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By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

It is known that stoichiometric NiTi transforms to a structure of lower symmetry near room temperature. The present investigation deals primarily with the changes in the electrical and magnetic properties which occur at the transformation. The effects of composition and various heat treatments on electrical properties are also discussed. In recent investigations by Purdy and Parr,' Wang et a1.,2 Dautovich and Purdy,~ Dautovich et a1.,4 and the authors, ~,' NiTi has been observed to undergo a martensitic phase transformation from the ordered CsCl (B2) structure to one of lower symmetry. The crystal structure of the low-temperature modification is still not completely worked out. This transformation occurs near room temperature for the stoichiometric composition. The thermodynamic, elastic, crystallographic, and microstructural characteristics of this transformation for some compositions have been previously reported.'-= In the present investigation, the changes in the electrical transport properties and magnetic susceptibility of NiTi when it undergoes the martensitic phase transformation have been measured. The approximate composition range covered is 48 to 52 pct Ti.* *All compositions are given in atomic percent._____________________ EXPERIMENTAL PROCEDURES AND RESULTS 1) Sample Preparation. The NiTi alloys were prepared from iodide titanium (>99.92 pct Ti) and vacuum-premelted carbonyl nickel (>99.95 pct Ni) by repeated arc melting under gettered argon and casting in a water-cooled copper mold. After the cast buttons were hot-forged at 800" to 950°C, the oxidized surface was removed by grinding and etching. Samples were cut from the worked polycrystalline buttons. After fabrication, the samples were annealed 1 hr at 900°C and water-quenched. The composition of the alloys was assumed to be the same as in the initial feed. This assumption was supported by material balance checks on 100-g arc-melted buttons which demonstrated quantitative recovery to within k0.02 pct. The oxygen content of the alloys was '150 ppma (weight) and the carbon content was 30 to 50 ppm. 2) Electrical Resistivity and Hall Effect. The electrical resistivity was measured over the composition range 48 to 52 pct Ti for temperatures varying from 4.2"K to 900°C. The high-temperature and many of the low-temperature experiments were carried out using conventional 4-probe dc techniques.7 The Hall coefficient and ac resistivity were measured at 20 cps using the apparatus shown schematically in Fig. 1. The equipment is basically an ac potentiometer: The resistive or Hall voltage of the sample is balanced by a comparison voltage provided by a dividing network across a standard series resistance. The off-balance signal is amplified by a Tektronix 122 amplifier and detected by a Princeton Applied Research (PAR) phase-sensitive detector. The precision of the resistivity and Hall coefficient measurements is i0.1 and i3 pct, respectively. The uncertainty in the data is increased by i2 pct from the precision limits because of uncertainty in dimensions and possible end effects. The temperature dependence of the electrical resistivity and Hall effect for a stoichiometric (50.0 pct Ti) NiTi sample are illustrated in Fig. 2. Above 75"C, this sample has essentially the B2 structure, while below about 0°C it is completely in the low-tempera-

Jan 1, 1968

By K. V. Lindell

THE 70-mile serpentine belt of eastern Quebec, producing 70 pct of the world's chrysotile, has 11 operating mines, two of which are underground, eight are open-pit, and one is both open-pit and underground. The combined operation, the Jeffrey mine, of the Canadian Johns-Manville Co., Ltd. is the largest producer in the group. Haulage All four of the separate operations falling under transportation at the Johns-Manville Jeffery Mine at Asbestos, P. Q., is handled by the company owned Asbestos and Danville Railway. A variety of equipment is operated over the 25 miles standard gage railway. Included in the scope of transportation are: 1-Hauling mill rock to the mill. 2-Hauling stripping and waste rock to the waste dump. 3-Hauling mill tailings to the tailings dump. 4-Hauling supplies from, and finished products to Danville. Main line tracks are permanent, but those within the pit and on the dumps have to be relocated constantly to follow the mining face and dump edges. Tracks within rock areas in the mine are laid on steel ties and can be moved by a bulldozer. Standard mechanical track shifters move tracks in dirt areas in the mine and on the dumps. Train-movements, both within the mine and over the out-lying tracks are controlled by a dispatcher located at the southwest rim of the pit. Steam locomotives haul all stripping, waste rock, and ore from the mine to the gathering yard at the northwest rim of the pit. Normally, two trains per operating shovel are used, with adjustment for optimum loading. In the event of shovel loading on the bottom level or in good stripping, service may be increased to three or four trains per shovel. From the gathering yard a 100 ton diesel-electric locomotive hauls the mill rock to the mill slips, a distance of about three miles. Electric or steam locomotives haul the waste rock and stripping to the waste dump located about two and one-half miles from the mine. Stripping cars are sprayed with a chloride solution and "gravelled" to prevent wet stripping from freezing in the cars during the cold months. Cars pass under a shaking screen which distributes an even

Jan 1, 1952

By A. M. Rahm

PROBABLY the majority of red brass sand castings are judged merely on the basis of outside appearance and the quality of machined surfaces. Many castings, however, must individually withstand a hydraulic or air-pressure test before being accepted as parts of more complicated machin-ery. Finally, there remains a comparatively small group of castings intended for uses of considerable responsibility where only the highest possible characteristics of the metal are acceptable, and for these specially cast test bars are required. The shape of the cast piece from which the test bar must be detached varies greatly from one country to another. The test bar as specified in the American Society for Testing Materials Specification B62-36 is widely used by the American foundry industry. The actual test piece is at the bottom of the cast block and has a riser about six times its mass. It is obvious that this test bar has an advantage over the actual casting. The latter rarely possesses a riser of as much as 30 per cent of its own weight and that riser cannot generally be located in so convenient a manner. Therefore, the characteristics of the test bar cannot possibly correspond to those of the casting itself. It must be taken into consideration that red brass if melted and cast in the best possible manner may show a tensile strength of 40,000 lb. per sq. in. with 35 per cent elongation in 2 in. Such a test bar would indicate that the metal was nearly perfect from the viewpoint of its gas and inclusion content. Barring some accidental defect, a casting cor-responding to such a test bar could be accepted as being quite sound. However, actual specifications do not demand such high characteristics; indeed, few specifications require over 30,000 lb. per sq. in. and 20 per cent elongation, while one Federal specification demands merely 27,000 lb. per sq. in. strength and 15 per cent elongation. It is obvious that

Jan 1, 1939

By Fred N. Kissell, Natesa I. Jayaraman

Introduction This paper describes a recent Bureau of Mines research project that resulted in a simple procedure for reducing the dust exposure of longwall shearer operators. This project involved the development and testing of a water spray and passive shield system to hold dust against the face and away from the shearer operators. This system is known as the Shearer- Clearer.

Jan 1, 1981

By Persifor Frazer

The mines which I am about to describe are all situated in the northern part of the States of Nuevo Leon and Coahuila, Mexico, between the twenty-sixth and twenty-seventh degrees of latitude. They might be grouped, orographically, into four classes: 1. Those in the Sierra de la Ygnana chain; 2. Those in the Sierra de Gomez chain; 3. Those in the Cerro Mercado; 4. Those in the Sierra de San Marcos chain. (See large map.) The first two of these may be further arranged in one geographical district, to which the name, "the Villaldatna. district," may be applied, and the last may be ascribed to the geographical district of " Monclova." Geologically described, the country rock, in which four of the six mines occnr, is a limestone, concerning which a few words will be said further on, to wit.: The Arroyo (gulch), the Montanos and the Pinitos (pines), in the Villaldama district, and La Paloma (the dove), or Iron Mine, in the Monclova district. The San Rafael appears to lie in granite, or a heavy-bedded gneiss, presenting most of the characteristics of the latter, though the contact plane of the limestone is not far off. It is certainly worthy of attention that the ore occurs in that portion of the crystalline rock, which is nearest to the limestone, and it has been thought by some observers to be a true contact vein. It is well known that veins of this character are very often distinguished for constancy and richness. Although the undersigned cannot entirely free himself from the impression that this proximity of different formations has had an important influence in the origin of the part of the vein on which this mine is situated; still he was unable to establish it actually at the contact of the limestone and granite, but rather a short distance within the latter. Two openings of the Riojas vein were respectively in limestone and in rotten whitish granite, but this fact, if established (as by the correspondence of the strike line of the vein in direction with that of a line joining the

Jan 1, 1884

By J. P. Denny

The constitution of the Ga-In system was determined by thermal methods. An experimentally determined metastable equilibrium line (an extension of the indium-rich liquidus) was obtained. The various alloys were studied metallographically using polished samples obtained by a casting method. These low melting alloys required a special dry-ice assembly to maintain a suitable temperature. RECENT interest in alloys that are liquid at room temperature has led to rather extensive investigation of gallium-base alloys. Widely distributed over the earth, gallium could be produced in substantially larger quantities than at present, if a significant demand existed.' One study' has established its presence in 12 out of 14 zinc blends, in all of 15 aluminum ores, in 4 out of 12 manganese ores, in 35 out of 91 iron ores, and in all of 7 magnetite ores. It occurs as a rule in minute amounts, however, leading to high extraction costs. Recent quotations run from $2.50 to $7.50 per g. During the course of the present investigation, portions of the system Ga-In have been redeter-mined, and the results of this study are presented herein. Thermal and metallographic methods have been employed. Lecoq de Boisbaudran, the discoverer of gallium, conducted the first investigation" on Ga-In alloys in 1885. The temperatures of incipient melting, and of completion of melting, were determined at four alloy compositions. In 1936, Hansen' constructed a eutec-tic-type phase diagram for the system Ga-In, based on . work. The existence of a Ga-In compound was regarded as improbable by Hansen, and subsequent investigations are in agreement. French, Saunders, and Ingle3 conducted a more complete study of the system in 1938, using thermal methods. Their phase diagram is a eutectic type, containing a unique concave-upward liquidus. The solid-solution range of gallium in indium was reported as 9.5 pct by weight, and that of indium as less than 1 pct, at the eutectic temperature. The eutectic composition, determined as being bracketed by the compositions showing a true horizontal at the eutectic temperature (16°C), was reported as 76 5-0.5 pct Ga and 24 i 0.5 pct In. Experimental Procedure The preparation of Ga-In alloys is simplified by the low melting points involved. Various compositions were prepared by melting in pyrex tubes, using a cover of distilled water or parafin to prevent the alloys from wetting the glass wall. In all cases, the melts were homogenized. by stirring. Where possible, both cooling and melting curves were determined. The extensive undercooling of gallium was found to prohibit a satisfactory cooling-curve analysis of gallium-rich alloys, however, and transition points on the gallium side of the eutectic could be determined only by melting curves. The inverse rate method of thermal analysis proved to be most satisfactory and was used to a great extent. Various heating and cooling rates were used, ranging from 0.2" to 5.0°C per min. Low temperature melting analyses were conducted within a constant temperature bath, maintained at about 70 °C. The alloys were solidified (under water or paraffin) within a pyrex tube, using dry ice; the tube was then sealed within a cold Dewar flask, the unit transferred into the constant temperature bath, and periodic temperature readings taken. The high temperature melting-curve determinations and all cooling-curve determinations were made in a vertical tube furnace. At near-eutectic compositions, the furnace was placed within a refrigerated room held at —20°C. Accordingly, the furnace on cooling approached —20°C asymptotically and permitted the determination of those phase transitions occurring below room temperatures. Temperatures were measured with a 30-gage iron-constantan thermocouple, immersed directly in the alloy. To prevent contamination of the melt, the leads and junction were coated with Lucite, applied by painting with a solution of Lucite in ethylene dichloride. Electromotive force measurements were made with a Leeds and Northrup precision potentiometer, type 8662. The couples were calibrated against the boiling point. of water and, at lower temperatures, against a calorimeter thermometer having a Bureau of Standards certificate. The melting points of gallium and indium used in the present investigation were determined as 29.-77° and 156.1°C, in good agreement with previously reported values of 29.78°C° and 156.4"C.' The spec-

Jan 1, 1953

By W. A. Krivsky, R. Schuhmann

Jan 1, 1962

By William P. Blake

THE importance to the growing steel industry of the United States of a domestic supply of ferro-manganese or "spiegel" of a high grade, induces me to bring to your notice some details of the method by which a superior article is produced in the Austro-Hungarian Empire. At Reschitza, Hungary, and probably at Laibach also (the Krainische Industrie Gesellschaft), ferro-manganese is made in a blast-furnace, with charcoal as fuel, and limestone as the flux. The ore is a ferruginous mixture, containing about 37 per cent. of sesquioxide of manganese. It is silicious, and somewhat resembles, in its appearance, the manganese ore from Red Island, in the Bay of San Francisco, California. It contains about 29 per cent. of silica and some alumina, shown by the subjoined analysis

Jan 1, 1876

By J. S. Pascover, J. K. Abraham

The influence of the early stages of precipitation on the kinetics and structure of martensite formation in Fe-27Ni and Fe-29.5Ni alloys containing from 0 to 10 pct Ti was examined with X-ray and electron microscopy techniques. The formation of a coherent, ordered preprecipitate had a profound stabilizing effect on the austenite. The Ms was decreased by increased titanium content and aging time up to a critical time. When the critical aging time was exceeded, the Ms was observed to increase markedly. The formation of the clusters was insuppressible and the volume fraction of clusters formed during the quench was a function of the titanium content. Martensite resulting from transformation of the clustered austenite is tetragonal with the c/a ratio increasing with titanium content. A model for the tetragonality is suggested. The morphology and substructure of the m artensite is inter-preted in terms of the above information and the cur-rent models of twinned martensite. ThE ramifications of precipitation in austenite to the properties of austenite have been the subject of numerous investigations. The current research is concerned with the influence of precipitation in austenite on the kinetics and structure of subsequent marten-site formation. In a previous investigation, Abraham et al.1 followed the aging reaction in an Fe-29.5Ni-4.2Ti* (at. pct) alloy using an X-ray diffraction technique. This technique, employing a Guinier camera, provided kinetic measurements through observation of the side band position as a function of aging time. The salient results of this work were: 1) The initiation of precipitation was not suppressed by quenching, i.e., there was a finite cluster zone size at zero aging time; and 2) The hardness of the aged austenite correlated extremely well with the zone size. During the previous work it was noted that the mar-tensite formed after aging was tetragonal, substanti-ating an earlier observation.2 Systematic investiga-tion revealed that the martensite was tetragonal in both the solution-treated then quenched, and the solu-tion-treated, aged, and quenched condition, and, furthermore, that a marked stabilization of the austenite occurred as a function of aging time. The present work is concerned with documenting the tetragonality and the stabilization phenomena as well as the ob- served microstruction with a suggested rationale for the behavior noted. EXPERIMENTAL PROCEDURE The compositions of the alloys are listed in Table I. The analyses were performed after the solution treatment of the strip material. Nickel was determined using the standard dimethy1-glyoxime procedure whereas titanium was determined colorimetrically with hydrogen peroxide and volumetrically by titrating with ferric iron. The materials were melted in a 5-lb vacuum induction furnace, cast into 2-in.-diam ingots, and forged in a temperature range of 950. to 1200°C to 1/2-in. slabs. The three higher titanium containing materials cracked during forging; therefore, to get the alloys into strip form, slices 1/8 in. thick were cut from the slab, homogenized 4 hr at 1150°C, then cold-rolled to a 0.04-in. thickness. The remaining slabs were hot-rolled, homogenized 4 hr at 1065"C, then cold-rolled to a final thickness of 0.03 in. All of the heat treatments were performed under a protective atmosphere of argon. The Ms temperature for most of the alloys is below room temperature; therefore, it was possible to solution treat, quench to room temperature, polish, and then observe the transformation optically on a cold-stage microscope. To determine the effect of aus-tenitizing temperature on Ms, eight of the alloys were treated at two temperatures, 1025" and 1120°C. No measurable variations in Ms were noticed. The remaining alloys were treated at 1025°C. The specimens, : by 5/16 by 0.03 in., were austeni-tized in a vertical tube furnace under a dynamic argon atmosphere. The bottom of the tube was submerged in water for quenching purposes. The question of stabilization that may be operating at room temperature was investigated and found to be negligible. Many of the specimens were held at room

Jan 1, 1970

By H. A. Baumann, C. C. Wright, T. S. Spicer

A LTHOUGH the efficiency of coal utilization has A improved steadily since the turn of the century as a result of continued research and development, little of this increase in efficiency can be credited to improvements in the single retort stoker. There are still numerous problems connected with the burning of coal on this type of unit, the solution of which would be a stimulus to coal and stoker sales and a boon to the user. Among the more critical of these problems is that of burning slack bituminous coal of strong caking tendency and containing large percentages of fine material. With the increased trend toward mechanical mining, it may be expected that in the future an even larger percentage of the coal available for use on this class of stokers will contain higher percentages of the fine sizes, thus aggravating an already serious problem. During the war, the problem of efficient and economic burning of available coals on the single retort industrial stoker, particularly the class 4 stokers (301 to 1200 lb per hr), became quite critical in many localities. In addition to the inherent problems associated with the use of this class stoker, the coals available were frequently not those best suited for use on this equipment and the manpower shortage made it difficult as well as expensive for the consumer to provide the labor necessary to keep the iires in reasonably satisfactory condition. Although exact figures on the number of class 4 stokers are not available, the yearly tonnages of coal consumed are of considerable consequence and have been estimated* at between 15 and 20 million the stoker research staff of the Mineral Industries Experiment Station of The Pennsylvania State College was requested to study the performance of the single retort industrial stoker and to undertake a program of research on the more efficient burning of bituminous coal on this class of unit. Various aspects of overall problem have been investigated since the inception of this program in 1942, only one of which is here reported. General Considerations There are numerous factors which appear directly or indirectly to affect the overall performance of bituminous coal underfeed stokers, such as the caking or matting properties of the coal, the contact relationships between coal and air, the ash fusion characteristics, the burning rate, and the design of the stoker and furnace in which the coal is burned. An analysis of the influence of each of

Jan 1, 1951

By H. A. Baumann, T. S. Spicer, C. C. Wright

A LTHOUGH the efficiency of coal utilization has A improved steadily since the turn of the century as a result of continued research and development, little of this increase in efficiency can be credited to improvements in the single retort stoker. There are still numerous problems connected with the burning of coal on this type of unit, the solution of which would be a stimulus to coal and stoker sales and a boon to the user. Among the more critical of these problems is that of burning slack bituminous coal of strong caking tendency and containing large percentages of fine material. With the increased trend toward mechanical mining, it may be expected that in the future an even larger percentage of the coal available for use on this class of stokers will contain higher percentages of the fine sizes, thus aggravating an already serious problem. During the war, the problem of efficient and economic burning of available coals on the single retort industrial stoker, particularly the class 4 stokers (301 to 1200 lb per hr), became quite critical in many localities. In addition to the inherent problems associated with the use of this class stoker, the coals available were frequently not those best suited for use on this equipment and the manpower shortage made it difficult as well as expensive for the consumer to provide the labor necessary to keep the iires in reasonably satisfactory condition. Although exact figures on the number of class 4 stokers are not available, the yearly tonnages of coal consumed are of considerable consequence and have been estimated* at between 15 and 20 million the stoker research staff of the Mineral Industries Experiment Station of The Pennsylvania State College was requested to study the performance of the single retort industrial stoker and to undertake a program of research on the more efficient burning of bituminous coal on this class of unit. Various aspects of overall problem have been investigated since the inception of this program in 1942, only one of which is here reported. General Considerations There are numerous factors which appear directly or indirectly to affect the overall performance of bituminous coal underfeed stokers, such as the caking or matting properties of the coal, the contact relationships between coal and air, the ash fusion characteristics, the burning rate, and the design of the stoker and furnace in which the coal is burned. An analysis of the influence of each of

Jan 1, 1951

By D. M. Waldorf

Steam permeability measurements have been made in the laboratory on several samples of natural reservoir materials. The steam temperatures and pressures were selected to simulate conditions which might exist in a reservoir during the injection of steam. For each sample tested, the experimental permeability to superheated steam was comparable to that measured with air and no evidence of plugging was detected. Some samples were exposed to water at various temperatures and plugging was found to occur in materials which contained significant quantities of monmorillonite clay. Temperature had little effect on the degree of plug-ning between 75 and 325 F. The measured pemeabilities tended to increase slightly with temperature, but the changes were small compared with the initial loss of per~neability on wetting. Sequential pemzeability measurements were made on two samples using air, water, steam, water and air, in that order. Both samples were water-sensitive and plugged extensively after the initial injection of water. Upon exposure to superheated steatm the samples dehydrated and their permenbilities to superheated steam were comparable to those initially measured with air. The remaining measuretnetzts with water and air confirmed that the water plugging was reversible and that the samples were not seriorrsly damaged during the tests. INTRODUCTION The swelling of water-sensitive clays during water floods has long been recognized as a potential source of reservoir damage. The recent extensive application of steam injection and stimulation has compounded this problem since both hot water and steam (as well as fresh water at reservoir temperatures) are, at sume time, in contact with the producing zone adjacent to the bore of a steam injection well. The purpose of this paper is to present data which compare the sensitivity of some natural sedimentary rock samples to water at various temperatures, and to super-heated steam. Some properties of montmorillonite clay are briefly reviewed, and comparisons are drawn between empirical data and the predicted behavior of the montmorillonite known to be present in the samples. PROPERTIES OF MONTMORILLONIT E CLAY Water initially adsorbs on dry N a -montmorillonite clay in discrete layers in the interlaminar space between clal platelets. The platelet spacing, which is 9.6 A (angstroms) for a dehydrated clay, has been observed to expand in discrete steps to 12.4, 15.5, 18.4 and 21.4 A spacings, indicating the formation of four discrete layers of regularly oriented water molecules.' The first two layers are easily formed by hydrating a dry sample to equilibrium in an atmosphere with carefully controlled humidity. The formation of the higher layers is more difficult. The usual X-ray diffraction patterns of the more highly hydrated samples indicate a gradual increase in the average spacing betwcen 15.5 and 19.2 A, followed by a discontinuous expansion to 31 A when the weight ratio of water to dry clay is between 0.5 and 1.2.' Platelet expansion above 31 A proceeds monotonically as the moisture is increased and no regular arrangement of the platelets ib observed. Water-sensitivity in sedimentary rocks is usually associated with Na-montmorillonite clay when it is in the noncrystal-line state. Mering3 found that the average lattice spacing of sodium montmorillonite hydrated at 68 F and 70 per cent relative humidity was 15.5 A, and that the spacing, at 92 per cent humidity was 16.5 A. The water adsorbed at the higher humidity has the same free energy as liquid water at 65.6 F. Kolaian and Low' used a tensiometer to measure the thermodynamic properties of water in diffuse suspensions of montmorillonite clays relative to pure water. They observed that water in suspensions as dilute as 6 per cent clay became partially oriented when left undisturbed. The bonding associated with this orientation was not extensive because the free energy difference between the water in suspension and pure water was only a few millicalories per mole. They also found that the measured free energy difference decreased rapidly with temperature and became negligible above 100 F. This evidence indicates that montmorillonites contained in sedimentary rocks would dehydrate to a crystalline structure when exposed to superheated steam, and that the rock permeability measured with steam would be equivalent to that measured with air. The effect of elevated temperatures on the swelline of montmorillonite clays in aqueous suspensions has not been investigated. The Gouy-Chapman diffuse-ion-layer theory has been used to predict the swelling pressure of clay suspensions in dilute salt solutions at room temperature with reasonable success. theory also correctly predicts the direction of the thermal response of Na-mont-morillonite swelling pressures in dilute salt suspensions, 9 Over the temperature range of 33 to 68 F, an increase in

Jan 1, 1966

By Donald B. Evans, Robert D. Pehlke

The solubility of nilrogen in liquid binary alloys of iron with Litanium. zivconium, columbium, vanndiurn, and tantalum was measured for alloy composiLions up to the solalbility limils of lhe alloy nitrides. All five alloying agents were found to decrease markedly the activity coefficient of nitrogen in liquid ivon. The metal/nitvogen mole ralios in the alloy nitrides formed were generally .found to be slighlly greater than 1.0, but in no case greater than 1.5. From the experimental data, the standard free energies of fortmation of titanium and zir-conium nitrides have been calculated for the Lemperaluve range 1550° to 1750 C. The solublily Products for columbium, tantalum, and vanadium nitrides are also reported. A number of research investigations have examined the effect of refractory metals on the solubility of nitrogen in liquid iron. Although data on zirconium are not available, investigators are in agreement that titanium, vanadium, columbium, and tantalum markedly increase the solubility of nitrogen in liquid iron. This fact alone makes desirable the acquisition of thermodynamic data for these elements in liquid iron. Since refractory metals are known to be stable nitride formers, they have been suggested as steel denitrifying agents, and some of their nitrides have recently been considered as containment materials for liquid iron and iron alloys. Most available thermodynamic data for these metals relate to their dilute concentrations, but effective thermodynamic treatment of these applications requires data at concentrations near the solubility limit of the alloy nitride. Although some work has been done at relatively high alloy concentrations in liquid iron (particularly for vanadium 2,3 and titanium 2,4), the results have been somewhat contradictory. Disagreement may be partly attributed to the fact that the compositions of most refractory metal nitrides have been shown to be nonstoichiometric, and to vary 2,5-8 depending on the temperature and nitrogen gas pressure with which the solid nitride phase is in equilibrium. One purpose of this study consequently has been to determine the compositions of the refractory metal nitrides precipitated from a liquid iron solution. EXPERIMENTAL PROCEDURE Rao and Parlee2 and Evans and Pehlke 9 have discussed the technique for measuring the solubility product of an alloy nitride phase in liquid iron by finding the point of departure of the nitrogen solubility from Sieverts' law. The method consists of measuring the solubility of nitrogen in a melt of iron containing a known concentration of a second metal as a function of the nitrogen gas pressure over the melt. In this study the second metal was one of the refractory metals titanium, zirconium, columbium, vanadium, or tantalum. When the nitrogen pressure at which the refractory nitride forms is reached, a deviation of the measured solubility of nitrogen in the melt from Sieverts' law is observed in the form of a "pressure halt." The concentration of nitrogen in the melt associated with this breakpoint in the nitrogen-absorption curve is then used to calculate the nitride solubility. The Sieverts method was used to measure nitrogen solubility as a function of nitrogen pressure and temperature. The experimental equipment for this technique has been previously described in detail. 1,9 Charge materials used were vacuum-melted high-purity iron (Ferrovac-E) and the best commercial grades of the refractory metals obtainable (in all cases at least 99.8+ pct pure). Recrystallized alumina crucibles were used to hold all melts except those containing zirconium, for which zirconia crucibles were necessary. Temperatures were measured by a disappearing-filament type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diameter sight hole in the crucible lid. By means of a technique previously described, 9 in which the refractory-metal nitride was precipitated at one temperature then redis-solved by raising the temperature 50°C and precipitated again at a higher temperature, it was possible to obtain data over a temperature range of up to 200°C on a single melt. It was found that this technique could not be used with melts containing zir-

Jan 1, 1965

By M. A. Elliott

The technology of gasifying coal to produce synthesis and pipeline gas has advanced significantly in the Past 20 to 30 years. This period has seen the extensive use of oxygen in coal gasification, the development of suspension gasification processes and fluidized-bed gasifiers, the operation of various gasification processes at elevated pressures, and operation of gasifiers under slagging conditions. These developments are discussed, and their application to commercial and pilot plant gasifiers is reviewed. Typical processes for synthesis gas production are described, and operating results are compared. Pipeline or high-Btu gas may be produced from coal either by catalytic conversion of synthesis gas to methane, or by the direct reaction of coal with hydrogen (hydrogasification) to produce a methane-rich gas. Neither of these methods has been applied commercially, but developments pertaining to each of them are reviewed, and general processing schemes are discussed. The use of coal as a raw material for manufacturing gas has a long and distinguished history. In fact, the gas industry began in the early 1800's when William Murdock demonstrated that it was feasible to produce and distribute gas made by retorting coal. Coal was used exclusively for gas manufacture until the middle of the 19th centruy, when Lowe invented the carbureted water gas process. In that process, coke was one of the raw materials used, so coal was still an important factor in gas manufacture. However the availability and relatively low cost of natural gas in the United States, and its widespread distribution by long-distance pipelines in recent years, has virtually eliminated the use of coal as a raw material for gas manufacture in this country. It should not be inferred from the foregoing that the technology of coal gasification has remained static in the United States and abroad. In fact, in the past two decades many new concepts have been developed in both the science and the technology of gasification. This progress has been a result of the considerable expansion in research on the fundamental chemistry and physics of gasification reactions, and in development work on gasification processes. This expansion in effort stems in part from increased interest in the use of gas as a raw material for the synthesis of chemicals and liquid fuels, and in part from the need to develop methods for gasifying coal and other solid fossil fuels to ensure a long-range supply of energy in the form of gaseous fuel. In these uses of gas, synthesis gas, a mixture of hydrogen and carbon monoxide in various proportions, is the starting material. It may be converted catalytically to gaseous and liquid hydrocarbons and other chemicals, or to hydrogen for use in hydrogenation or reduction reactions. Since coal is our most abundant fossil fuel, it is inevitable that one day it will regain its prominence as a raw material for gas manufacture. It is of interest, therefore, to consider the present status of gasification technology, directing attention particularly to advances made in recent years. Inasmuch as many comprehensive treatises l-3 and review4-7 of gasification technology are available, no attempt will be made in the present review to cover all processes in detail. Instead, the discussion will be concerned chiefly with typical processes embodying the advances that are most likely to be generally applied. ADVANCES IN GASIFICATION TECHNOLOGY For purposes of this discussion the starting point will be the conventional processes that were used for many years for the complete gasification of coal. These were: 1) carbonization in coke ovens followed by gasification of coke with air and steam in cyclic water-gas generators, and 2) fixed-bed air-blown producers. Both of these methods have obvious deficiencies when we consider that the ideal complete gasification process would be a single-stage, continuous

Jan 1, 1961

By Hansheinz Portisch, Harold Margolin

A surface expansion was found to occur sometime after etching in Ti-A1 alloys containing 9.5 to 12.5 wt pct Al. The structure formed, grew, and disappeared with tzrrze. The surface expansion was followed by microscope observations and interferometric and lattice parameter measurements. Activation energy measurements for the growth of the "expansion structure" and chemical analysis indicated that the phenomenon occurred as a result of hydrogen pzckup during etching. It is proposed that hydrogen initially enters octahedral sites of Ti3Al coherent with a Ti and later shifts to the tetrahedral sites. It is postulated that expansion occurs when hydrogen enters the tetrahedral sites. The expansion structure disappeared, it is proposed, because of diffusion of hydrogen from the surface into the body of the alloy and because of loss of coherency of Ti3Al. In examining Ti-A1 alloys, Ence and arolinl observed markings on the surface of specimens. These markings did not appear after electropolishing only, but rather appeared only after etching. The markings appeared to grow as a function of time after etching and later seemed to disappear. Although the markings had some similarity to precipitates, showing, frequently, a Widmanstatten type of arrangement, the observation that other microstructural markings continue to be seen within the new structure suggested that it was actually not a precipitate. The source of this structure was unknown and an attempt was made in the present investigation to develop some understanding of its nature. It has been labeled expansion structure. 1) EXPERIMENTAL PROCEDURE A) Alloys. Alloys in the range 6.5 to 14.5 wt. pct A1 were studied. Bars, 4 in. sq, forged from Bureau of Mines (73 Bhn) titanium consumably arc-melted 4-lb ingots,' as well as 50-g arc-melted buttons of desired aluminum contents were used. The 50-g buttons also used Bureau of Mines titanium (73 Bhn) and aluminum of 99.99 pct purity. Buttons containing up to 8.5 wt pct A1 were hot-rolled from a furnace at 900' . Those with higher aluminum contents were hand-forged on a titanium anvil, and heated with an oxygen-hydrogen torch in the region of 1200" to 1300°c. Frequent reheating kept the samples at the desired temperature range. After a reduction of about 30 pct, the samples were water-quenched. To eliminate any contamination picked up either during hot rolling or forging, at least 1 mil of the surface of the sample was taken off. B) Heat Treatment. Prior to heat treatment all alloys were vacuum-annealed to remove hydrogen. Samples were annealed at 900' until a vacuum of 10'5 mm Hg was established. After this treatment, the samples were wrapped in molybdenum sheet and heat-treated in argon-filled quartz capsules, which were broken under water or iced brine at the conclusion of the heat treatment. All heat treatments under dynamic vacuum were performed in a rapid-quench furnace. This consisted of a molybdenum-lined quartz tube attached to a vacuum system and through a stopcock to a beaker of water. At the completion of the heat treatment the vacuum stopcock was closed, the furnace shut off, and dropped below the quartz tube. Then immediately the inlet stopcock was opened and water admitted until the tube was filled. The steam formed was allowed to escape through the inlet stopcock. This method was used in heat treatments up to llOO°C. C) Metallography. Specimens for metallographic examination were ground, then electropolished using a Disa Electropol machine with a perchloric acid electr01te. Specimens were etched with R-etch.3 A standard etching time of 3 min was used, with the specimen being agitated during immersion. D) Sample Preparation for X-ray Analysis. Samples 0.2 to 0.5 mm in diam were produced from heat-treated rods which were turned to 2 mm diam on a lathe and then rotation-etched. An etchant consisting of 1 pt HF, 7 pt HN03, and 12 pt HzO was satisfactory. With the rod rotating in a vertical position at 50 to 100 rpm, a needle with uniform dimensions could be obtained. Care had to be taken to insure that the rod was at the center of rotation, otherwise cavitation developed. If a small unevenness developed, it was possible to grind it off with a fine emery paper. E) X-ray Diffraction. All X-ray work was done on a North American Phillips X-ray diffraction apparatus and a Jarrell Ash microfocus X-ray unit. The Phillips unit was used with a copper target and nickel filter. The Jarrell Ash unit was fitted with a cobalt target and iron filter. For the Phillips unit 35 kva and 20 ma were used, whereas for the microfocus unit with the 100-p fixed-focus gun 40 kv and 1.5 ma were used. It was found that alignment of cameras on the Jarre11 Ash unit was very critical. The X-ray beam contains an intense area which is not the beam center. The cameras were aligned with the intense region by monitoring the beam coming out of the camera with a Geiger counter. Adjustments were made until a maximum intensity was obtained. A Phillips diffractometer with a Brown chart recorder furnished some of the lattice parameter data. The divergence slit up to 80 deg 28 was I deg; above 80 deg, a 4-deg opening was used, while the scatter slit was1 deg and the receiving slit had a 0.003-in. opening. The general scanning rate was 1 deg per min, while peaks of special interest were rescanned at -j deg per min. For elevated-temperature X-ray diffraction a Uni-cam High Temperature Camera with a film diameter

Jan 1, 1969

By George H. Deike

UNDERGRADUATE interest in coal mining engineering has dropped to an alarmingly low level. Most companies having co-operative scholarship programs have been forced to abandon them for the duration.

Jan 1, 1944

By H. DeWitt Smith

THE mine operated by the United Verde Copper Co. is situated near Jerome, Ariz., on the eastern flank of the Black Hills, at an elevation of approximately 5500 ft. (1676 m.) above sea level. The mine and the town of Jerome are located on a steep hillside, which slopes rapidly to the valley of the Verde River. The smelter town of Clarkdale is situated in the Verde valley 4.1 mi. (6.5 km.) distant in an air line from Jerome, and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel & Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 mi. long and has a compensated 4 per cent. grade. At Clarkdale, it connects with the Verde Valley branch of the Santa Fe R. R. The narrow-gage (36-in.) line of the United Verde & Pacific Ry. was, until 1919, Jerome's only rail connection with a main trunk line. This road connects with a branch line of the Santa Fe system at Jerome Junction, after traversing 26 mi. of mountainous country. From the time of its location, in 1876, until its purchase by Senator W. A. Clark, of Montana, in 1889, the United Verde mine was worked on a small scale and shipments of high-grade gold-silver ore were made from the surface workings. Until 1894, when the narrow-gage railroad to

Jan 8, 1920

By S. J. Green, R. D. Perkins

Little data exists on the high strain rate behavior of geologic materials. Uniaxial stress tests by Kumar1 and by Serdengecti and Boozer2 present some results to strain rates in the range 10 to 103 per sec. The two references cited are the only ones the authors found for high strain rates. Techniques for experiments at high strain rates are not well developed and, in general, leave questions with respect to interpretation of data when the material behaves in a brittle manner. The most reliable data at very high strain rates (104 to 106 per sec) are found in some recent flat-plate work3-5 where experimenters have impacted one plate into another, thereby creating a uniaxial strain loading. The standard uniaxial stress-strain curves cannot be obtained directly from these tests; however, yield (or fracture) may be studied by measuring the "elastic" wave magnitude. These data then may be compared to uniaxial stress data by resorting to some preassumed yield/fracture criteria. Even with the most liberal interpretation of existing data, little can be said of the effects of high strain rate on stiffness, yield/fracture, and post-fracture behavior of geologic materials. It is the purpose of this work to begin to add to the understanding. The data presented here are intended to provide material information for use in calculating the response of geologic materials to high rate deformations. These data can be applied directly to determine parameters such as the elastic modulus and Poisson ratio as a function of stress. Furthermore, these data can be used to derive an understanding of yield/fracture and the effect of rate on the yield/fracture surface. The work presented is a first step, and is

Jan 1, 1972

By J. J. Fritts, J. L. Patrick, T. L. Wright, C. O. Ensign, W. S. White, J. W. Trammell, J. C. Wright, D. J. Hathaway, R. J. Leone

The copper deposit at White Pine, Michigan, from which a little more than 5 per cent of United States primary copper currently is produced, is a large stratiform orebody, 4 to 25 feet thick and several miles across. The present ore column, containing about 1.2 per cent copper as chalcocite and native copper, is confined to the basal beds of the Nonesuch Shale. This upper Keweenawan (Upper Precambrian) formation is a distinctive gray siltstone unit, about 600 feet thick, overlying and overlain by thick red-bed sequences. All these rocks contain abundant volcanic debris, but the latest known igneous activity within 50 miles antedated the Nonesuch Shale. The rocks are unmetamorphosed and only moderately deformed, mainly by tilting and faults. Pyrite, presumably syngenetic, is the only prominent sulfide throughout most of the Nonesuch Shale. The basal beds of the formation, however, contain disseminated copper minerals instead of pyrite and constitute the cupriferous zone. On a regional scale, the top of the cupriferous zone cuts across bedding, and ranges from an inch or so above the base of the formation in some areas to more than 50 feet in others. However, within the cupriferous zone the distribution of copper shows remarkable stratigraphic control. Certain beds are copper-rich compared to the beds that lie between them and the differences persist throughout the White Pine region. Several darkgray thinly laminated beds in the lower 10 to 25 feet of the Nonesuch Shale are rich enough and sufficiently close enough together to constitute a mineable thickness where they lie within the cupriferous zone. Pyrite is the characteristic sulfide of the Nonesuch Shale as a whole. The principal sulfide mineral of the cupriferous zone at the base of the formation is chalcocite. The succession of minerals outward and upward from the center of the cupriferous zone is native copper-chalcocite-bornite-chalcopyrite- pyrite. The bornite and chalcopyrite are confined to a narrow fringe at the margin of the cupriferous zone. This pattern of mineral zones is believed to represent reaction between syngenetic pyrite and introduced copper. The main copper mineralization is independent of structure and apparently antedates deformation. Details of the geometry of the cupriferous zone indicate the possibility that copper was introduced from the underlying sandstone prior to lithification. The source of the mineralizing solutions and their copper is not known.

Jan 1, 1968

By Ross Blake

THE St. Joseph Lead Co. became interested in the Tri-State district in 1921 through acquisition of prospecting and development rights on approximately 20,000 acres of land extending northeastward from the Picher mining field, mostly in Kansas. Prospecting with churn drills was begun the same year and the first commercial ore body was found on the Jarrett tract at the then northern limit of the main Picher field. Operations at this mine began in 1923. Kansas Explorations, Inc., was organized in 1923 by the St. Joseph Lead Co. as a wholly-owned subsidiary to carry on its operations in the Tri-State District from an office at Joplin, Mo. As prospecting of the original acreage proved largely negative, attention was subsequently turned to other sections of the district. Numerous additional leases were acquired and prospected. The Company was successful in developing into operating properties the Jarrett, Isherwood, Robinson, Sullivan and Lotson tracts and, in more recent years, the Ritz, Snapp, Buckingham, Gibson and Jasper mines.

Jan 1, 1947