. pressure. , In general, all equations. reacting e in .the liquid or the gaseous phase have-well-defined constant physical conditions which govern the equilibrium point and reaction velocities. In a reaction where we have one or more solid phases, the temperature conditions requisite for the unbalancing of the stable system are found to vary. These variations are due to the fact that in a solid there is a very complex molecule and it is not, a question solely of the tearing away of two interlocked atoms, but also of the destruction of a complex molecule containing hundreds, or possibly thousands, of smaller molecules.

Jan 7, 1913

By R. O. Day, R. S. Dean

In constructing a theory of the flow and hardening of metals, v necessarily make use of such phenomena as seem to be universal1 observed in metals. It is, therefore, a matter of concern to the con structors of such mnemonic systems if one or two of the group classific as metals show anomalous behavior. Such egregious phenomena observed in pure or nearly pure iron in the reaction of its mechanic properties to low-temperature annealing after cold work and to increase temperature of testing. In short it has been generally observcd tha iron, as an outstanding exception among metals, increases its hardnes and strength by low-temperature annealing after cold work,' and alt by increase of testing temperature to the range of 150" to 300" C. The investigation here recorded was made then with the object ( ascertaining if similar phenomena were observed in high-purity iro and, if not, to the presence of which impurities these phenomena coul be traced. Experimental Procedure Three kinds of iron were taken for a study of hardening by rehcatin after cold work: 1. Vacuum-melted electrolytic iron; melted in an Arsem furnace in a magnesia crucible. That this iron was of high purity is indicated b a magnetic permeability above 20,000. 2. Electrolytic iron melted in air in a small laboratory furnace. 3. Armco iron, commercial material. These materials in the form of forged bars, annealed at 980" C. in vacuum, were reduced 30 per cent. in thickness by cold rolling and the reheated to temperatures varying from 100' to 500' C. The Rockwe hardness number was measured after each treatment. The results and shown in Fig. 1, curves 1, 2 and 3.

Jan 1, 1929

By AIME AIME

LEWIS EMANUEL YOUNG was elected a Director of the A.I.M.E. at the last Annual Meeting as a representative of District '4, including. Ohio, West Virginia, and western. Pennsylvania and New York. He also represents the Coal Division, in which industry lie has actively participated- for nearly twenty years. Dr. Young was horn in Topeka, Kan., Oct. 1, 1873, received mining degrees from Penn State and ,-Iowa. State, and a Ph.D., from Illinois. The first part of his professional life was spent in teaching first as instructor in mining at Iowa State, second .as professor of mining at the Colorado School' of Mines, third as director of the School of Mines and Metallurgy at Rolla, Mo., and finally he taught business

Jan 1, 1937

By Jürgen Brune, Purushotham Tukkaraja

This editorial introduces a special focus issue on mine ventilation innovations. It highlights key areas such as ventilation on demand, automation, thermal management, atmospheric monitoring systems, and prevention of mine fires and explosions. The issue aims to address the critical role of mine ventilation in maintaining the health and safety of miners.

Mar 21, 2022

By T. L. MacKay

Oxidation rates of single-crystal and poly crystalline zirconium in oxygen at temperatures from 307° to 815°C obey the parabolic rate law for short ex-posure time, 4 to 6 hr. The activation energy for the oxidation of single-crystal zirconium between 420° and 790°C is 42.6 ± 0.7 kcal per mole, and in the temperature range 307" to 600°C the activation energy for oxidation of poly crystalline zirconium is approximately the same. The high-activation energy is indicative that diffusion through the bulk oxide film is the primary mode of mass transport for both types of metal. The higher oxidation rates for poly -crystalline zirconium in this temperature range were attributed to differences in the orientation of the grains in the metal with respect to the oxidizing surfaces. Above 600°C, vain growth was observed in polycrystalline zirconium, and the oxidation rates approached those of single-crystal zirconium. ThE kinetic data of previous oxidation studies1-' of zirconium in oxygen have been interpreted by both parabolic and cubic rate laws. There is some evidence that there is a transition from the parabolic to the cubic rate law at prolonged exposures, but the question is still controversial. For the parabolic rate law activation energies are reported in the range 18.6 to 35 kcal per mole, and for the cubic rate law in the range 38 to 47 kcal per mole. So far as the mechanism of zirconium oxidation is concerned, inert marker studies10,11 have indicated that the oxidation proceeds by oxygen (anion) diffusion through the oxide film toward the metal-metal oxide interface. Pemslerl2 observed that the orientation of the grains in the zirconium metal substrate affected the rate of formation of the oxide film on the surfaces of the grains and that the orientation dependence of the corrosion rate persisted beyond the initial stages of reaction. The rate of oxidation was a minimum when the c axis of the grain was parallel to the surface of the sample, and rose to a maximum when the c axis was inclined at about 20 deg to the plane of sample surface, and decreased again at higher inclinations. cox13 observed that in 300°C steam a thin oxide film was formed initially on zirconium and that this oxide film, which exhibited interference colors, became dark first along the grain boundaries and then over the whole surface in an inhomogeneous manner as the film thickened. Cox proposed a mechanism in which oxygen diffused along preferred paths created by grain boundaries in the metal and formed a much thicker film at or near the grain boundary than on the central zone of the grain. In the present study, the oxidation rates of single crystals of zirconium were measured in oxygen and compared with the oxidation rates of polycrystalline zirconium of the same bar stock. It was felt that such a comparison would elucidate the role of grain boundaries in the metal substrate. SAMPLE PREPARATION Single crystals of zirconium were prepared by following the procedure of I3apperport,14 starting with 1/4-in. rod purchased as crystal-bar zirconium. Zirconium rods 2 in. long were wrapped in tungsten foil and sealed in quartz tubes at pressures of less than 10-6 mm of mercury. Large single crystals were grown by thermal cycling above and below the a-/3 transformation temperature, 862°C. Several specimens were simultaneously subjected to the same cycling procedure, heating to 1200°C, holding for 4 hr, then cooling in the furnace and holding at a temperature of 840°C for 5 to 10 days. This cycle was repeated five or six times for each set of specimens. The grain size of the crystal-bar zirconium before thermal cycling was between 10 and 30 p. Fig. 1 shows the microstructure of an end section of as-received crystal-bar zirconium. A longitudinal section of each zirconium rod after thermal cycling was polished and examined under polarized light, see Fig. 2, and the largest single crystals were selected for this study. Zirconium rods 1/8 in. in diameter and 1/2 in. long with spherical ends were machined from the single crystals and from the as-received bar stock. An X-ray examination showed that the c axis of the single crystals made either a 34-deg or an 89-deg angle with the rod axis. The specimens were chemically etched for 2 min in solution consisting of 15 parts hydrofluoric acid (48 pct), 80 parts nitric acid, and 80 parts water. The chemical polish removed 1 to 2 mils from the surface. EXPERIMENTAL The Sartorius vacuum microbalance used in this study has a sensitivity of 0.5 pg and a capacity of

Jan 1, 1963

By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.' More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.' This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.' These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer's6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

By Erhard M. Winkler

The rapid decay and disfiguring of stone monuments in urban and desert rural areas has challenged conservators to protect stone surfaces from premature decay. They attempt to halt the natural process of stone decay and possibly to restore the original strength lost mostly by chemical weathering and the loss of binding cement. Ageneral solution is not possible because the physical and chemical characteristics must be considered for different stone types. The failures of stone preservation and restoration are greater in number than the cures. The need for repair of stone decay goes back to evidence of Roman replacement of decaying stone. The presence of excess water in buildings has long been recognized. Moisture tends to enter masonry from air in humid climates, a most important but often underrated factor (Fig. 1) suggesting that sealing should be the answer. Undesirable staining and efflorescence result in accelerated scaling. Today, the great variety of chemicals available to the modem conservator for sealing. consolidating, or hardening stone fall into two very different categories: surface sealers and penetrating stone consolidants, or a combination of both. SEALERS Sealers develop a tight, impervious skin which prevents access of moisture. Surface sealing has saved monuments from decay by eliminating the access of atmospheric humidity. Pressure tends to develop behind the stone surface by moisture escape. Efflorescence, crystal growth action, and freezing can cause considerable spalling (Anderegg, 1949). Flaking results when moisture is trapped behind the sealed surface. Yellowing and blotchiness are also frequently observed. The following sealants are in common use today: linseed oil, paraffin, silicone, urethane, acrylate, and animal blood on stone and adobe. Extensive cracking and yellowing has resulted soon after application. In the past many such treatments have created more problems than cures: 1. Linseed oil and paraffin have been in use for centuries. Embrittlement and yellowing occur rapidly because these are readily attacked by solar ultraviolet radiation. 2. Animal blood as paint has temporarily waterproofed adobe mud and stone masonry. The origin of blood paint has a religious background rooted in the Phoenician and Hebrew cultures. Instant water soluble dried blood can substitute for fresh blood. Winkler (1956) described the history and technique of the use of blood. 3. Silicones have proven very effective and are long lasting. In contrast, acrylates, urethane, and styrene are generally rapidly attacked by UV radiation (Clark et al., 1975). Sealing of Different Rock Types Granitic rocks have a natural porosity traced to 4.5% contraction of quartz, during cooling of the parent magma, compared with only 2% contraction of all other minerals; protection against the hygric forces may require waterproofing of granite in some in- stances. The Egyptian granite obelisk in London is an example. Soon after its relocation from Egypt to London, Cleopatra's Needle was treated, in 1879, with a mixture of Damar resin and wax dissolved in clear petroleum spirit; surface scaling became evident after half a year of exposure to the humid London atmosphere. The treatment of the ancient granite monument from Egypt has denied access of high relative humidity (RH) in London to the trapped salts inherited from the Egyptian desert and has protected the monument from decay (Burgess and Schaffer, 1952). The sister obelisk set up in Central Park, New York City, has fared less favorably because similar treatment was done too late, only after the salts hydrated and hundreds of kilograms of scalings disfigured the obelisk surface (Winkler, 1980). Surface coating of other common stones may be needed. Crystalline marble absorbs moisture from high RH atmospheres: dilation may ensue when curtain panels bow as the moisture starts to expand during daily heating-cooling cycles. A good sealer may prevent the moisture influx provided that no moisture can enter from the inside of the building. Limestones, dolomites and all carbonate rocks are subject to dissolution attack by rainwater, especially in areas where acid rain prevails (Fig. 2). The interaction of sulfates in the atmosphere with the stone can be halted by waterproofing to avoid the formation of soft and more soluble gypsum. The stone surface attack can be diminished if nearly insoluble Ca-sulfite crusts can form, instead of Ca-sulfate. Replacement of fluorite or barium compounds at the stone surface acts as a hardener, rather than a sealant. Sandstones have generally high porosity and rapid water travel can occur along unexpected routes and from any direction. Any surface sealing may do more damage by scaling and bursting than if the stone is left without treatment. Sealing of sandstones is therefore not advised at any time. Testing the efficiency of sealants: Several authors discuss waterproofing materials, silicones, urethanes, acrylates and stearates, as to their water absorption, spreading rates of water on the treated surface, water vapor transmission, resistance to efflorescence, and general appearance (Clark et al., 1975). De Castro (1983) measured the angle of contact of a microdrop (0.004 cm3) on a stone surface as characteristic of the wettability. Laboratory tests and limited field performance are described by Heiman (1981). The crest of a Gothic sandstone arch, which was sealed with silicone,

Jan 1, 1994

By George V. Smith, Daniel E. Sonon

Various mechanical properties of the Ni-Co-C alloy system were investigated to delineate the strengthening effect of carbon. Carbon concentration, cobalt concentration, vain size, temperature, and strain rate were varied so that thermal activation analysis and the Hall-Petch analysis could be used to evaluate the strengthening effect of carbon. Increasing carbon increased the strength of nickel and a Ni-60 pct Co alloy , with the effect becoming more pronounced at lower temperatures. Yield stress depended linearly on carbon concentration in nickel, but it depended on the square root of carbon concentration in the Ni-60 pct Co alloy. The Hall-Petch slope of nickel increased with carbon concentration; however, that of the Ni-60 pct Co alloy did not. The yielding behavior of these alloys was sensitive to composition, grain size, and temperature. Cobalt eliminated serrations in the flow curve of carbon-containing nickel at 300' and weakened them severely at higher temperatures. Pairs, or clusters, of carbon atoms appear to be responsible for the observed strengthening behavior. FLINN' conducted several experiments with carbon in nickel in an effort to provide information on the strengthening effect of interstitial impurities in solid solution in fcc metals and alloys. Strengthening which increased with decreasing temperature led him to conclude that carbon causes Cottrell locking in nickel. Fleischer2 analyzed Flinn's data and calculated that the strengthening effect of carbon in nickel was smaller by a factor of fifty than the strengthening effect of carbon in a! iron. Fleischer2 termed the magnitude of strengthening of carbon in nickel "gradual" and that of carbon in a! iron "rapid". He attributed "gradual" hardening to hydrostatic strains and localized changes in modulus of elasticity around solute atoms, whereas he attributed "rapid" hardening to tetragonal strains around solute atoms. Sukhovarov et a1.3-7 reported strain aging and serrated plastic flow in nickel, both of which they attributed to the presence of carbon. Serrated plastic flow has been rationalized by a process involving a series of dislocation pinning and multiplication steps.8, This process is more probable when screw dislocations are strongly pinned. Screw dislocations cannot be pinned by pure hydrostatic forces from the symmetrical strains of an interstitial impurity in an fcc lattice, except for small, second-order effects. However, they might be pinned by localized changes in modulus of elasticity around solute atoms,' by the pinning of the edge components of the partial dislocations of an extended screw dislo~ation,'~ or by clustered groups of solute atoms whose net elastic stress field is unsymmetric. The purpose of the present work was to investigate various mechanical properties of the Ni-Co-C a1loy system which are sensitive to pinning effects in order to delineate the specific pinning mechanism of carbon. Carbon concentration, grain size, temperature, and strain rate were varied so that thermal-activation analysis and the Hall-Petch analysis could be used to evaluate the pinning mechanism. Cobalt was added to lower stacking fault energy so that the number and extension of split, screw dislocations would be increased in order to test the possibility of pinning by carbon at extended screw dislocations. EXPERIMENTAL PROCEDURE Nickel and cobalt (both 99.98 pct-. pure) were melted with graphite in stabilized zirconia crucibles and cast at lo-' Torr to form Ni-C and Ni-60 pctCo-C alloys. Two ingots were heated to 1250°C and were forged to 1-in.-sq bars. These bars were machined to 4-in.-round bars, and then swaged cold to 0.144-in. -diam rods. Reductions in area of approximately 75pct were used with intermediate anneals at 900°C for 1 hr. The carbon content of batches of 0.144-in.-diam rods from each ingot was reduced to two levels by annealing 5-in. lengths in palladium-purified, dry hydrogen at 1100°C for 25 and 100 hr. The remaining material from each ingot was annealed at 10"5 Torr for 1 hr at 1100"~. These treatments gave a total of three carbon levels for both the nickel and the Ni-60 pct Co alloy. The 0.144-in.-diam rods were swaged to 70-mil wire, cut into test specimens, and then re crystallized at lom5 Torr in capsules for 1 hr at temperatures ranging from 760" to 1050" ~. The capsules were broken and the specimens were immediately quenched into water. Average grain size was measured using Hilliard's method of circular intercepts." Annealing twin boundary intercepts were counted in addition to grain boundary intercepts to establish an average grain size. Average grain sizes ranged from 5 to 140 p depending on the cobalt concentration and re-crystallization temperature. Tension tests were made in duplicate at various temperatures at a crosshead speed of 8.34 x 10"4 in. per sec with an Instron Universal Testing Machine. Specimens of 1-in. gage length with soldered ball ends were used at atmospheric and cryogenic temperatures. Pinch grips were used on specimens at elevated tem-

Jan 1, 1969

By G. Borelius

ABOUT the turn of the century, Gibbs' thermo-dynamic theory of heterogeneous equilibrium, on the one hand, and the experimental methods of thermal and microscopic analysis, on the other, gave to the physical metallurgist his first scientific tool, the equilibrium diagram. The classical equilibrium diagram of a binary alloy system shows the boundaries between ranges of homogeneous and heterogeneous equilibrium in their dependence of concentration and temperature. A homogeneous solid sohtion which on cooling passes such a boundary is assumed to precipitate, forming a mixture of two phases with different concentrations. The equilibriunl diagram and the equilibrium theory, however, give no information about the time scheme of the process or the intermediate states passed during precipitation. For this reason it satisfies neither the practical need of the metallurgist nor the curiosity of the physicist. As a matter of fact, in the heat treatment of alloys for technical use the objective very seldom is the equilibrium state. Thus good mechanical properties of construction material are connected, for the most part, with some intermediate state. As these intermediate states are thermodynamically unstable, there is, from a theoretical point of view, always to be expected a decay of the good properties with time; and it is a matter also of practical interest to know whether this natural life time of a material is of the order of, say, ten or thousands of years. Thus, for many reasons, there is a current demand to complete our knowledge of equilibrium through knowledge of the kinetics of the precipitation phenomena. From the point of view of the physicist, the most interesting question in this case is whether there are any general laws governing the kinetics. According to a generally accepted view, precipitation is ruled by two more or less independent phenomena, the formation of nuclei of a new phase and the growth of these nuclei. It is also commonly accepted that there is a tendency for the velocity of growth to increase with increasing temperature because of the increasing mobility of the atoms. There is also a tendency for the velocity of growth to decrease in the neighborhood of the two-phase boundaries. So far, however, very little is known quantitatively about this fundamental phenomenon in the case of solid metallic systems. In our laboratory attention has been directed especially toward the nucleation phenomena, and a series of measurements have been carried out with the guidance of a work- ing hypothesis (based on experiences from previous work on order-disorder transformations in alloys) about the influence on the nucleation of thermo-dynamic potential barriers. However, before discussing the experiments, the theoretical ideas will be considered. In a binary solid solution the arrangement of atoms on the lattice points approaches with increasing temperature a state of full randomness, as illustrated by the ball model of Fig. 1, that might represent a [111] plane of a face-centered alloy with 30 pct "black" and 70 pct "white" atoms. In reality the atoms are changing places continually with their neighbors so that the picture should rightly have been a moving one. On account of this thermal motion the concentration of black atoms within a certain group of, say, a hundred or a thousand lattice points fluctuates with time around the bulk concentration of 30 pct in a manner governed by statistical laws. With decreasing temperature two independent changes in this state grow more and more important. First, the mobility of the atoms decreases, and second, the forces between the atoms will have an increased influence on the fluctuations. In alloys with a tendency for precipitation, which are the concern of this lecture, the distribution function of concentration fluctuations will broaden, so that the relative probability of great local variations from the bulk concentration increases. Fig. 2 gives an example of such a fluctuation. When the alloy is supercooled below the solubility limit into the range of two-phase equilibrium, the fluctuations will now and then at some point give rise to a state that resembles the equilibrium state and thus will form a stable nucleus that is capable of growing by diffusion processes. In discussions with colleagues and in the literature, I have often encountered the idea that three or four atoms of the dissolved metal could form a nucleus of the new phase. A look at the ball model might be enough to indicate that this cannot be true. If it were true, there should be nothing but nuclei, whereas we know from experiment that nucleation must be a rather rare occurrence. In fact we have, as will be mentioned later, certain reasons to believe that the nuclei are formed by fluctuations containing some hundreds of atoms, which should be the order of the number of black balls in the fluctuating group of the figure, if it were extended into three dimensions. As a working hypothesis we have assumed that the fluctuations producing nuclei, though large and rare, still are ruled by the distribution laws of fluctuations of the supercooled solid solution in its initial state. Thus the probability of nucleation will be connected to the thermodynamic properties of the solid

Jan 1, 1952

By Thomas P. Forbath

THE sudden realization that known sulphur reserves amenable to mining by the Frasch hot water process are nearing exhaustion focused attention on widely scattered surface deposits throughout the world. These deposits are not necessarily of lower sulphur content than ores located underneath Louisiana or Texas salt domes which usually average about 30 pct sulphur disseminated in limestone matrix. Their near surface occurrence, however, renders exploitation by the Frasch process impossible. As is well known, the Frasch process depends on the presence of 500 to 1000 ft of overburden and cap rock above the sulphur deposits to permit melting underground sulphur in place by diffusing hot water under pressures of 200 to 600 psig in the formation and raising the molten sulphur to surface by air lift. This process renders possible the production of pure sulphur which is 99.5 pct pure without any subsequent treatment. Surface deposits contain sulphur in the same range of concentrations as the salt dome deposits, i.e., from 10 to 50 pct sulphur, associated with various gangue materials such as silica, limestone, and gypsum. The pirincipal distinction, then, does not lie in the percentage of sulphur contained in the ore, but in the geological nature of the deposit. A recent study' of the world sulphur supply situation estimated 1950 sulphur production in the free world countries at 5.6 million long tons, of which the United States produced 5.2 million tons, or 93 pct of the total. While America's domestic needs alone would have been covered by national production, about 1.4 million tons were exported during the same year. Despite all the steps which are being taken to restrict use of elemental sulphur and to force the fullest possible development of alternate sulphur sources here and abroad, the deficit in elemental sulphur production will probably increase with time. As a result of intensive prospecting for oil throughout the Gulf Coast area discovery of significant new salt domes is held unlikely. With the growing scarcity of sulphur and what appears to be an inevitable rise in price, recovery from deposits not amenable to Frasch-process mining assumes greater economic importance. Untapped Reserves The most important deposits in this category are located in Sicily, where elemental sulphur occurs in Miocene limestone and gypsum formation. Sulphur content of these ores ranges from 12 to 50 pct with an estimated average of 26 pct. Although quantitative estimate of these reserves is not available it is held that they exceed 50 million tons of sulphur. Similar deposits occur also on the mainland which contribute about one-third of Italy's total current annual production of 230,000 tons, but these are known to be nearing exhaustion. Significant surface deposits of volcanic origin are located in South America, Japan and western United States, silica being characteristic gangue con-stituent. The largest of these deposits are in South America. More than 100 extend over a zone 3000 miles long, paralleling the west coast of South America. 'Total sulphur content of these deposits has been estimated to be as high as 100 million tons. The main islands of Japan also possess at least 40 known volcanic sulphur deposits with probable reserves of 25 to 50 million tons.' Prospected reserves in western United States might amount to 2 million long tons, principal deposits being located in the northwestern part of Wyoming, southern Utah, and eastern California. Volcanic deposits of lesser importance are found around the Mediterranean, in Turkey and Greece, and in Africa, Egypt, Abyssinia, and Somaliland. Beneficiation Methods Different methods of beneficiation have been used in these various locations. In Italy the Calcarone kiln and Gill regenerative furnaces are used exclusively. Both utilize heat liberated by burning part of the sulphur in the ore to liquify or vaporize the remaining sulphur, which is recovered by solidification or condensation. The Calcarone kiln is of conical shape, generally 35 ft in diam at base and 18 ft high. A kiln of 25,000 cu ft capacity burns for about two months and yields about 200 tons of sulphur. The Gill furnace consists of a series of chambers with domed roofs. Sulphur is burned and melted in one chamber at a time and the hot combustion gases are used to preheat the ore charge in the subsequent cell. These furnaces operate on a cycle of 4 to 8 days. The recovery yield of both systems is about 65 pct. Sulphur losses amount to 25 pct through the combustion to sulphur dioxide; about 10 pct is retained in discarded calcines. Ores containing less than 20 pct are not considered suitable as furnace feed. These methods are not only wasteful because of the low recovery obtained, but represent a serious atmospheric pollution problem. Sulphur produced ranges from 96 to 99 pct purity and thus does not match Texas or Louisiana sulphur. Owing to the present shortage, sulphur in the Middle East sells

Jan 1, 1954

By M. Cohen, D. J. Blickwede

Quantitative observations concerning the carbide phases in high speed steel are of importance for two general reasons: (1) the carbides, being inevitable constituents of the final structure, exert a direct influence on the properties of the steel; and (2) a substantial proportion of the total alloy content is tied-up in the carbides, and hence the extent of their solution on austenitizing governs the composition of the steel matrix. The latter relationship has a vital bearing on the response of the steel to tempering as well as on its performance in subsequent service. Accordingly, in the course of a long-term study of the behavior of high speed steels, the authors were confronted with the problem of securing quantitative data on the carbide phases. The obvious method for acquiring such information is to isolate the car-bides from the steel and subject them to chemical, X ray diffraction and other measurements. There are well-known extraction techniques which involve the chemical or electrolytic solution of the less noble matrix (ferrite, marten-site or austenite), thus leaving a residue of the carbide phases. However, the results obtained must be scrutinized carefully1,2 since the carbides may be affected by the chemical or electrolytic action. It is the purpose of the present paper to describe the experiments leading to an electrolytic-extraction technique for quantitatively isolating the carbides from both I and hardened high speed steel. Particular attention is paid to the amount, as well as the composition, of the carbides so that the matrix analysis becomes ascertainable by subtraction from the overall steel composition. Illustrative results are given for the M-2 grade of tungsten-molybdenum steel. Review of the Literature The chemical method of dissolving the matrix selectively with respect to the carbides makes use of dilute non- oxidizing reagents such as hydrochloric or sulphuric acid. Although this simple procedure has led to the determination of the cementite composition,3,4 it achieved only limited success because of the interaction between the acid and the carbide residue. Some of the carbides may not only be destroyed in this way, but the hydrogen released is likely to remove part of their carbon as hydrocarbon gases. The electrolytic technique of isolating carbides has the advantage of rapidly dissolving the specimen (anode) in the presence of less reactive solutions than are practicable with the chemical method. This reduces the possibility of chemical attack on the carbides, and furthermore, the hydrogen evolved during the electrolysis is released at the cathode which is not in close proximity to the carbides. The common electrolytes adopted for this purpose are hydrochloric and sulphuric acids.5-l1 Aqueous solutions of ferrous salts have also been used.12,13 A considerable advance in experimental technique was introduced by Treje and Benedicks14 who developed a double-compartment cell for electrolytic extraction, the anode and cathode chambers being separated by a porous diaphragm. A solution of 15 pct sodium citrate, 2 pct potassium bromide and 1 pct potassium iodide was selected for the anolyte, while the catholyte consisted of a 10 pct solution of copper sulphate, with copper serving as the cathode. This type of cell has a number of desirable characteristics: 1. The anolyte has a pH value close to 7, at least at the beginning of the run. 2. The iron that dissolves from the anode-specimen forms a water-soluble complex ion with the citrate, thereby preventing the precipitation of iron hydroxide (which would contaminate the carbide residue) despite the neutrality of the solution. 3. Copper deposition instead of hydrogen evolution occurs at the cathode, and this avoids an increasing concentration of hy-droxyl ions which (in an otherwise neutral solution) might cause the precipitation of insoluble hydroxides. 4. Contamination of the anode chamber by copper sulphate is inhibited by the porous diaphragm. Houdremont and coworkers15 applied the above method (with the further refinement of excluding oxygen during the electrolysis, washing and drying) to the extraction of carbides from a series of plain carbon steels after various heat treatments. They had quantitative success only with specimens in the annealed condition, and concluded that the size and shape of the carbide particles play an important role in the isolation process, with large spheroids exhibiting the least tendency to decompose during the electrolysis. Up to the present time, the citrate double-cell has not been used to any extent for isolating the carbides of high alloy steels, apparently on the grounds that the complex carbides are more resistant than cementite to attack in the simpler acid electrolytes. In particular, Bain and Grossmann7 and Gulyaev10.10a have employed the hydrochloric acid cell for their investigations of the carbides in high speed steel.* It will be demonstrated here that this type of cell is capable of yielding quantitative results in the case of high speed steel, and actually has certain advantages over the more complicated double cell. However, in order to provide a rigorous test of the quanti-tativeness of electrolytic procedures for the problem at hand, both methods were studied in considerable detail.

Jan 1, 1950

By J. Chipman

There is no better way of paying tribute to the memory of a scientist than by developing and carrying forward those ideas which he has contributed to science and which are for us the very essence of his immortality. For a lecturer who has not had the great privilege of stdying under Professor Howe or 'ven of knowing him in person, these ideas must be transmitted through the printed word. It is our great good fortune that Professor Howe left to us a rich heritage of publication, not only in his classic monograph on the "Metallography of Steel and Cast Iron" but in a wealth of earlier hooks and papers in the transactions of this Institute arid of other scientific and engineering bodies. An outstanding characteristic of this published record is the great breadth of interest and of vision which it portrays. His was riot a narrow specialization in only the scientific aspects of ferrous metallographg. On the contra1y many of his important contributions had to do with a far broader field of metallurgicial endeavor. He insisted that his students be well grounded in 1 he fundamentals underlying the whole field and not led into the narrow groove of specific applications. Among his first major publications we find papers on copper smelting, extraction of nickel, the efficiency of fans and blowers, thermic curves of blast furnaces, the cost, of coke, and the manufacture of steel. These are the papers of a metalhurgical engineer and it was among engineers that Henry Marion Howe made his early and well-merited reputation. These early engineering contributions display very clearly the strongly sctientific inclination of their author. The classic work on "The Metallurgy of Steel" published in 1890 contains a thorough and critical discussion of all that was known at the time concerning the alloys of iron and of what we would now call the physical metallurgy of steel. In addition it describes steel-making processes in use and some that had become obsolete, and points out in critical fashion the reasons for success and failure. Steel mill design and layout were included as well as some pertinent discussion of refractories. The book is indeed an embodiment of one of Howe's outstanding characteristics—breadth. It is both the science and the engineering of steel production as known in that day. One of Howe's earliest technical papers was entitled "What is Steel?" That was nearly seventy-five years ago when many new processes and new kinds of steel were being developed. The time was ripe for such a question and the answers which Howe was able to give were helpful in understanding the phenomena of heat treatment. Twenty-five years ago Professor Sauveur repeated the question as the title of the first Henry Marion Howe Memorial Lecture. It seemed to him that this question, "What is Steel?," had served as Howe's motto throughout the remainder of his life. Today I shall present for your consideration a question of another sort: "What is Sletallurgy?" Perhaps it is not too much to hope that in the answer we may obtain a clearer and possibly broader view of the nature of our science and our profession. The time is ripe for giving careful consideration to what we mean by metallurgy. If our Metals Branch is to become in fact an American institute of Metallurgical Engineers, it is essential that we understand what is meant by metallurgical engineering. I am convinced that the best interests of the profession have not been served by a narrow interpretation of these terms. We must now place emphasis on the breadth of metallurgy as a science and as an engineering profession. With its usual brevity and wit. Webster's dictionary definesmetallurgy as "the science and art of extracting metals from their ores, refining them and preparing them for use." I shall riot assume that the words "science" and "art" and "metal" are so well understood as to require no defining but others among our contemporaries are better qualified than either your lecturer or the dictionary to present the broad meanings of these terms. When we say that metallurgy is among the oldest of the arts we are not classing it with painting or sculpture or music but rather with the making of tools or weapons or the building of bridges or chariots or cathedrals. In short we are saying that metallurgy is among the oldest of the engineering professions. The question " What is metallurg ? " has been one of rather more than ordinary concern to those of us who have the task of developing a curriculum for the education of students in this field. This development has been going on in a number of universities over a period of some years. but there seems to be as yet no unanimity as to what such a curriculum should contain. I believe there is fairly complete agreement that it must be founded upon sound

Jan 1, 1950