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By L. F. Mondolfo

An investigation of the relationship between properties of the elements and type of binary diagram formed was conducted. It was found that, for each type of equilibrium diagram, the factors for the size, valence, electronegativity, period, melting point, entropies of fusion, and sublimation calculated for each pair of elements cover a range of values. However, these factors show sufficient relationship to the equilibrium diagram so that the correlation of several of them can be used to predict the type of diagram formed, or at least limit the choice to only a few types. ThE goal of the metallurgist concerned with alloy development has always been to find a method that predicts the properties that can be obtained when a certain metal is added to another one. In most cases a qualitative predictiton of properties can be made if the equilibrium diagram is known. However, this means that for new metals the alloy development has to start with the experimental determination of the equilibrium diagrams. Because this determination is at least as complicated and time-consuming as the determination of the properties themselves, most alloy development has taken place by trial and error, and the study of the equilibrium diagrams has followed rather than preceded the creation of new alloys. Alloy structures and properties depend on the interaction between electrons and a complete knowledge of these interactions would permit prediction of structure and properties of alloys. Unfortunately direct measurement of these interactions is extremely difficult and somewhat doubtful and only properties that depend on them can be measured easily and with certainty. Study of the relationship between properties of the elements and equilibrium diagrams is not new. Besides the well known Hume-Rothery rule of the necessity of an atomic diameter fit within 15 pct for extensive miscibility in the solid, and the wide knowledge of the effect of such factors as size, electronegativity, electron-atom ratio on solid state features,"' work relating to liquid state and liquid-solid reactions can be found in the literature. Of particular interest is the work by Axon,3 who investigated the effect of size and melting point on a selected number of eutectic and monotectic dia-

Jan 1, 1962

NORTH AMERICA Number Members Alaska 43 Canada 340 Mexico 205 Newfoundland 4 United States Alabama 39 Arizona 120 Arkansas 11 California 699 Colorado 168 Connecticut 89 Delaware 18 District of Columbia 140 Florida 20 Georgia 6 Idaho 78 Illinois 214 Indiana 77 Iowa 12 Kansas 24 Kentucky 33

Jan 1, 1936

By Edmund M. Warner

Any city dweller who has walked alone along a remote mine passageway has to be impressed by the eerie silence-the total absence of noise except for one's own breathing and scuffing of boots on the bottom. An underpound mine can have tremendous contrasts, from complete silence to the ear piercing clatter of percussion drills working in the mine roof. Noise in underground mining machines is both useful and detrimental. Without characteristic noises that are recognizable to miners, operators would have a more difficult job operating their machines. Noise serves as a warning of approaching machinery, and changes in noise give indication that breakdowns may occur. But excessive noise is a health hazard. In recognition of this fact, our congress included noise exposure as a part of the "Coal Mine Health and Safety Act of 1969." As [Fig. 1] indicates, allowable noise exposure is established by specifying a time duration permitted at different noise levels. This is the well known "Walsh-Healey" criteria which govern noise exposure in many industries. In most industries noise exposure is not a constant value. Noise emitted from coal mining machinery varies widely, and therefore interpretation of compliance is not a simple matter. Time, environment, instrumentation and machine productivity, as well as the designed machine characteristics affect the results. It is the purpose of this paper to present the underground coal face machinery noise problem from a manufacturer's point of view. Manufacturers are very much aware of their responsibility to alleviate the noise problem. Not infrequently, orders are received from coal operators that a given new machine must comply with "The Coal Mine Health & Safety Act" noise regulations. Such a request is indicative of the misunderstanding which exists with machine users, while indicating their desire to comply with the law. Obviously, if all machinery could be designed and used at some arbitrary low noise level, it would be possible to simplify the regulations. However, there still remains the pervasive problem of existing machines. Extensive investigation to create practical retrofit kits for existing machines, to substantially reduce noise have been only marginally successful. Certain machine mechanisms are inherent noise makers. The only really good solution is to substitute a quieter mechanism. Such overall new designs have been undertaken, and several examples are mentioned later in this paper. Before describing machine noise problems, it is necessary to define noise values. Noise levels are measured in decibels. The designation "DBA" is decibels measured on the "A" scale, or one in which the frequency sensitivity of the instrumentation is about the same as the human ear. The numbers are often misinterpreted because it is a logarithmic, rather than an arithmetic scale. In comprehending the numbers, it should be remembered that any increase of 3 dB doubles the sound power. In practical terms this means that two noises of equal power at the same distance away increases a dB reading by three. Consider [Fig. 2] showing a simplified case of a worker on a machine subject to

Jan 1, 1980

By H. L. Eiselstein, F. P. Huston, B. B. Betty

An extensive program for the establishment of creep data on high-nickel alloys has been in progress during the past seven years. This paper presents the accumulated data on two solid solution alloys, cold-drawn, annealed Monel and cold-drawn, annealed Inconel. Data on these two alloys in other conditions will be published at a later date. Monel, a nickel-copper alloy, is normally considered a corrosion-resistant material, but it will be shown that it also has considerable creep strength, validating its use at temperatures up to and including 900°F. Inconel, a nickel-chromium-iron alloy, is definitely a heat-resisting alloy possessing good creep strength and oxidation resistance up to iiooOF., and because of its oxidization resistance has been used successfully at much higher temperatures for lightly stressed parts. The literature contains but meager data on the creep properties of high-nickel alloys. Howevcr, Bennett and McAdam have presented a substantial quantity of creep data for cold-drawn Monel.1 The material as tested was not representative of mill production for it was cold-drawn to a reduction of area of 40 per cent as against 13 per cent, which is the mill standard for Monel. Twenty-two individual tests were run on each alloy in the investigation described in the following pages. The data and curves presented herein represent an integration of all the tests to obtain the most accurate picture of the creep properties of these alloys. Neither of the two alloys was found to be embrittled by the combination of temperature and stress, as evaluated by room-temperature tensile and impact tests that were made following creep testing. These data indicate that no tendency toward embrittlement exists. It is recommended that 6300 lb. per sq. in. be used as a working stress for cold-drawn, annealed Monel at 900°F. and 13,200 lb. per sq. in. for cold-drawn, annealed Inconel at the same temperature. Table 8 lists recommended working stresses, based on 80 per cent of the stress to produce a minimum creep rate of 0.01 per cent per 1000 hr., for Monel and some steels. Equipment The equipment used for these tests consists of Colville creep-testing machines manufactured by the Tinius Olsen Testing Machine Co. The load is adjusted, depending on the stress level, to give an error in the stress of not more than ± 0.1 per cent. This is based on considerations of lever sensitivity and the stress used for the standard (A.S.T.M. Tentative Standard E22-38T) 0.505-in. diameter creep specimen having a 2-in. gauge length. The single-specimen furnaces are provided with primary and secondary windings, from

Jan 1, 1945

By D. O. Hobson, J. O. Stiegler, C. J. McHargue

The effects of alloy composition, deformation temperature, heal treatment, ad inlerstilial contamination on the occurrence of deformation twins were studied. The twinning transition temperature varied with composition and was a maximuni of 140°C for the 40 pcl V composition. Tire remperature range of the transition was very narrow. Alloys of 20 to 70 pet V could he cold-rolled and exhibited profuse twinning. The alloys which did not twin at room temperature (10, 80, and 90 pel V) could plot be cold-rolled. Oxygen additions systematically lowered the transition temperatures for all vanadium contents. The transition temperature for a 30 pet V alloy increased with annealing temperature, apparently due to changes in dislocation density and configuration. Twinning did not nucleate fracture in any specimen in the 20 to 60 pet V composition range. THERE is great current interest in the refractory metals and alloys as structural materials. An important factor in considering the ductile-brittle behavior of such materials is the role of mechanical twinning as a deformation mechanism. Mechanical twins have been observed after deformation at low temperatures or at high loading rates in the pure metals iron,1 vanadium,2,3 columbium,4,5 tantalum,6 Chromium,7 molybdenum,8 and tungsten.9 Binary alloys in which mechanical twins have been observed include: iron with silicon,10 phosphorous," or aluminum;12 and chromium, molybdenum, or tungsten with rhenium.13-17 The increase in low-temperature ductility obtained by alloying the Group VI-A elements with rhenium is very important with regard to fabricability, and there has been considerable effort to understand the so-called '(rhenium effect". Factors suggested to explain this effect include:'' 1) increase in solubility of interstitial impurities with alloying (electronic effect): 2) changes in the nature of grain boundary phases; 3) changes in interfacial energies of grain boundaries and stacking faults: and 4) promotion of twinning. Although an outstanding characteristic of these alloys is the profuse twinning that accompanies low-temperature deformation, most studies of the rhenium effect have been concerned with the other factors. During recent studies of refractory-metal alloys, it was noted that solid solutions of columbium and vanadium exhibited high hardness and strength at room temperature and elevated temperature and, surprisingly, also showed considerable ductility at room temperature and below. These alloys deformed by twinning at room temperature when subjected to slow loading rates. It appeared that the low-temperature ductility resulted at least in part from the relaxation of stresses by twinning in a system where slip is difficult. The reason for enhanced twinning behavior in some bee solid-solution alloys is unknown. There have been suggestions18,19 that, as in fee alloys, the

Jan 1, 1965

By David B. Reger

The exhaustion of oil and gas in the United States is proceeding at a rapid pace. This is especially true in fields where the light oils that furnish the most fuel for internal-combustion engines arc found, leading to a late estimate by Arnold that the petroleum resources are 36 per cent. exhausted.l The further remark by Dr. David T. Day at the New York meeting of the Institute, in February, 1916, that the operators of the country are now scarcely able to supply the ever-increasing demand for gasoline, leads the writer to believe that a determined effort will soon be made to secure deeper producing horizons in those regions that now furnish high-grade oil, and in which pump stations and pipe lines offer convenient means for the economical handling of new production. A study of Arnold's table shows further that the States that produce paraffin oil exclusively are 45 per cent. exhausted, this figure being much higher than the average of paraffin and asphalt States altogether. The most extensive of all the paraffin-oil-producing areas is the Appalachian Field, extending with the Appalachian Geo-Syncline from western New York southwestward through western Pennsylvania, western West Virginia, Ohio, Kentucky, and Tennessee, where oil of high gravity is always secured. Of these States, Pennsylvania and West Virginia rank highest in the quality of their product. In West Virginia, the oil sands dip to a lower level than in any other locality in the Appalachian Geo-Syneline, the Pittsburgh Coal of the Pennsylvanian being only 50 ft. above sea level along the Nineveh Syneline at Wileyville, Wetzel County.² The very significant fact that the sands of the Mississippian and Upper Devonian Measures furnished the richest oil pools of the State along this

Jan 1, 1917

By Tell Ertl

THE term oil shale is defined. Foreign oil-shale developments are outlined briefly, The richest and most extensive oil-shale deposits in the United States lie in Western Colorado. The Bureau of Mines is opening two adjacent areas for underground mining in Western Colorado. From the first area the oil shale is mined selectively as required by the retorting plant. The second area is being developed as a unit of a full scale oil-shale mine to ascertain the most practical methods of mining oil shale and to determine costs. In both of these mining areas, research will be carried on to develop new and improved practices for mining oil shale.

Jan 1, 1947

By O. G. Paasche, Yuan-Shou Shen

THERE is a disagreement among the various authors about the exact manner of transformation of ZrCr2. Rostokerl and others2 stated that ZrCr2 had a C-14 (MgZn2) type of structure below 1000°C and a C-15 (MgCu2) type of structure at temperatures above 1000°C. Alisova3 and others4 reached the opposite conclusion and stated that the transformation temperature is close to the melting point of ZrCr2. A literature survey shows that various investigators3'= who homogenized the specimens at a temperature higher than 1000°C have concluded that ZrCr2 had the C-15 structure at room temperature. Meanwhile, Jordan et al.4 reached similar conclusions without annealing the specimen. Other investigators1,2,6,7 who X-rayed the specimens in the as-cast condition without annealing reached different conclusions. The investigation reported herein was conducted with the aim of exploring the exact manner of transformation of ZrCr2 by various heat treatment tests. The alloys for this examination were prepared from iodide-reduced zirconium crystal bars, 99.9 pct purity, and electrolytic chromium, 99.9 pct purity. They were melted in a nonconsumable electrode arc furnace with water-cooled copper crucible in a helium atmosphere. The melting loss of each alloy was less than 1.5 pct by weight. Chemical analysis of a randomly selected specimen indicated that there was a very close agreement between calculated and analyzed compositions. Before being heat-treated each specimen was encapsulated in a vycor or quartz tube inside which an argon atmosphere was maintained at a pressure of lower than 1 atm. In determining the crystal structure of each specimen with a Debye-Scherrer camera, the standard procedure8 for X-ray quality analysis (Hanawalt method) was followed. The different series of heat treatment tests in this investigation are tabulated in Tables I and 11. The tests in Series I, specimens from 1-1 to 1-9, which were similar to Rostoker's experiment1 indicated that the transformation temperature seemed to fall between 870° and 900°C and that the crystal structure of ZrCr2 at lower temperature seemed to be of the C-14 type. However, once the compound is transformed to C-15 type, it is impossible to reverse the transformation back to the C-14 type by first heating the specimen above 900°C and then annealing it slowly below 900°C as shown in Experiments II-1 to II-3. Thus, it appears that the specimen of ZrCr2 will transform from C-14 to C-15 structure when heated above 900°C but will not transform from C-15 to C-14 when annealed slowly passing 900° C even after the extremely slow cooling process such as indicated in the experiment of Specimen II-3. As a valid transformation temperature is a temperature at which the transformation is reversible, therefore the temperature 900°C (or other temperature close to 900°C) is not the transformation temperature for ZrCr2 and the C-14 structure is not the stable structure of ZrCr2 at lower temperatures. The C-14 structure is retained at room temperature because the transformation to C-15 structure is very sluggish and the fast cooling after melting does not allow enough time for the transformation to take place. Additional energy is required to alter the metastable condition of the C-14 structure. The sluggishness of this transformation was again demonstrated through another series of experiments. Four specimens with C-14 structure were taken. Then they were annealed at 900°C but each specimen was soaked for a different period of time, Table 11. X-ray diffraction patterns of this group indicated that the C-14 structure gradually disappeared as the soaking period was lengthened. The figures listed under the column "C-14 Structure, pct" were estimated from the intensity of the d = 2.330 line of the diffraction pattern corresponding to the structure. Notice that the intensity of this line became weaker for longer soaking periods. To determine the transformation temperature of ZrCr2, specimens with C-14 structure (as-cast condition) were annealed at 1300°, 1400°, 1500°, 1550°, and 1600°C, respectively. A final specimen was first heat-treated to 1500°C in order to transform it to C-15 structure, then heat-treated at 1600°C again. From the X-ray analyses of this series of tests, Specimen Nos. III-1 to III-6, it is evident that a transition from C-15 structure at lower temperatures to the C-14 structure occurs at some temperature between 1550° and 1600°C.

Jan 1, 1969

By J. Landau, A. Dim, R. Houlihan

Recent developments in the application of solvent extraction in hydrometallurgical processing make it desirable to reassess the present state of availability of suitable equipment for these applications. The range of solvent extraction applications now includes very large scale applications with a modest demand on separation performance (the treatment of some base metals) and applications in which the decisive factor is a very high requirement on separation performance. The extraction column to be described in the present paper is of the type in which mechanical energy is provided for the two- liquid system inside the column. The active elements for this are reciprocating sieve plates designed and mounted so as to uniformly load the driving mechanism, to eliminate vibration of the plant, to have sufficient control over the degree of dispersion of the dispersed phase, and to reduce axial mixing effects, which are highly detrimental to the separation performance of production-scale plant. The operating features of the reciprocating-plate column will be illustrated mainly by experimental results obtained on a 4" diameter column in the extraction of uranyl nitrate with TBP. Some mechanical features of the operation of reciprocating-plate columns will also be discussed.

Jan 1, 1973

By Dell H. Adams

COAL EXPLORATION Coal exploration may be defined as the acquisition of data necessary to define and acquire a block of coal which can be mined at a profit. Unlike ore minerals, coal resources are widespread and relatively abundant with supply exceeding demand in almost every case. Thus simple discovery of coal is generally not enough. The chemical and physical variability of individual coal seams, the capital intensive nature of coal mine development, and the changing patterns of utilization require that a multiphase, three-dimensional evaluation be made of each potential reserve. Factors which must be investigated include not only the quantity and quality of the coal but also the geologic, hydrologic, and engineering characteristics of the seam and its surrounding strata. Acquisition of property to provide a secure base for exploration and mine development is equal in importance to the geologic and engineering programs. The successful development of a coal reserve requires that control of coal and, in the case of a strip mine, the surface be in the form of contiguous blocks of sufficient size to support mining. PHASES OF EXPLORATION The high capital risks of coal exploration and land acquisition dictate that a multiphase program be utilized to minimize initial risk. In such a program, phased development of the data insures that each increase in capital expenditures will be justified by a corresponding increase in the level of confidence in the ultimate success of the project. Each phase is designed to provide sufficient data and property control to facilitate the decision whether to proceed to the next phase of development or to discontinue the program (Table 1). The first phase of a typical exploration program consists of a pre-

Jan 1, 1981

By T. M. Geffen, H. N. Hall

One-third to one-half of the original oil is left in most reservoirs even after thorough gas driving or waterflooding. In contrast, essentially all of the oil contacted con be recovered by flooding with a solvent (a fluid miscible with the reservoir oil). It is not economical to fill a reservoir with solvent since the value of the solvent would very likely exceed that of the oil. A practical method would be to inject a small bank of solvent to displace the oil. This solvent bank in turn could be driven through the rock by a less valuable scavenging fluid, such as natural gas which is also miscible with the solvent. Such a method of oil recovery was studied in the laboratory using long (up to 95 ft) core systems. It was found that, as the solvent moves through the reservoir, the front end of the solvent bank becomes mixed with the oil and forms a relatively short mixing zone between undiluted crude oil and pure solvent. An engineering correlation was obtained which can be used to predict the length of this zone. Displacement of the solvent by natural gas can be achieved with complete miscibility (above the critical pressure of the gas-solvent system at reservoir temperature) or with partial miscibility at lower pressures. Under conditions of complete miscibility, it was found that the length of the gas-solvent mixing zone could be predicted from the correlation developed for the solvent-oil mixing zone. With partial miscibility, two phases exist and the solvent is displaced by a modified gas drive in which vaporization and condensation occur. Equations are developed to predict the performance of this type of displacement. Two plans are suggested for application of miscible fluid displacement. one for miscible displacement of the solvent and the other applying to lower pressures where partial miscibility occurs during solvent displacement. Calculations based on the laboratory tests indicated that a bank of solvent with a volume of less than 10 per cent of the hydrocarbon volume under consideration will generally be adequate to obtain high oil recovery from the portion of the reservoir contacted in miscible fluid displacement. INTRODUCTION The conventional methods by which oil is displaced from reservoir rock—solution gas drive, conventional gas drive, and waterflooding—are all processes in which the oil is expelled from the rock by direct displacement with a fluid immiscible with the oil. Because of the immiscible type displacement, complete recovery of the reservoir oil is not achieved. In economically successful flooding operations, as much as 50 per cent of the original oil may be abandoned in the reservoir as unrecoverable. The use of a solvent (miscible with oil, such as LPG) as an injection fluid does not have the undesirable displacement features common to the use of gas or water (immiscible with oil). It can be readily appreciated, however, that it would not be economically feasible to displace the oil and entirely replace it with a solvent. A process was therefore devised for use in field operations in which only a small volume of solvent would be required to obtain essentially complete oil recovery in the portion of the reservoir contacted. In this process, the solvent acts as a buffer between the reservoir oil and injected gas, allowing the natural gas to displace indirectly the oil with much greater efficiency than if the gas displaced the oil directly. DESCRIPTION OF OIL RECOVERY PROCESS The solvent oil recovery process will be described in

Jan 1, 1958

By Will B. Jamison

Man's material advance from one level of civilization to the next has involved the development of new, more useful tools and the utilization of energy greater than he alone could produce. These two essentials for material progress have developed at an ever increasing rate in the last century. While the first really successful use of mechanical energy derived from burning fuel was in James Watt's steam engine which pumped water from coal mines in Cornwall about 1770, there was still very little use of mechanical energy in mining by 1900 except for pumping and hoisting. Compressed air, having some of the characteristics of steam and which operated engines not unlike steam engines or steam hammers, powered the first attempts to mine coal with energy greater than human muscle could provide. When direct current-powered traction cars replaced horse-drawn transportation cars on city streets, it was natural that direct current locomotives should begin to replace animal and human power in mine haulage. Slowly, trolley and battery locomotives were developed and introduced. With d-c systems being established for haulage, it was natural that improved cutting machines should be developed and powered by d-c motors. Thus began the years of

Jan 5, 1960

By A. R. Kinkel

THE Shasta copper-zinc district of northern California lies in the foothills of the Klamath Mountains at the northern end of the Sacramento Valley. It contains two main areas of base-metal ore deposits, the East Shasta and West Shasta districts shown in Fig. 1. The East Shasta includes the area from the Afterthought mine, near the settlement of Ingot on U. S. highway 299 East, to the Bully Hill mine, on the north side of the Pit River, 9 miles to the northwest. The West Shasta, a well-defined northeast-trending district about 8 miles long and 2 miles wide, west of the Sacramento River, Fig. 2, is the western part of the ore-bearing area formerly known as the Shasta copper belt. Referred to in the older writings as a copper arc, this belt was thought to form a crescent extending entirely around the head of the Sacramento Valley, the convex side to the north. Recent studies by the U. S. Geological Survey in cooperation with the California State Division of Mines show that there are two districts, one at each end of the so-called copper arc, which are distinct in geologic structure and ore occurrences, and that there is only sporadic and unconnected copper mineralization between them. Ore deposits of the two districts are similar in mineralogy, that is, they are largely massive pyritic ores containing copper and zinc with minor amounts of gold and silver, but the structure and structural control of ore deposition are different. The ores of the East Shasta district are replacements of steeply dipping shear zones in Triassic rhyolite and shale, whereas those of the West Shasta district are replacements of gently dipping rhyolite of Middle Devonian age and are essentially flat-lying. Thus there is marked lateral control of orebodies by shear zones in the East Shasta district and equally marked vertical control of orebodies by the stratigraphy in the West Shasta district. Geologic Setting The Paleozoic rocks of the West Shasta district range in age from Middle Devonian (?) to Missis-sippian. The oldest formation exposed is the Copley greenstone, probably Middle Devonian. It is composed of volcanic flows, volcanic breccias, and tuffs, all of mafic composition, but contains minor amounts of shale and rhyolitic tuff. Largely submarine in origin, it rests upon a base of older marine sediments, as shown diagrammatically in Fig. 3. The lower part of the formation is made up principally of flows, many of which are ellipsoidal, and the upper part contains most of the pyroclastic material. The formation is at least 3700 ft thick. The Balaklala rhyolite overlying the Copley greenstone is made up of many rhyolitic flows and beds

Jan 1, 1956

Discussion of the paper of F. C. NEWTON, presented at the New York meeting, Feb-ruary, 1915, and printed in Bulletin No. 9S, February, 1915, pp. 473 to 477. H. 0. HOFMAN, Boston, Mass.-The results of these large-scale experiments, which were carried on at Perth Amboy, show that there are many differences between theoretical conceptions and their applications to work on a large scale. The author has given reasons why the results of bringing a desilverizing kettle to the high melting point of the zinc-silver alloy, Zn3Ag2, melting at 665° C., are not satisfactory. In all probability the alloy is dissolved in the lead; it may also be decomposed by the lead; the practical result is that this high temperature does not work. It remains now for the laboratory man to carry on systematic experiments

Jan 5, 1915

By T. D. Tiemann

The chemical and mineralogical composition of Caribbean bauxite ores are described. Extraction of alumina by several processes from both Haiti and Jamaica bauxites is discussed and data presented. IMMENSE deposits of bauxite occur in the Caribbean islands of Hispaniola and Jamaica in the high plateau lands and have been excellently described by 0. C. Schmedeman.' The bauxite occurs as deposits in catchments or etched depressions in Tertiary limestone believed to have been deposited in the Eocene and Oligocene periods.' In appearance both the Haiti and Jamaica bauxites resemble a relatively high iron clay and have indeed been mistaken for such.' They are very soft and friable and disperse readily on vigorous agitation in water. The color range in general is light brown to red. Chemically, the outstanding characteristic of the bauxites is the low silica and high ferric oxide content. The extremely low silica makes them particularly valuable for the production of alumina in the Bayer plant since silica is responsible for the loss of both alumina and soda chemically combined as XNa,OYSiO2,ZAl2O2. The ferric oxide, only traces of ferrous iron are present, offers no interference in the production of high grade alumina. Typical oxide analyses of three types of ore are given in Table I2 and a list of the elements occurring in spectrographic quantities in Table 11." The size of the individual particles in the ore makes successful petrographic examination extremely difficult. The ores contain some relatively coarse grains of heavy minerals such as ilmenite, magnetite, and rutile, but other than occasional crystals of a few microns, the greater portion of the minerals are submicroscopic in size and approach colloidal dimensions. The mineralogic composition of the ores has been investigated by X-ray and differential thermal analysis.' These investigations indicate that the predominant mineral phases present are gibbsite (A1203.3H2O), boehmite (Al2O3.H2O), hematite (Fe2O3), and goethite (Fe2O3-H2O). There is no evidence of the occurrence of diaspore (Al2O3.H2O) in either the Haiti or Jamaica ores, but some type of "amorphous" alumina may be present in some of the bauxites of Jamaica." The temperature stability regions in the alumina-water system have been investigated and are given in recent literature. In the temperature range where the hydrated forms are stable, as determined by hydrothermal bomb methods," ibbsite is the stable phase to 155°C (311°F), boehmite from 155°C (311°F) to 280°C (536oF), and diaspore from 280°C (536°F) to 450°C (842°F). Although quite similar in many characteristics, the Haiti and Jamaica ore show a divergence in mineralogic composition that is reflected in the extractability of the alumina described in later paragraphs. Two principal differences occur in mineralogic composition. The iron-bearing mineral in the Haiti ores is predominantly hematite, while in the Jamaica ores goethite is predominant.4 Directly related to the extraction of alumina are the two minerals, gibbsite and boehmite. Boehmite is relatively high in the Haiti ores and in some of the less soluble Jamaica ores, while gibbsite predominates in the ores in Jamaica amenable to the American Bayer process of extraction. Pedersen and Related Processes In general, all processes for the extraction of alumina involving sintering or fusion of bauxite ores with limestone, soda ash, or a combination of limestone and soda ash followed by leaching, are based on the formation of alumina compounds that. yield alumina soluble in the subsequent leach. The principal idealized reactions in respect to alumina and silica for the three types of processes are as follows: Soda Ash Sinter: A12O3 + Na2CO3 = Na2O-Al2O, + CO2 SiO2 + Na2CO3 = Na2O . SiO2 + CO2 A12O2 + SiO2 + Na2CO3 = Na2O.Al2O8. SiO2 + CO2 Leach (with excess water): H2O + Na2O-A12O3 = 2 NaOH + A12O3 (insolution) H2O + Na2O-SiO2 = 2 NaOH + SiO2 (in solution) Soda Ash— Limestone Sinter: Na2CO2 + A12O3 = Na2O.A1203 + CO2 2CaCO3 + SiO2 = 2CaO . SiO2 + 2CO2 Leach (with excess water): Na2O' A1208 + H2O = 2NaOH + A13O3 (in solution) These latter reactions are the basis of the sinter process currently used for the recovery of soda and

Jan 1, 1952

By H. Biloni

A metallographic study of solute segregation produced during controlled solidification of Sn-Pb alloys has previously been reported.' It was found that the growth conditions which produced well-developed cellular substructures led to severe segregation, and even at solute concentrations of 0.2 wt pct Pb regions of a lead-rich phase were formed at the junctions of cell boundaries (nodes). Similar sample preparation and etching techniques have now been applied to several tin alloys at more dilute concentrations. The crystals were solidified uni-directionally under less-severe growth conditions so that the predominant interface structure was composed of two-dimensional cells.* Binary alloys with lead, using 9.999 pct Sn as a solvent, and ternary alloys with lead and bismuth or lead and antimony, using zone-refined tin as a solvent, were examined. The liquid was decanted from the growing crystals in all cases to reveal the interface structure and ensure that two-dimensional cells were being formed. However, since interference may arise from a liquid layer that clings to the interface during decanting,3 an examination of the segregation pattern was always made behind the interface. In all cases, the structure within the bulk of a crystal at greater than 1 cm behind the decanted interface was substantially the same as that nearer the interface. Representative photomicrographs of the dilute Sn-Pb alloy are shown in Figs. 1, 2, and 3. Most observations are similar to those of the previous investigation. For example, the solute concentration at the cell walls is higher than in the intercellular regions; where cell boundaries meet, the segregation is enhanced; the macromosaic or stria-tion substructure and grain boundaries show enhanced segregation; there is also a depletion of solute at cell walls near a striation boundary, as Spittle et a1.4 have observed at decanted interfaces. Not all these observations can be seen in the photos shown since attention has been focused on a special feature; as evident in the photomicrographs, cer-

Jan 1, 1965

New Jersey Zinc Co. - The Plants Canon City Palmerton Depue

Jan 12, 1953

By H. W. Weart, S. Sarian

The effect of temperature, impurities, and capillarity on the morphology of solid particles in a liquid matrix is investigated. For the NbC-liquid iron system, at least, it is found that those particles which are dissolving will assume a spherical shape; all others will take the equilibrium shape. An aniso-tropic-isotropic transition in the interfacial tension is observed at about 1725°C and is believed to be due to cooperative roughening of the interface on an atomic scale. The presence of boron as an impurity lowers the transition temperature. It is the purpose of this paper to present some observations on the shape of particles in a system consisting of solid particles of nonuniform size in a liquid matrix and to propose an explanation for these observations. Although qualitative only, these observations, which were made largely in the course of a study of particle-growth kinetics,' are presented separately to draw attention to them. They reveal the effect of particle size, temperature, and surface-active impurities on particle shape in the solid NbC-liquid iron system, and are unique in demonstrating for the first time the reversible effect of temperature and impurity concentration on the anisotropy of the energy of the solid-liquid interfaces involved. Some of the changes are readily demonstrated with the few particles whose shapes can be clearly shown in a single photomicrograph, but others are more subtle, and their recognition depends upon some experience and the study of a much larger sample. For this reason, a certain amount of judgment must be acknowledged to underlie their detection, but every effort was made to maintain proper scientific objectivity in evaluating the observations. The observations will be presented first, and then an explanation rationalizing them will be offered. Brief reminders of the relevant theories will be inserted into the discussion at the appropriate points. EXPERIMENTAL The observations were made of the shape of NbC particles dispersed in liquid iron. All specimens were prepared by pressing NbC powder and car- bony1 iron powder treated according to standard powder-metallurgical procedures. Except as noted, all specimens were heated to 1900°C for 1/2 hr. In investigating the effect of temperature, specimens were quenched from 1900°C to various lower temperatures, and held long enough (48 hr) to allow shape changes to be completed. Boron, in the form of amorphous powder, and oxygen, in the form of niobium oxide powder, were added as impurities to some specimens. Nitrogen was introduced into some specimens as an impurity by heat treating the samples under a partial pressure of nitrogen gas. Effect of Temperature. It was first observed that increasing temperature had a marked effect in rounding the corners and edges of the particles. At 1900°C the particles are all very nearly spherical and remain so even when the holding time is extended to 48 hr. As can be seen from Fig. 1, there is virtually no evidence of the presence of low-index planes. At 1300°C, however, most of the particles are prismatic with very slightly rounded edges and corners, Fig. 2. (In making these shape comparisons, attention should be focused on the larger particles, even though the smaller ones would be expected to be the first to change shape, owing to the shorter diffusion distances involved. The cause of the mixed particle shape will be explored later.) It was established that these structures are re-

Jan 1, 1965

By John D. Verhoeven

A technique has been developed for carrying out normal freezing experiments with a current density of 2000 amp per sq cut passing through the solid-liquid interface. The equation relating the effective distribution coefficient to the equilibrium distribution coefficient in electric field-aided solidification, originally developed by Huckc et al.,1 has been modified for the case of concentrated solutions. Preliminary experiments on the Sn-Bi system give qualitative agreement with the equation. The data are analyzed by a slightly novel use of the normal freeze equation which allows one to determine the effective distribution coefficient more easily. Very extensive mixing in the liquid was found at these high current densities and it is postulated that the mixing results from a vertical component of the magnetic Lorentz force generated by the electric current. In the search for techniques of obtaining ultrahigh-purity metals the inefficient but very effective technique of electrotransport has received little attention. Electrotransport is most effective in the liquid state and a natural application, therefore, is to apply an electric field across the liquid zone of a zone-melting experiment. The present investigation was undertaken to study the effect of an electric field upon solidification of metals, so that the usefulness of electrotransport in such solidification experiments as zone melting could be determined. In zone-melting and normal-freezing experiments it is difficult to achieve complete mixing in the liquid in the immediate vicinity of the solidifying interface. Consequently a solute build-up will occur at the interface in the portion of the liquid where complete mixing does not occur (an equilibrium distribution coefficient, ko, less than one, and unidirectional atom motion will be implied throughout). This local solute build-up produces a corresponding rise in the solute concentration in the solid so that the ratio of the solute concentration between the solid and the bulk liquid is larger than the equilibrium distribution coefficient. This ratio is defined as the effective distribution coefficient, k,. The differential equation describing the solidification process may be derived by applying the continuity equation to an expression for the net solute flux at the interface. The solution to this differential equation then allows one to determine the solute distribution in the liquid and the relationship between k0 and ke. One of the most useful solutions to this equation was first derived by Burton, Prim, and Slichter,' in which they assumed that a) the equilibrium distribution of solute was maintained on the plane of the interface, 11) the solute build-up ahead of the interface in the liquid disappeared at a distance 6 from the interface, and c) the solute distribution in the liquid was invariant with time. The following well-known relation between ko and ke was then obtained, where R is the rate of solidification and D the diffusion coefficient of the solute in the liquid. This equation appears to correlate the data from a number of different types of solidification experiments very well. Application of an electric field across the solid-liquid interface can produce an additional flow of solute atoms as a result of the electrotransport. When the polarity of the field is such as to direct the electrotransport flux away from the interface the solute build-up may be diminished, even to the point of producing a solute depletion and a consequent ke smaller than ko. The quantitative description of this process and the resulting form of Eq. [I] was first given by Hucke et al.1* and then inde- where E is the electric-field intensity and U is the differential mobility, i.e., the velocity of the solute atoms with respect to the solvent atoms per unit electric field. Both authors follow the method of Burton, Prim, and Slichter in their derivation, the only difference being the additional electrotransport term in the flux equation. It has been pointed out1,3 that Eq. [2] predicts the possibility of a noticeable increase in the purification of materials by solidification in an electric field. The validity of Eq. 121 has not been checked experimentally and it is possible that other factors' arising from the presence of an electric field across

Jan 1, 1965

By Samuel S. Adams

Potash, the generic term for a variety of potassium-bearing minerals, ores, and refined products (Table I), owes its importance as an industrial mineral to the potassium requirement of growing plants. The term "potash" originally referred to potassium carbonate produced by the leaching of wood ashes. This process, for which the first U.S. patent was issued in 1790, was the basis for the largest United States chemical industry in the early nineteenth century. The agricultural use of potash soon eclipsed the chemical applications following the German discovery in 1840 that potassium is essential to plant growth. The initial discoveries of large deposits of soluble potassium minerals, essential for agriculture applications, were made in 1857 in Germany and in 1914 in the United States. More than 90% of the 20.4 million short tons K2O produced in the world in 1970 (Eilertsen, 1971 ) was derived from marine evaporite deposits and approximately 90% was used in fertilizers. The potassium content of an ore, mineral, or product is customarily expressed as % K,O, a unit of measure which is neither a natural nor synthetic compound of potassium (1 .O% K is equivalent to 1.2046% K,O) . Geology Potassium, the seventh most abundant element in the earth's crust, is present in silicate minerals in igneous, sedimentary and meta- morphic rocks. Potassium is also a major constituent of many surface and subsurface brines (Table 2). Economic potash deposits are essentially restricted, however, to widespread, thick accumulations of marine chloride evaporite deposits. These deposits yield high grade, large tonnage ore bodies, many of which are amenable to low cost mining and beneficiation. The products from these deposits are, moreover, ideal for use in fertilizer because of the high relative solubility of the potassium chloride and sulfate evaporite minerals. World potash production and reserves for such de- posits so vastly overshadow other sources of potassium that the following discussion will be limited largely to potash deposits in marine evaporites with brief reference to certain potash-rich brines. Approximately 85% of current domestic production is from bedded salt deposits and much of the balance is from brines. Marine evaporite deposits are accumulations of salt minerals deposited in structural sedimentary basins through the evaporation of sea-water or mixtures of seawater and other brines. The salt minerals are precipitated in assemblages and sequences of assemblages as determined by the compositions of the brines and the solubility relations in the salt systems (D'Ans, 1933). The evaporation of seawater normally yields carbonate minerals as the first precipitates (Table 3). Further evaporation and concentration of the brine leads to the precipitation, in succession, of sulfate, chloride, and supersaline mineral assemblages including the salts of potassium and magnesium. The common minerals, ores, and products of potassium deposits are listed in [Table 1]. Many potash deposits contain accessory evaporite minerals together with a variety of detrital and authigenic silicates (Braitsch, 1971).

Jan 1, 1975