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By Richard W. Smith

There are three distinct varieties of phosphate rock, in Tennessee, known commercially as: (a) the "brown" rock, which is the residual product of the weathering and natural concentration of certain phosphatic Ordovician limestones; (b) the "blue" rock, which is an unaltered phosphatic stratum of Mississippian or Devonian age; and (c) the "white" rock, which is the result of chemical replacement and deposition. Before 1894, South Carolina and Florida had supplied most of the phosphate of the United States, South Carolina leading until that date and Florida from then until the present time. In December, 1893, the blue phosphate of Tennessee was discovered almost simultaneously on Swan Creek, in Lewis County, by two independent parties—by one as the result of a careful and systematic search for a workable deposit of the long known kidney phosphate, and by the other through mistaking it for a "bloom" of coal. Leases were taken and, with further prospecting disclosing other deposits in the region, the development progressed as rapidly as could be expected without railroad transportation. In January, 1896, Judge S. Q. Weatherly, who was interested in the development of the blue phosphate, while riding along the road south of Mt. Pleasant, noticed some slabs of a brown rock in place above the limestone. He took samples, and had them analyzed, thus discovering the high-grade brown phosphate of this district. This discovery was kept a secret until July, 1896, when mining was started at the village of Mt. Pleasant. Development proceeded rapidly, many owners obtaining their capital by the sale of their rock fences, which were largely composed of slabs of high-grade brown phosphate. The development of the brown rock, which is richer and more easily mined than the blue, caused Tennessee to advance from a poor third in production to second, surpassing the output of South Carolina, and being excelled only by Florida.

Jan 1, 1927

By Richard R. Zupp, David A. Stevenson

An experimental method to determine the carbon activity in various solid solutions was developed. Samples of the solid solutions and an Fe-C reference sample were equilibrated with respect to carbon content by annealing them in a Hz-CHI gas mixture in a closed cell. The carbon content of each sample was determined, and the carbon activity was obtained from the carbon content of' the reference sample and well-established data for the dependence of the carbon activity on the carbon content in Fe-C alloys. The influence of vanadium on the activity of carbon in austenitic Fe-C-V alloys at 1000°C was determined by this technique. A general semiempirical correlation was developed to describe the dependence of the activity coefficient of- carbon on the composition of ternary austenitic iron-base alloys containing interstitial carbon and a substitutional solute. The correlation is particularly useful in predicting the partitioning of- carbon between various alloys. THE influence of substitutional solutes on the activity of interstitial solutes in metallic solid solutions is important in the theory of alloy phases. Solid solutions of particular interest are the fcc austenite phases of ternary Fe-C-Z systems, in which carbon is the interstitial solute and Z represents any substitutional solute. Carbon-activity data are also needed in these solid solutions to solve practical problems; the quantitative treatment of diffusion-controlled transformations' is an examvle. Experimental information is available for ternary austenitic solid solutions containing Mn,2 Si,2 and A16 as the substitutional solute. Because qualitative preliminary studies indicated that vanadium appreciably decreases the carbon activity,14 the present investigation was undertaken to determine the influence of vanadium on the activity of carbon in austenite. Although Flender and ever" measured carbon activity over a range of compositions in the Fe-C-V system, they were primarily interested in determining phase boundaries in the ternary system, so most of their measurements were outside the composition range for stability of single-phase austenite. Petrova and Shvartsman' also made limited measurements of the carbon activity in Fe-C-V alloys. The dependence of the carbon activity on the carbon content of an alloy may be determined by passing COCOz or H2-CH4 gas mixtures of carefully measured composition over the alloys, determining their equilibrium carbon content, and utilizing the relevant equilibrium relationships. smith16 used this technique with both CO-COZ and HZ-CH4 gas mixtures to determine the dependence of carbon activity on carbon content in pure Fe-C alloys. His data, which are in good agreement with those of some previous and subsequent investigators,6'17 but not with those of others,lfl'ao are usually considered to be the most reliable. Although the same method can be applied to Fe-C-Z alloys, it is difficult experimentally, because the appropriate gas mixtures are almost pure CO or Hz. A simpler technique is to simultaneously equilibrate the Fe-C-Z alloys and pure Fe-C alloys with the gas mixtures, and then use Smith's data to determine the carbon activity in the pure Fe-C alloy. A number of investigators have employed this technique. others Have used the partitioning of carbon at the interface of a diffusion couple prepared from an Fe-C alloy and a Fe-C-Z alloy. In the present study, a closed-cell method was developed by which carbon was selectively transferred via a gas medium between pure Fe-C alloys and Fe-C-V alloys which were not in physical contact. A similar method was developed independently by Heckler and winchel14 and used to study the Fe-C-Ni system. EXPERIMENTAL METHOD A schematic diagram of the experimental arrangement is shown in Fig. 1. In a typical experiment, a 5-g Fe-C sample was placed in one compartment of a quartz cell, and a 5-g Fe-V sample was placed in each of the other compartments. The cell was evacuated, outgassed, backfilled with approximately 125 Torr of hydrogen, and sealed. After being placed in a fur-

Jan 1, 1967

By C. R. St. John, R. W. Lindsay, Charles R. Austin

MANY of the factors influencing the creep behavior of ferrous alloys have been investigated and reported upon in the literature, including such variables as grain size, steelmaking practice, nature and stability of the microstructure, and the effect of alloying elements in steels. However, with respect to the latter, the microstructures involved are usually heterogeneous and as a result the effect of the addition is related to its effects on the various phases present in the microstructure. In the instances where this structure consists of ferrite and carbide, the behavior of the alloy addition will be related to its action in strengthening ferrite and in opposing temperature softening of ferrite as well as coalescence of carbide. The present paper is the third in a series comprising a comprehensive review of investigations on the properties of iron binary alloys. 1.2 Its purpose is to describe the results of isolating one microstructural phase, namely ferrite, and studying its creep characteristics in both the unalloyed and alloyed conditions. This should aid in establishing to a large degree the importance of ferrite in the creep behavior of steels consisting of the previously mentioned ferrite-carbide aggregate. REVIEW OF PREVIOUS WORK In view of the fact that the present investigation deals only with the effects of silicon, manganese, chromium, molybdenum, nickel, and cobalt, and to a certain extent with the effects of carbon, the review of previous literature will be confined to these elements. Practically no references were encountered dealing with the influence of these elements on the creep characteristics of the isolated phase. However, various contributions have dealt with the creep behavior of low-carbon steels alloyed with the elements under consideration. A particularly concise review in this respect is given by Bullens (Battelle)3 and much of this material has been drawn upon. The definite improvement in creep resistance and high-temperature strength conferred by molybdenum is well known. Published suggestions by the A.S.M.E.4 permit of an increase of some 2000 to 5000 lb. per sq. in. in permissible design loads over a temperature range from 650° to 1000°F. as a consequence of additions of 0.40 to o.60 per cent of this element in carbon steels of the order of o.25 to o.35 per cent carbon content. Babcock and Wilcox Tube Co.5 has published data showing the pronounced increase in stress necessary to cause one per cent creep per 10,000 hr. when additions of 0.5 or 1 per cent molybdenum are made to a plain carbon steel. These data apply to temperatures over a range from 800° to 1000°F.

Jan 1, 1945

By Wm. I. Weisman, Sid McIlveen

Sodium sulfate is an important industrial chemical, being one of perhaps a dozen or so chemical commodities produced and consumed in the United States in quantities exceeding 1 Mt/a. In recent years approximately half that production has come from natural sources, whereas 27 years ago only 25% was derived from these sources. Table 1 illustrates the history of production of natural sodium sulfate in the United States. Production of natural sodium sulfate from various types of deposits is the main source of this chemical in Canada and Mexico, and probably in Argentina, Chile, Spain, and the USSR. Mineralogy and Physical Properties Sodium sulfate is widespread in occurrence and is a common constituent of many mineral waters, as well as seawater. Atmospheric precipitation contains sulfate; it is one of the major dissolved constituents of rain and snow (Davis and DeWiest, 1966). Many of the saline lakes throughout the world contain varying amounts of sodium sulfate. Because sodium is usually the dominant cation, some workers make an anionic distinction, referring to lakes containing predominately sulfate as bitter lakes and those containing predominately carbonate as alkali, or soda lakes (Bateman, 1950). Sodium sulfate in its natural form is found as the hydrous salt mirabilite (commonly called Glauber's salt), and as thenardite, the anhydrous variety. The largest quantities occur in the form of mirabilite. Sodium sulfate is found in varying degrees of purity, from theoretically pure efflorescent crystals of mirabilite to combinations and admixtures of other salts and impurities. It is a common constituent of some brines; from this source much is extracted commercially. [ ]

Jan 1, 1983

By F. V. Lenel, J. A. Dromsky

The influence of thermal and mechanical treatments upon the elevated-temperature stability, the microstructure, and the mechanical properties of aluminumaluminum oxide alloys is investigated. Compacts from atomized and flake aluminum powders were sintered at temperatures just below the melting point of aluminum in a vacuum of 10-4 Torr for several hours and were then hot-extruded. During this treatment the hydrated oxide present on the surface of the powder particles decomposes, the water vapor produced reacts with the aluminum forming additional oxide, and the hydrogen developed is removed by diffusion to the surface. Extrusions of compacts so treated are stable at temperatures up to the melting point of aluminum and do not form blisters and internal defects typical of extrusions from untreated powder. Electron micrographs of extrusions from unsintered compacts show long parallel oriented platelets typical of the IN previous investigations1,2 the properties and structure of aluminum alloys were described which had been produced by cold compacting aluminum powder and then hot pressing and extruding the compacts. Both the structure and the properties of these alloys differ significantly from those of commercially produced aluminum-aluminum oxide alloys. When commercial alloys are produced, they are given a sintering treatment in air at about 600°C between cold compacting and hot pressing.3 During this treatment the hydrated oxide, which forms the coating on the aluminum-powder particles from which the alloys are prepared, is decomposed.4 The chemically bound water which is released reacts with the aluminum and forms aluminum oxide and hydrogen. Most of the hydrogen is eliminated by hydrated oxide skins on the original powder particles, while the oxide particles in extrusions from sintered compacts are broken up. The strength of extrusions from treated powder is somewhat lower, but their ductility is considerably improved over that of extrusions from untreated powder. The slip-trace patterns on electron microgvaphs of extrusions which had been strained in tension before replication indicated that the grain size of the extruded alloys was approximately the same as that of the original powder particles. Coarse-grained alloys were produced by severe cold work and annealing of the extrusions. They have significantly lower room-temperature strength, but about the same ductility as the vacuum-sintered fine-grained alloys. The size and shape of oxides in the coarsegrained alloys is similar to those of the fine-grained alloys, but the particles are somewhat more uniformly distributed. diffusing to the interior or exterior surfaces of the compact, but it is difficult to eliminate all of it because the solubility of hydrogen in solid aluminum is very low even near its melting point. Extruded alloys which are not sintered before hot pressing and extrusion appear quite sound upon metallo-graphic examination, but develop severe surface blistering and internal fissuring when they are heated to elevated temperatures after extrusion. Fissures and blisters have been observed even in commercial alloys which had been sintered in air, although they are much less severe.' Because of the importance of this sintering treatment it was studied in this investigation in a modified form, using vacuum sintering rather than sintering in air, to insure more complete elimination of occluded hydrogen. The technique is described and the effect of the treatment upon the structure of the alloys is documented. It has been known for some time that extruded aluminum-aluminum oxide alloys are very finegrained, but an exact delineation of grains in electron micrographs has not been possible. In the conventional metallographic-etching techniques etchants attack the interface between the second-phase particles and the matrix in the alloys much

Jan 1, 1964

By W. R. Crane

MINING of the red iron ores of the Birmingham district has been carried on energetically during the past 50, years, and their development has created a large iron and steel manufacturing, center, the only important one in the South. The district produces approximately 10 per cent. of all the iron ore of the United States (80 per cent. of the Alabama ore mined is red ore) ; also, 43 of the 419 blast furnaces of the country are in the district tributary to Birmingham. The rapid growth of the district has been made possible through investigations that resulted in radical changes in furnace practice, and a still greater impetus will come from the study of the low-grade, high-silica ores, as a result of which they will be made amenable to treatment by concentration. Mining practice in this district has been comparatively simple because of the occurrence of the ore; but with the-rapid extension of the work-ings and the disturbed condition of the ore bed at some distance from the outcrop, more difficult conditions are encountered and the tendency is toward worse rather than better conditions. Should the high-silica ores of the lower bench of the Big Seam become available through beneficiation, mining practice will have to be modified to meet the new conditions, which will be rendered more difficult by the increased weight of cover that will exist at considerable distances from the outcrop. Support of workings will require greater attention and the efficient and economical operation of the mines will depend largely on the successful solution of the problems of working-and handling the ore.

Jan 9, 1924

By J. Chipman, J. C. Fulton

Reduction of Si from slag to carbon-saturated iron is a very slow reaction. The rate is nearly independent of stirring but is accelerated markedly by increased temperature. In a slag containing 45 pct SiO2, 38 pct CaO, 17 pct Al2O3, the energy of activation is approximately 130 kcal. AT temperatures of 1450" to 1600°C occurring in the hearth of the iron blast furnace, chemical reactions are normally expected to proceed with great rapidity. Many of the reactions of iron making are indeed quite rapid and attain a condition corresponding roughly to a state of equilibrium before metal and slag are tapped from the furnace. The one conspicuous exception is the reaction by which carbon in the coke or metal reacts with silica in the slag to deliver silicon to the metal. From the practical viewpoint the slowness of this reaction is indeed fortunate, for if it were fast enough to reach equilibrium during the time of contact, it would be difficult to produce pig iron of the desired low silicon content. The one other reaction which under certain circumstances can also be very slow is the transfer of sulfur from blast-furnace metal to slag. In their laboratory exeriments on this reaction, Hatch and Chipman found that at least 5 hr were required for the attainment of equilibrium in a small crucible and that the reaction was not accelerated by increasing the rate of stirring. Subsequently it was shown2 that the presence of a reducible oxide MnO greatly inhibited sulfur removal, and finally that SiO2 itself3 under some conditions has sufficient oxidizing Dower to interfere with sulfur transfer. The kinetics of sulfur removal are now rather well understood,4 and it has been shown3,5 that when the silicon content of the metal is high enough to prevent reduction of SiO,, the desulfurizing process is rapid. Thus the observations of slow removal of sulfur are associated with the coincident slow reduction of SiO2, a process which transfers both silicon and oxygen to the metal phase. It is, of course, the oxygen which interferes with sulfur removal. An explanation of the slowness of the silica reduction reaction has not been obtained. The sulfur transfer process has been shown by the authors5 to be at least partially transport-controlled in the absence of interference by silica. Under the experimental conditions. 99 pct of the total transfer at 1600" was accomplished within an hour. Under similar conditions the reduction of silica may not proceed half-way to equilibrium6 in 8 hr. It is scarcely imaginable that silica reduction could be transport-controlled when the slag contains 44 pct SiO2 and the metal about 1.4 pct C. The experiments reported here show definitely that it is controlled by a slow step or steps in the chemical reaction. One might expect to find such a slow step in the breaking of SiO bonds or in the slow removal of oxygen by carbon at the slag-metal or metal-crucible interface or by bubble formation. EXPERIMENTAL PROCEDURE The experimental procedure used in this investigation was similar to that used in the study of the kinetics of desulfurization.5 A sketch of the graphite crucible and stirrer used in the current work is shown in Fig. 1. The quantity of metal and slag used was adjusted so that the slag-metal interface was located between the top and bottom blades on the stirrer; the top of the slag layer was above the top blade. The stirrer shaft was hollow down to the metal level and served as thermocouple well or optical pyrometer target. Stirring speeds of 0 to 500 rpm were used. A carbon monoxide atmosphere was maintained in the furnace by flushing the gas over the slag surface, except in run No. 220 when it was bubbled

Jan 1, 1960

By Oscar A. Glaeser

THE mine and plant of the United Verde Copper Co., located in Yav-api County, at Jerome, Arizona, have been described in various technical publications and, therefore, a brief outline of its essential features will suffice. The orebodies are of the schist replacement type, the main sulfide mass being a large lens-shaped body approximately 7 acres in cross-sectional area. In general, the mineralization is found along the iron-schist contact, with the orebodies extending about 1000 ft. along this contact and varying from a few feet to 250 ft. in width. The mine is located on a mountain slope and has openings into it on three horizons, as follows: 1. Raises and ore passes open vertically into the shovel pit. These extend down to the 1000-ft. level, where they terminate as loading bins in the Hopewell adit. The main fan intake air shaft, which also extends vertically down to the 1000-ft. level, has its surface opening on the hillside at the extreme north end of the shovel pit, and the main mine air return exhausts through a raise at the extreme south end of the shovel pit. 2. The 500-ft. level adit. 3. The Hopewell adit on the 1000-ft. level. The mine has a vertical downward extent of 2000 ft. below the 1000-ft. level. Underground operations are carried on through two main shafts, both of which are wholly underground. Shaft 5 is the ore-hoisting shaft. It has three compartments and extends from the 800 to the 3150-ft. level. Shaft 6 is the service shaft, and is used for lowering and hoisting men and material. It has a large cage compartment and three smaller compartments for counterweights, ladderway, and pipe and power lines. This shaft extends from the 500 to the 2550-ft. level, and is now being extended to the 3000-ft. level. An air shaft for the downward movement of fresh air from the fan has been provided, and extends to the 2550-ft. level at this time. Work has been started to extend this air shaft to the 3000-ft. level. A return airway for vitiated mine air, in the form of raises and short connecting drifts, extends downward to the 2100-ft. level. The underground mining operations extend from the 300 to the 3000-ft. level. There are about 45 stopes in active operation on the 17 levels

Jan 1, 1929

By D. Hnrrington

THE Dust Symposium was attended by approximately 100 persons, nearly all of whom remained from the starting hour (2 p. m.) until the use of the auditorium was demanded for another meeting at 5:30 p. in. In calling the meeting to order, D. Harrington made a few remarks as to the importance of the health dust problem in mining as well as in general industry and expressed gratification that the subject is now out in the open and that mining people are desirous of ascertaining the facts. B. F. Tillson acted as chairman of the meeting. The milling executive who desires to know what to do to prevent his workers from being unduly exposed to the dust hazard can get much out of the paper by D. E. Cummings, who has been doing much work in mines trying to keep -the dust in the air within safe limits. His recommendations indicate that the main protection of the worker in mines is by adequate ventilation, supplemented by the extensive use of water in drilling, as well as in water curtaining to condition air both in regard to dust content and to temperatures. Blasting was shown to be one of the chief causes for dust and it was recommended that whenever feasible all blasting should be delayed to the end of the working shift.

Jan 1, 1935

By W. C. Browning

The influence of the hydroxyl factor is more damaging to formations penetrated and causes greater consumption of drilling mud additives than previously realized. This hydroxyl effect on clays is essentially independent of the cations present in the drilling fluid and thus differs from the base exchange reactions that have preoccupied mud chemistry with sodium and calcium bentonite concepts for nearly two decades. The new organic polyelectrolyte-con-ditioned muds haw made it possible to use materials other than sodium hydroxide to maintain the alkalinity of such muds. The properties of silicates, as indicated by their dissociation characteristics and buffering action, are such that they can control he pH and alkalinity of drilling muds at the desired level and, at the same time, minimize undesirable hydroxyl effects associated with sodium hydroxide. This use of silicate compounds is different and distinct from prior applications of silicates as deflocculants or shale preservers. Laboratory and field data presented in this report show that silicate compositions can be utilized to adjust the alkalinity of drilling muds and, at the same time, minimize hydmxyl-promoted clay cleavage. INTRODUCTION Studies for improving the efficiency of rotary drilling techniques must consider the chemistry of drilling fluids and of the formations being penetrated. The chemical aspects of drilling must be studied in conjunction with and in relation to the mechanical factors if, for example, penetration rates are to be optimized. Drilling fluid technology has been largely influenced by chemical reactions of the montmorillonite (bentonite) clay minerals. Most of the literature of mud chemistry concerns the properties of bentonite. Clays of the kaolin or illite type, which are nonswelling, are not generally regarded as sources of drilling mud problems. If these nonswelling shale clays are considered, they are commonly regarded as inert solids. Particularly noteworthy is the fact that the relation of surface and colloid chemistry to massive shale bodies has received only scant attention from drilling technologists. Clay studies reported in the drilling mud literature have dealt, for the most part, with the properties of clays in a finely divided state, and often in very dilute suspensions. Yet frequently during drilling, shale problems not related to the rheology of clay suspensions develop in massive non-bentonitic shale sections of zero or near zero permeability. This paper is concerned with surface chemical reactions that can influence the behavior of these non-bentonite clay masses in such a manner as to adversely affect drilling operations. Browning and Perricone1,2 have pointed out that some of the most troublesome shales to drill, such as the Atoka, contain no montmorillonites. They also pointed out that mud problems can frequently be mitigated by reduction of clay cleavage achieved by using drilling fluids with a minimum of available hydroxyl ions. If pronounced clay cleavage occurs during drilling, the borehole may soften, increasing the possibility of sloughing. In addition, the resulting increased incorporation of high-surface-area clay solids into the mud system can reduce penetration rates and necessitate greater chemical treatment. This increase of shale, of colloidal or near-colloidal dimensions, into the drilling mud is due to clay aggregate cleavage and not to base exchange or swelling reactions, such as occur with bentonites. Searle and Grimshaw3 point out the difference between cleavage or slaking reactions of nonswelling clays (such as illite and kaolinite) and the swelling of bentonite. They further state that the speed of slaking is increased in alkaline water. Eitel1 cites Salmang and Becker, who recognized that clay surface reactions impart plasticity and workability to clay masses. Their results clearly show that all liquids which contain hydroxyl groups in their molecules favor the workability of clays. The ancient technique of aging clays in the moist condition to increase their "workability" is evidence that these clay cleavage phenomena are of considerable importance. The same hydration cleavage that occurs during the aging of nonswelling clays for ceramic use also acts to break up cuttings and soften the borehole during drilling operations. The mechanism of cleavage of the crystalline aggregates of illitic, kaolinitic and other nonswelling clays; and the chemical means of controlling this cleavage are therefore of considerable significance to the drilling mud chemistry. Inasmuch as there is little reference in the drilling mud literature to the cleavage reactions of nonswelling clays, the structure of these clays and certain properties that relate to the mechanism of clay cleavage will be reviewed briefly. STRUCTURE OF NONSWELLING CLAYS Clays such as kaolinite, illite and montmorillonite are compmed of alternate layers of (1) silicon-oxygen tetra-

Jan 1, 1965

By R. Maddin, A. Lawley

Single crystal Mo-Re alloys (99.99+ purity), grown by electron bombardment floating zone heating, were deformed in tension at temperatures from -196° to +200°C. At -196oC, Mo-6 pet Re and Mo-20 pct Re alloys deform by slip on systems of the type (101) [1ll]. Above-78oC, the operative slip system is of the type (112) [111], (101) [1ll], or (211) [1ll], depending upon orientation. Mo-39 pct Re alloys deform by twinning and slip at all test temperatures with a (112) [111] type twinning system. Critical resolved shear stress for slip and twinning is calculated as a function of composition and temperature, and the mechanical properties compared with those of less Pure polycrystalline alloys. HEXAGONAL close-packed rhenium, c/a = 1.615, is highly soluble in molybdenum. The bee molybdenum-rich solid solution extends to approximately 42 at. pet Re* at 2500°C,' Fig. 1. Recent work on polycrystalline alloys has shown conclusively that the addition of rhenium to molybdenum improves both the fabricability and the low-temperature ductility.2"5 Similar behavior is observed for W-Re and Cr-Re alloys.5 Initially, Geach and Hughes2 found that the Mo-30 pct Re alloy could be cold rolled to approximately 90 pct reduction before the onset of cracking. The remarkable effect of the rhenium was later confirmed by Jaffee et al. 3-5 with an optimum condition of maximum strength combined with maximum ductility at the Mo-35 pet composition. At higher rhenium contents, the ductility was severely impaired due apparently to the presence of brittle tetragonal s phase, Fig. 1. In the Mo-35 pet Re alloy, at least 110 ppm (parts per million) oxygen could be tolerated before cold workability was reduced. By comparison, the corresponding tolerance figure in unalloyed molybdenum is ~ 10 ppm. The effect of rhenium was considered in terms of: 1) a reduction in oxygen solubility in the lattice; 2) a redistribution of intergranular oxide from grain boundary films to isolated spheres; and 3) the promotion of twinning as a further mode of plastic deformation. Paradoxically, twinning is often associated with brittle fracture in iron and the silicon irons.6'7 Work to date has been restricted to are-melted and powder metallurgy polycrystalline material of ~ 99.9 pet purity. The present investigation was initiated for the purpose of determining the mode and crystallography of plastic deformation of a series of bee Mo-Re alloy single crystals over a wide temperature range from -196o to +200°C. Using high-purity zone-melted material (~ 99.99 + pet purity), the specific role of rhenium in the molybdenum lattice may be understood more fully since effects due to grain boundaries and oxide redistribution will be absent. At the same time, the study provides a comparison of single and polycrystalline deformation behavior. EXPERIMENTAL TECHNIQUES A) Preparation and Purity of Single Crystals. Alloys in the form of either are-cast and swaged or sintered and ground bar, 0.120 in. diam, were obtained from the Chase Brass and Copper Co. Alloy single crystals ~ 8-in. long were grown from the

Jan 1, 1962

By Granville S. Borden

The fruits of industry are divided between capital, labor, and governments. Capital takes its redemption and remuneration through profits or dividends; labor takes its share through wages; governments take their share through taxes. Each must have a just share, and the question of what is a just share and the question of who-shall make the allocation are vital current political and economic issues. Certain political philosophies con- tend that government should take all the fruits and that some dictator or politician should have irrevocable discretion and power to distribute the fruits. Believers in democracy and free enterprise adhere to the view that capital is entitled to redemption and fair remuneration; that labor shall have a fair wage; and that governments shall make equitable levies. But since all human beings, both individually and in groups, are inherently selfish, there are many variable views in regard to the question of what ratios shall be applied in a division of the fruits and who shall have the power to fix these ratios. Perhaps all parties should devote more energy to means of increasing the crop, and not so much time to quarreling over a division of the existing crop. Moreover, all three parties must guard against killing the goose that lays the mineral eggs. For example, if the tax burden becomes oppressive and the taxpayer refuses to carry it, then business stagnates, with consequent unemployment, reduction of profits, and curtailment of government revenue. If a producer assumes the increased tax burden, marginal operations must be closed down, and again the consequences are increased unemployment and diminished government revenue. Quite often an increase in a rate of tax results in a reduction of government revenue. Perhaps the worst detrimental feature of selfishness and greed on the part of any one of the three distributees of the fruits of industry is the retardation of expansion of the enterprise. Growth means new jobs, more government revenue, better trade, and better standards of living. Explorations and discoveries have resulted in tremendous contributions

Jan 1, 1959

By J. S. Hegwer, P. M. Dunlap

An improved acid for the treatrrzent of sulfate-con-raining limestones and dolomites is described. The acid is designed to reduce he reprecipitation of dissolved calcium sulfate and the possibility of plugging permeable flow channels. In addition, this improved acid has a much lower reaction rate than that of regular acid; the advantages of a "retarded" acid are obtainable. Field testing of the acid has shown it suitable for use in sulfate-containing formations. Substantial improvements in productivity generally resulted. INTRODUCTION Acid treatments of limestones, dolomites and other formations bearing carbonate deposits are frequently unsuccessful when the calcareous formation contains sulfate, either as anhydrite (CaSO,) or gypsum (CaSO4. 2H2O). Preliminary dissolution in acid followed by redeposition of calcium sulfate appears to be a major factor contributing to poor well performance after acidizing. The precipitate is usually the gypsum form of calcium sulfate, but in higher temperature formations it may be anhydrite. The freshly precipitated crystals are nearly always very small and needle-like. They may occupy a gross volume many times that of the original anhydrite crystals and will obviously constitute an impediment to flow through newly enlarged flow channels. It is believed that the redeposition problem is most severe when anhydrite lines the fracture systems and large pores which supply the effective permeability of a formation. Microscopic inclusions of calcium sulfate also present large sulfate surface areas for dissolution in acid. In either case, great amounts of calcium sulfate may dissolve before the acid can be spent on formation carbonates. For regular spent acid (originally 15 per cent hydrochloric acid) the precipitate could be as much as 270 Ib gypsum/1000 gal acid. Two techniques have been applied by the industry for reducing sulfate plugging during acidizing. The method'.' commonly employed in the field is the attempted removal of a quantity of regular treating acid before it has reacted completely with the formation. This is practiced because the solubility of calcium sulfate is greater in a solution that is still acidic than in one which has been largely spent on the formation rock. The chance of precipitative plugging is therefore reduced if the withdrawal is successful. However, it is often impossible to get the acid out of the formation before precipitation occurs. A second possible method, which at first glance appears practical, involves addition to the acid of sequestering agents which form strong soluble complexes with calcium ions. These chemicals do increase the "solubility" of calcium sulfate in fresh acid, but to a lesser extent in spent acid. The sequestering agents have, therefore, proved unsatisfactory because the amount of sulfate eventually deposited from the spent acid may be greater than that from regular acid. Another logical approach to the problem of calcium sulfate reprecipitation is the prevention of the initial dissolution of calcium sulfate by the common ion effect. This may be accomplished by adding a soluble calcium salt to the fresh acid. The use of calcium salts in treating acids is not entirely new. An earlier suggested use of a soluble calcium salt in hydrochloric acid apparently failed to recognize the full extent to which the solubility of calcium sulfate could be suppressed. The present study extends this earlier work and adds certain improvements toward the development of a practical anti-anhydrite acid. LABORATORY DEVELOPMENT Calcium Sulfate Solubility Table 1 shows the results of a laboratory study performed to establish the effect of calcium chloride concentration on gypsum solubility. Because of the strong tendency of calcium sulfate to form supersaturated solutions, accurate solubilities are difficult to determine. These solubility data probably are reliable to within ± 15 per cent. The solubility of calcium sulfate in 15 weight per cent hydrochloric acid increases with increasing temperature. This trend is also followed in hydrochloric acid which cantains calcium chloride. This is contrary to the solubility behavior of calcium sulfate in water, wherein the solubility decreases with increasing temperature.

By Robert Henry Bradford

This investigation was undertaken at the suggestion of Prof. Henry M. Howe, of the Department of Metallurgy, Columbia University, who, in a letter to the author, dated October 23, 1900, wrote as follows, suggesting the subject of this dissertation : "The extraction of silver from copper mattes by either the Ziervogel or the Augustin process depends upon converting the silver into silver sulphate by means of the sulphuric anhydride evolved from the decomposition of ferrous sulphate and cupric sulphate, which are formed during the roasting operation itself from the iron and copper sulphides present. "It occurred to me, some time prior to the autumn of 1897, that these processes might be made much easier by adding to them, at the proper stage, ferrous or cupric sulphate, or both, in the form of green or blue vitriol. That is, instead of having to rely solely on our ability to generate these sulphates in this very delicate roasting operation, my idea was that we could add a small quantity of already-prepared sulphate at the proper state of roasting, viz., at or before the period when the solphatizing of the silver occurs. The comprehensive audit of the accounts of a mining company is extremely important in its relations to the legal situation and obligations of the corporation, the personal liability of the directors, and the interests of the investing public. A consideration of the subject as affecting the professional duties and fixing the responsibility of a mining engineer engaged in the expert examination of a mine or in charge of mining operations, is equally important, though this phase of the question is not often presented systematically.

Jan 1, 1903

By R. W. Borio, T. S. Spicer

Inflammability and crossing point apparatus were used to study the influence of increasing amounts oi such inerts as ash, fly-ash, pyrite, limestone and Portland cement with several pulverized bituminous coals. The results indicate that it requires large proportions of inerts to substantially suppress the ease of ignition. The ignition phase of the combustion of solid fuels has been under study periodically since 1900. With the advent of pulverized coal firing some 60 years ago, a technique now dominating the coal utilization field, the ignitibility characteristics have become increasingly important. Much of the early work was directed toward the prevention of coal dust explosions and improved mine safety rather than combustion. Many factors affecting ignitibility have been studied and numerous methods devised in an effort to measure the ignition temperature and these have been reviewed by other authors. A recent survey was made by Finney and Spicerl in 1959, so a discussion of previous work will be omitted. Despite these efforts, the initial stage of combustion, termed ignitibility, is still a little understood phenomenon. In fact, no ASTM method has been adopted for the calibration of this illusive property. However, a D-5 Subcommittee XVI on Ignitibility of Coal and Coke of ASTM (now inactive) defined ignitibility:' "The ignitibility of a fuel is that char-

Jan 1, 1963

By W. M. Weigel

The general term "sand" applies to a multitude of similar materials consisting of fine granular mineral. As usually understood, it means the ordinary natural product used for structural purposes and made up largely of grains of quartz. Quartz sand constitutes by far the greater bulk of the production, but there are other grades used for industrial purposes, such as molding sand, glass sand and many others, that may be grouped under the general name of special sands. Under this general group would fall filter sand, sand-blast sand, engine sand, potter's sand, abrasive sands of all kinds, sand for pulverizing, roofing sand, flooring sand, fire or furnace sand, standard sand, burnishing sand, sand for magnesium oxychloride cement-plasters and sand for chemical and metallurgical purposes. Sources of Supply Sand is a widely distributed natural product and even the better grades are low-priced commodities. For these reasons development has occurred near points of consumption where sand meeting the requirements is available. Some special grades, however, cannot be prepared from any sand bed and shipments are often made over considerable distances when the only developed deposit is remote from the consuming center. This is true of filter sand, sand-blast sand, sand for pulverizing and some of the others when chemical purity or grain size, coupled with the need of a properly equipped plant for preparation, are required. New Jersey is a large producer of filter, engine, sand-blast, fire, and pulverizing sand. Pennsylvania, and West Virginia produce special sands for pulverizing, fire sand, abrasive sand, engine sand and sand for chemical and metallurgical use. Ohio produces much sand-blast, fire and abrasive sand, and some filter sand. Illinois and Minnesota produce

Jan 1, 1926

By Ted C. Briggs

Nitrogen exists in two broad categories commonly designated as elemental nitrogen and fixed nitrogen. Elemental nitrogen is found in nature as a diatomic molecule and constitutes about 78%, by volume, of the earth's atmosphere. Fixed nitrogen is a common term used for nitrogen that is chemically bound to other elements. Although elemental nitrogen is very abundant, nonleguminous plants cannot utilize nitrogen unless it is in the chemically combined form. The content of this chapter is confined to fixed nitrogen since the uses and properties of elemental nitrogen and the fixed nitrogen compounds are different. Bacteria associated with legumes are able to fix atmospheric nitrogen, but not to the extent or in the locations required by modem agriculture. The need to use fertilizers containing fixed nitrogen compounds to grow food crops has been recognized for hundreds of years, and from antiquity farmers have used organic wastes such as animal manures, vegetable wastes, sewage sludge, fish scraps, etc., containing these compounds for fertilizers. The organic materials have a low nitrogen content, however, and cannot support large-scale food production. Known commercial-size deposits of natural nitrates containing much higher nitrogen content exist only in Chile, and the possibility of the discovery of other significant deposits is remote. The Chilean deposits were the major source of nitrogenous fertilizers until about 1913, when the Haber-Bosch process for the production of synthetic ammonia was developed. In the Haber-Bosch process, nitrogen reacts with hydrogen, at high temperatures and pressures and in the presence of a catalyst, to form ammonia. At present Chile is the only country in the world with a nitrate mining industry, and, although the mining of natural nitrates is an important industry in Chile, natural nitrates are relatively unimportant, worldwide, because of the adoption of fixed nitrogen processes. The relative amount of the world demand for fixed nitrogen that is derived from natural nitrates has declined in recent years and will continue to decline. Modern farmers are sophisticated in economic calculations such as cost to benefit ratios and, for the most part, they purchase plant nutrients which give the highest return on their investment. Natural nitrates cannot compete on a fixed-nitrogen cost basis with anhydrous ammonia and its derivative products. In a limited sense, the fixed nitrogen industry is mining the air. Modern plants use air, water, and, in most cases, natural gas to produce the ammonia that is now the key building block of the fixed nitrogen industry. To present an accurate picture of the industry, this chapter on nitrogen follows a format somewhat different from that of other chapters in this volume.

Jan 1, 1975

By A. W. Furbank

In reviewing the aerial cameras produced in different countries, it becomes apparent that in nearly all of them an attempt has been made to secure the greatest possible angle of view. This angle, of course, is determined by the objective. The objectives most commonly in use in aerial cameras have a maximum angle of 65". The objective developed for this new Zeiss camera combines freedom from distortion and brilliant definition, with an angle of 95". Aerial mapping, it is claimed, has been placed on a different economic basis, and new possibilities presented, particularly in connection with automatic stereoscopic plotting instruments, to which some short references are made. One way of enlarging the angle of view is to couple several instruments with their axes convergent, thereby producing a multilens camera. Typical of cameras of this sort in the United States is the Bagley four-lens camera, which later was developed into the five-lens camera (T3-A) of the U. S. Air Corps. More recently, in order to get away from the unfavorable Maltese cross image field of the five-lens camera, and to obtain a more practical form, two five-lens cameras were combined. By using them in tandem and rotating them by 45" relatively to each other, a ten-lens camera was produced, covering an octagonal ground area, with a total angle of view of 140". Similar designs have been evolved in other countries. In all of them, however, a number of difficulties have arisen, quite apart from their large weight and high cost. Because of their complex mechanism, numerous shutters and magazines, and the high precision with which these parts must be interadjusted and synchronized, these cameras are far from dependable. Moreover, a multilens camera by itself does not yet constitute a complete outfit for producing pictures suitable for photogrammetric survey. Because all the component pictures, except the central one, are obliques, it is always necessary to employ rectifying apparatus which transforms the marginal views to the perspective of the central one. In multilens cameras with many individual magazines, it is not convenient to

Jan 1, 1941

By A. W. Furbank

In reviewing the aerial cameras produced in different countries, it becomes apparent that in nearly all of them an attempt has been made to secure the greatest possible angle of view. This angle, of course, is determined by the objective. The objectives most commonly in use in aerial cameras have a maximum angle of 65". The objective developed for this new Zeiss camera combines freedom from distortion and brilliant definition, with an angle of 95". Aerial mapping, it is claimed, has been placed on a different economic basis, and new possibilities presented, particularly in connection with automatic stereoscopic plotting instruments, to which some short references are made. One way of enlarging the angle of view is to couple several instruments with their axes convergent, thereby producing a multilens camera. Typical of cameras of this sort in the United States is the Bagley four-lens camera, which later was developed into the five-lens camera (T3-A) of the U. S. Air Corps. More recently, in order to get away from the unfavorable Maltese cross image field of the five-lens camera, and to obtain a more practical form, two five-lens cameras were combined. By using them in tandem and rotating them by 45" relatively to each other, a ten-lens camera was produced, covering an octagonal ground area, with a total angle of view of 140". Similar designs have been evolved in other countries. In all of them, however, a number of difficulties have arisen, quite apart from their large weight and high cost. Because of their complex mechanism, numerous shutters and magazines, and the high precision with which these parts must be interadjusted and synchronized, these cameras are far from dependable. Moreover, a multilens camera by itself does not yet constitute a complete outfit for producing pictures suitable for photogrammetric survey. Because all the component pictures, except the central one, are obliques, it is always necessary to employ rectifying apparatus which transforms the marginal views to the perspective of the central one. In multilens cameras with many individual magazines, it is not convenient to

Jan 1, 1941

By M. L. Samuels

DURING the period from 1910 to 1920, there was a lively interest in. the subject of grain growth and many papers were published, followed by interesting discussions. Questions dealing with the fundamentals of grain growth-why and how it occurs-were treated in papers by Howe,1 Jeffries,2 Sauveur,3 Chappell,4 Beilby,5 Mathewson -and Phillips,6 McAdam,7 Carpenter and Elam,8 Stead and Carpenter,9 Ruder,10 as well as others. Since that decade, much indeed has been done regarding the practical control of grain size, and it is now possible to order material having a size specified in the American Society for Testing Materials classification. Also, one hears the term "spliced boundaries" used in connection with certain tungsten lamp filaments" wherein it is important to prevent "sagging" between consecutive turns of the helix.12 This practical use of a certain knowledge as to the things that influ-ence or even control grain growth should not be taken as an indication that the subject has been thoroughly explored and that nothing more can be learned from fundamental studies. It is with this thought in mind that a report of some observations and experiments on abnormal grain growth is believed justified. Abnormal grain growth is met with in heat-treating high-carbon steels in the austenitic range,13 in the harden-ing treatments of high-speed steels,14,15 and in the low-temperature annealing of strained low-carbon steels as in sheet and wire material. Entirely aside from these instances of exaggerated grain growth, which some might consider as freakish, it is thought that abnormal growth is simply a case where the growth forces and the forces tending to prevent growth are almost, but not quite, evenly balanced. Information relative to grain-growth characteristics in general may be obtained from a study of abnormal growth conditions, which may be looked upon as vantage points. Reflection will show at once that if growth forces are great in comparison to inertia or resistance to growth, many crystals start to grow and, for that reason, none becomes very large, whereas if inertia is predominant no growth at all takes place. Under conditions in which

Jan 1, 1938