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By D. Turnbull, J. H. Hollomon, J. C. Fisher

The concepts of nucleation and of growth have adequately described the isothermal phase transformations to which they have been applied.ls2 However, these concepts have not yet been used successfully to describe the kinetics of a number of transformations that are not observed to take place isothermally. A typical reaction of this type is the austenite to martensite transformation in steels, for which the new phase appears only during cooling of the parent phase. If the cooling is interrupted, transformation ceases; yet had the cooling continued, transformation would also have continued. Nuclei of a new phase do not leap into existence all at once by the simultaneous cooperation of a large number of atoms or molecules of the parent phase; rather they are formed at finite rates by gaining or losing atoms one at a time from the surrounding materiaL3,4 Further thermo-dynamic considerations require a finite concentration of small transitory nuclei of all unstable phases to exist at equilibrium in a stable phase.= For steel in particular, nuclei of ferrite (a iron) exist at equilibrium in austenite (y iron) at temperatures where austenite is the stable phase. If a high-temperature phase a be cooled sufficiently rapidly from temperature TI above the a-ß equilibrium temperature To, to temperature T-1 below To where ß is the stable phase, the equilibrium distribution of ß nuclei corresponding to the high temperature will be retained. There are two limiting possibilities of particular interest: I. The steady state rate of nucleation of ß may be appreciable at T_1, and may require a concentration of sub-critical nuclei exceeding that retained from the high temperature. Time will be required then for the concentration of nuclei to build up to the steady state value, and an induction period will be observed during which the rate of nucleation will increase to the steady state value. 2. The steady state rate of nucleation of ß may be negligible at T-l, while the critical size for continuous growth of ß nuclei, which decreases with increased subcooling of the a phase, may reach a value so small that some. of the retained high-temperature nu-

Jan 1, 1949

By Will L. Clark

He who enters a mining claim within an Indian reservation of the United States of America acquires no rights thereby, because of the fact that the lands within such Indian reservation are not a part of the public domain, and cannot be located or acquired as mineral land. However, where such an entry is authorized as to a particular reservation by an Act of Congress, such claims as may be ontered under such authorization are thereby segregated from the reservation, and the Indian title is oxtinguished. Under the Choctaw Constitution, any citizen of that nation, in other words any Choctaw Indian, who discovered a coal mine, acquired an exclusive right to all coal within a radius of 1 mile. The laws of the Chickasaw nation provided for the formation of corporations to develop coal and other mines, with authority to contract with others to develop and work the mines. Under these laws, leases were made; but Congress subsequently abrogated all existing leases, prohibited all persons from receiving royaltics from such mines, and provided that all coal within the nation should remain the common property of the tribes. , Such leases are now expressly prohibited by an Act of Congress (32 United States Statutes at Large, 655). All leases of mineral lands upon Indian reservations must now be made under regulations promulgated by the Secretary of the Interior, and the royalties must' be paid into the United States Treasury for the benefit of the tribes. In Canada the Indians have no rights to the royal mines and minerals, and the government can make no stipulation with the Indians which would affect the rights of the Province in which the lands are situated. Therefore, while it is true that under our present law no rights can be acquired to a mining claim within an Indian reservation, it seems to be fully within the authority of Congress to make laws, giving such rights to mineral locators as it may deem necessary or expedient. There is a demand for a general law that will permit mining upon Indian reservations, and I am informed that most of the members of both houses of Congress from the Western States are in favor of Congress pass-

Jan 1, 1915

By B. B. L. Seth, H. U. Ross

A generalized rate equation for the reduction of iron oxide was derived from which two particular equations were obtained: one for rate controlled by the transportation of gas, the other for rate controlled by the phase-boundary reaction. Pellets of pure ferric oxide having diameters of 8.5 to 17.5 mm and a density of 4.8 g per cm3 were prepared and reduced by hydrogen at 750° to 900°C. From the analysis of data obtairzed, it was observed that neither the phase-houndarv reaction nor the transportation of gas controlled entirely the rate of redziction. Rather, the mechanism of reduction can he divided into three stages. In the beginning, the process seems to depend predominantly on the surJrce reaction, hut after a layer of iron is formed the diffusion of gas becomes the controlling factor. Towards the end, however, the rate falls sharply due to a decrease in porosity. The times predicted by the generalized equation for a certain degree of reduction showed an excellent agreement with those obtained experinmentally for pellets of varying sizes. WIDE interest in iron oxide reduction has resulted in many valuable studies pertaining to thermody-namical properties, equilibrium diagrams, and chemical kinetics. Although the thermodynamical properties and equilibrium diagrams are now known with a fair degree of accuracy, the mechanism and rate-controlling step in the reduction of iron oxides presents a problem to research workers which is still unsolved. This is because the field of chemical kinetics is so highly complex. Besides the chemical reaction between oxide and reducing gas, several other processes are occurring simultaneously such as solid-state diffusion of iron through intermediate oxides (FeO and Fe3O4), the diffusion of reducing gas inwards and of product gas outwards, and the sintering of iron if reduction is carried out above the sintering temperature of iron. Furthermore, there is a large number of variables, including the nature and flow rate of the reducing gas, the chemical composition and physical properties of the ore, the temperature of reaction, particle size, and so forth, all of which can affect both the mechanism and the kinetics of reduction. Despite the controversy and diversity of opinion about the mechanism of iron oxide reduction, three main schools of thought have emerged. According to the first, the rate is controlled by the diffusion of gas through the boundary layer of stagnant gas; the second claims that the rate is proportional to the area of the metal-oxide interface, while the third believes the transportation of reducing gas from the main stream to the metal-oxide interface and of product gas from the metal-oxide interface to the main stream to be the rate-controlling step. 1) The boundary-layer theory is true mainly for packed beds where the flow of gas through the bed is important. For a single particle, the boundary layer may be prevented from being the rate-controlling step if a gas flow rate of reducing gas above the critical flow rate is used. 2) Several workers have reported a linear advance of the Fe/FeO interface which provides excellent support for the belief that reduction is controlled by the surface area. McKewanl has given formal shape to this concept with mathematical derivation and has shown it to be valid for reduction of several iron ores, hematite, and magnetite, both by H2 and H2, H2O, N2 mixtures. Some other investigators, however, do not find this theory to be entirely valid. Deviations have been observed2 and further confirmedS3 Hansen4 also agrees that deviations do occur, at least in the latter stages of reduction, while from the data of several investigators summarized by Themelis and Gauvin,5 it is clear that the theory is not always applicable and further that, when it is applicable, it does not hold in the final stages of reduction. 3) Among those who claim the transportation of gas to be the rate-controlling step are Udy and Lorig,6 Bogdandy and Janke,7 and Kawasaki el a1.8 The validity of the theory has also been acknowledged indirectly by other research workers who show that the sintering and recrystallization of iron cause a decrease in reduction rate, for it is only if the transportation of gas is important that this sintering has any bearing. However, the theory has been rejected by some because they have failed to obtain

Jan 1, 1965

By W. J. Skewes, C. T. Holland

Properly constructed stopes are necessary underground for proper ventilation and safe, healthful working conditions. Mining companies are concerned with providing the best possible stoppings at an economic cost. It is important to consider 1) proper materials, 2) construction that ensures maximum performance from the material used, and 3) keeping costs within reasonable limits for the unit operation—stopping—involved. The authors investigated all aspects of the problem and have attempted to layout a study program to provide information on all phases. Mining companies every year purchase huge amounts of material for the construction of ventilation stoppings. This material by the time it is in place in the stoppings will cost the company many thousands of dollars. In addition and more importantly these stoppings are supposed to confine air travel along certain well defined paths into areas where it is needed to provide safe and healthful atmospheres for workmen. The cost of forcing this air through the mine is large and in general increases as the total quantity increases. Consequently, if the stoppings leak, increased cost results and in addition unsatisfactory ventilation may prevail in the mine. Therefore, it is essentia1 to provide the best possible stoppings at an economic cost. When attempting to provide the best stoppings possible at an economic cost, three aspects of the problem must be considered. These are 1) getting the most suitable material for stopping constructions, 2) constructing the stopping so as to get the best performance from the material used, and 3) keeping the cost of stopping construction to a minimum for a suitable stopping. This investigation is concerned with all phases of the problem and has attempted to lay out a study to provide information on all of them. In order to develop information on the best stopping material available it seemed wise, after con- sidering the job a stopping must do, to investigate the following aspects of material used for stoppings: 1) strength in compression, 2) compressibility or yield under load, 3) porosity, and 4) permeability. To provide information on the best manner of construction the following aspects of air leakage through the stopping were investigated: 1) when the stopping is built of dry stacked materials—i.e., the joints are not mortar-laid (See Fig. 1); 2) when the stopping is built of dry stacked material and then plastered on one side (see Fig. 2); 3) when the

Jan 1, 1961

By G. W. Crane

When ore was discovered on the Tintic Standard property in the spring of 1916, new developments were immediately started both north and south of that property, on the supposition that in East Tintic the ore would be found to occur in northerly trending channels, similar to those so characteristic of the older camp. But 9 years of developments have failed to establish the existence of such a channel. This is due undoubtedly to important differences in the geology of the two camps, that were not recognized, and is indicative of the danger in the general tendency toward interpreting the geology of East Tintic too strictly in terms of that of the older camp. It should not be forgotten that while the two sections have had practically the same geological history, the net results of a long series of geologic processes have developed in them conditions that differ so widely and in so many particulars that the necessity of regarding them as essentially different districts seems apparent. In an effort to emphasize this fact, this paper is devoted chiefly to a comparison of the geological conditions as found in the two camps and is addressed more particularly to those familiar with the geology of the Tintic district. Following a short description of the several ore discoveries and of the Tintic Standard mine is a brief discussion of the evidence of ore channels in East Tintic. For my information regarding the Tintic Standard mine, I am indebted to the courtesy and generous assistance of Messrs. Wade and Snow of the Tintic Standard Mining Co. East Tintic District The Term East Tintic district is here used to represent that eastern part of the Tintic mining district lying between the productive portion of the old camp of Tintic on the west, the foot hills of Goshen Slope, on the east, the Denver and Rio Grande Railroad on the north, and Silver Pass on the south, all in Utah County. As represented by the geological map, Fig. 1, it includes an area about 4 miles wide, east and west, and 5 miles long, north and south, within which the Tintic Standard mine is about centrally located. The map is a compilation of data supplied, for the most part, by the Chief Consolidated Mining Co. and represents the

Jan 1, 1927

By D. L. McElroy

It is too broad a statement to say that the mine car is the most important unit in a haulage system, but almost every mining man will admit that it is one of the most important. The mine car is to the mine haulage system what the railroad car is to the railroads; the main purpose in each instance is to move the greatest number of ton-miles of material at the least cost. The data presented in this paper are taken from a study of mine haulage conducted by the School of Mines of West Virginia University at 42 mines in 8 coal fields of Wrest Virginia. The study was made possible by a graduate fellowship of the School of Mines and the cooperation of the mining companies of the state. Three important factors in the use of mine cars in West Virginia are: (I) the number of mine cars in use per loader; (2) the capacity of mine cars; (3) the distribution of mine cars. ("Loaders" in this paper refers to all men loading coal, whether manually or mechanically.) During the World War many mine managers were annoyed by the reduction of efficiency and production caused by railroad-car shortages. Today relatively little complaint is heard about a shortage of mine cars, yet possibly 50 to 75 per cent. of the mines in West Virginia are suffering from this cause of reduced production and increased costs. The railroads have solved their car shortage by placing in service more cars of larger capacity and better design. Many coal mines in West Virginia should solve a part of their cost problems by the same simple procedure. Such a procedure requires an initial outlay of capital, but there is little doubt that this will be repaid, with a good return on the investment. Determining Number of Cars Needed There can be no mathematical rule to determine the number of cars which should be in use per loader in a coal mine, because numerous factors such as concentration of mining, system of haulage, car capacity, speed of haulage, distance of working places from tipple, and so forth, affect materially the number of cars in use. These factors in turn are more or less determined by height of bed, character of roof and coal,

Jan 1, 1931

By Daniel D. Pollock

The il'lott and Jones theory of thermoelectricity predicts that the absolute thermoelectric power of alloys of transition and noble metals should be a maximum when the concentration of the noble metal is approximately 55 to 60 at. pct. An examination of the emf of a series of relatively pure alloys of copper and nickel shows that the predicted maximum occurs at about 57 at. pct Cu. This excellent agreement with the theory is considered to substantiate the Mott and Jones theory of thermoelectricity for binary alloys of transition elements. This theory is extended to show that the emf behavior of dilute, ternary copper-nickel base alloys, which contain approsimately 60 pct Cu and 40 pct Ni, may be described in terms of a scattering mechanism. The scattering effect of a third element is demonstrated to be a function of its valence and its period in the periodic table. Small amounts of solute elements have additive scattering effects upon the emf of the Cu-Ni base. The Mott and Jones equation is modified to include this scattering parameter. This adaptation accurately describes the thermoelectric behavior of ternary and quaternary CLL-Ni base alloys. An empirical form of the modified Mott and Jones equation is derived which permits the calculation of thermoelectric power with an average error of less than 0.4 pct at 500 "C. CONSTANTAN has long been used as a thermocouple element. Its approximate composition varies from 50 pct Cu, 50 pct Ni to 65 pct Cu, 35 pct Ni. Small amounts of manganese, iron, and other elements have been used to modify the composition in order that the resultant emf vs platinum conforms to nationally accepted table. Adjustments of this type are made on a purely empirical basis. Constantan was originally made in Germany and was imported into this country for thermoelectric and electrical resistance purposes. During World War I, the supply of this material became seriously depleted. The work of Bash4 was done in this period in order to develop a satisfactory substitute for the imported material. Bash's empirical work on Cu-Ni alloys is still the basis for all commercial constantans made in this country. No reexamination of the electrical properties of this system has been made, despite the fact that it is now well known that Bash's alloys contained impurities which strongly affected their thermoelectric behavior.

Jan 1, 1962

By A. L. Holley

THOSE who are familiar with working gas furnaces will perhaps admit that the ordinary producer is the least satisfactory feature of the- whole system, chiefly by reason of its great waste of fuel, both above and below the fire. The waste of fuel in cleaning the fire has not, as far as I am aware, been carefully measured ; it has been roughly estimated at various works as averaging twenty per cent. to twenty-five per cent. The coke that falls into the ash-pit is largely mixed, if not stuck together with clinker; when this coke is not recovered and utilized (and where coal is cheap it does not pay to recover it), the waste is certainly as high as above estimated. Cleaning a fire on a grate (especially a fire of dirty coal, like much of our Western coal), by inserting a few temporary grate-bars, then withdrawing the regular grate-bars and letting the whole lower part of the fire tumble into the ash-pit, must necessarily be wasteful of fuel, but it has been found to be the most practical system. The fire under a boiler should be thin, to insure perfect combustion; hence it may be moved from one side to the other, so that .the clinker and ashes may be uncovered and removed. But a producer fire should be so thick that carbonic oxide only shall rise from it ; a thick fire cannot be thus manipulated. In several of the French works the ordinary producer without grates is employed ; the whole body of the fire rests on the floor of the ash-pit. It did not seem to me that less fuel was wasted here than with grates in cleaning fires. The bottom layer of the fire had to be drawn out with hooks, and there was nothing to prevent much coke from coming away with the clinker and ash. A producer shaped like a cupola furnace has many advantages, but if grates are employed the waste of coke in cleaning is not lessened. But the waste at the bottom of the fire is only a part of the waste in the ordinary producer. Mr. Emmerton, chemist to the Joliet Iron and Steel Company, has lately made a number of gas analyses from the producers of that company, worked with impure Illinois

Jan 1, 1880

By N. A. Gokcen, S. Fujishiro

THE pressures of Mn(g) in equilibrium with Mn7C3 and graphite have been measured by McCabe and Hudson' and Butler, McCabe, and paxton2 by means of graphite, zirconia, and Ta-Mo Knudsen cells. The details of corrections in their measurements were somewhat different from those of the authors;3'4 hence, further independent results at higher temperatures seemed to be warranted. The stoichiom-etry of Mn7C3 in equilibrium with graphite and its stability up to the vicinity of 1373 °K have been satisfactorily established by Kuo and persson5 (See also Hansen and Anderko).' The method of investigation has been described elsewhere in detail.3'4 The carbide was prepared in the manner described by McCabe and Hudson. In order to avoid possible reactions with refractory oxides, only graphite cells were used for the effusion experiments. The authors' results are the runs M-1, M-2 and M-3 listed in Table I, together with those of McCabe and co-workers. The heat capacity, c;, of Mn7C3 is not known; therefore McCable et al. plotted their data as log P vs 1/T and the results were only expressed first' as, and later2 as logP=- -14220+6.06 without further thermodynamic calculations. However, it is possible to estimate closely the necessary heat capacity as follows: When H; - &98 of CrC, or MnO, is plotted vs x, corresponding to various compounds, with temperature as the parameter, it is seen that the relationship is represented by a line of very small curvature. This relationship is also followed by other compounds which do not exhibit solid state phase transformations. In view of the fact that chromium and manganese have the atomic numbers of 24 and 25 respectively, it is reasonable to assume that H; - H;ae vs x for MnC, follows the same type of lines as those for CrC, for which adequate data are available.7 Similar correlations appear to be valid for oxides of two neighboring metals for which reliable data are available. The procedure is thus to move the lines for CrC, vertically (parallel to the axis of HT - H298) until they coincide with the points for MnC1/3, the only carbide of manganese whose H; - HO298 has been

Jan 1, 1963

By Harrison Schmitt

The definitions of the terms commonly used in connection with metamorphism at elevated temperature near igneous contacts are re-examined. As the study of tactite zones associated with igneous contacts progresses, more and more emphasis is put on the localization of the ore by structural forms. The generally early age of the silicates and late age of the sulphides is well established. Postsilicate structural deformation is likely to localize ore bodies. The silicates are often replaced by the ore minerals. we may not be far from proving that the elements involved in the formation of silicate aureoles are merely normal "volcanic" emanations, that silica, lime, magnesia, and alumina, and probably soda and potash, are likely to undergo local transfers only. The work of Newhouse suggests the agents of the formation of sulphides in deposits of various classifications are the volcanic emanations. Introduction The purpose of this paper is to define the terms commonly used in connection with the subject, to briefly review and discuss the broad features of the aureoles, to indicate some of the features lately recognized: to discuss the genesis, and to suggest how the associated ore deposits can best be studied and developed. When developing a subject in mining geology one is soon conscious of the vast amount of pertinent literature and that most relevant ideas, no matter how obscure, have been considered. One can only hope to make some small contribution in point of view, a few confirmatory observations, or, perhaps, suggest a small new idea indebted to the most recent data. It is nearly impossible, also, to give specific credit, and adequate credit, to all the contributors to a given subject. This study, furthermore, was not intended to cover the field exhaustively, nor is the bibliography complete. Definition OF Terms There is much confusion in the use of the broad terms concerned. Needless to say, metamorphism means change of form; metasomatism, change of substance. The term contact metamorphism, however, has been widely misused possibly by a majority of economic geologists and engineers. As originally adopted by European investigators it meant changes effected largely by heat (thermal effects) in the rocks invaded by plutonic intrusives, but did not include those local changes usually at the immediate contact brought about by the addition of substance, i.e., by metasomatism. The term has become clouded. In Europe it has

Jan 1, 1949

By Harrison Schmitt

The definitions of the terms commonly used in connection with metamorphism at elevated temperature near igneous contacts are re-examined. As the study of tactite zones associated with igneous contacts progresses, more and more emphasis is put on the localization of the ore by structural forms. The generally early age of the silicates and late age of the sulphides is well established. Postsilicate structural deformation is likely to localize ore bodies. The silicates are often replaced by the ore minerals. we may not be far from proving that the elements involved in the formation of silicate aureoles are merely normal "volcanic" emanations, that silica, lime, magnesia, and alumina, and probably soda and potash, are likely to undergo local transfers only. The work of Newhouse suggests the agents of the formation of sulphides in deposits of various classifications are the volcanic emanations. Introduction The purpose of this paper is to define the terms commonly used in connection with the subject, to briefly review and discuss the broad features of the aureoles, to indicate some of the features lately recognized: to discuss the genesis, and to suggest how the associated ore deposits can best be studied and developed. When developing a subject in mining geology one is soon conscious of the vast amount of pertinent literature and that most relevant ideas, no matter how obscure, have been considered. One can only hope to make some small contribution in point of view, a few confirmatory observations, or, perhaps, suggest a small new idea indebted to the most recent data. It is nearly impossible, also, to give specific credit, and adequate credit, to all the contributors to a given subject. This study, furthermore, was not intended to cover the field exhaustively, nor is the bibliography complete. Definition OF Terms There is much confusion in the use of the broad terms concerned. Needless to say, metamorphism means change of form; metasomatism, change of substance. The term contact metamorphism, however, has been widely misused possibly by a majority of economic geologists and engineers. As originally adopted by European investigators it meant changes effected largely by heat (thermal effects) in the rocks invaded by plutonic intrusives, but did not include those local changes usually at the immediate contact brought about by the addition of substance, i.e., by metasomatism. The term has become clouded. In Europe it has

Jan 1, 1949

By J. C. Bayles

It is seldom the privilege of one who contributes to the Transactions of a technical society, to describe a new industry in which, by processes employed for the first time, are attained results of conspicuous value. There are but few such patches of virgin soil worth the tilling, within the area circumscribed by the industries which have experienced a regular and uniform development. New and startling methods in production are often announced as about to be introduced; but, as a rule, they take their place among the " large desires with most uncertain issues," or give new significance to the historic words of an eminent statesman concerning " the bright beginnings and the bitter end of a halcyon and vociferous proceeding." In this paper I shall have the pleasure of briefly describing a new industry which has been established without announcement or proclamation — the manufacture of serviceable pressure pipes of great strength, from strips of steel or iron wound spirally, heated only along the overlapping edges, welded by hammering and finished into tubes of uniform diameter, and of such length as mag be found convenient in handling and transportation. As such tubes are now manufactured on a considerable scale, in a range of sizes which will soon include everything between 4 inches and 30 inches, and as much larger as may be needed, both process and product are likely to be of interest to engineers in all departments of professional work. The raw material of the industry is the ordinary sheet-iron or steel of commerce, of such lengths and widths as it is convenient to roll. The range of the ganges of the metal which can be employed has riot yet been determined. The lightest metal thus far successfully made into pipe is No. 29 iron, and the heaviest a steel gauging somewhere between 12 and 14. Heavier machines are now building which will bend steel .165 of an inch in thickness, or No. 8 of' the Birmingham gauge. Probably No. 20 or No. 22 will be the lightest used in making commercial pipes; hut the experiment with No. 29 was interesting as showing the readiness with which the flame can be controlled. To get a welding heat with such thin

Jan 1, 1888

By D. A. Dahlstrom

In the paper, a comparison was made between flowsheets using the screen bowl centrifuge and disc filters, respectively, as the primary dewatering device. The authors very effectively show that by raising feed temperature, mechanical dewatering is enhanced through reduced viscosity of the water. When a final coal moisture of 10% is required, the net effect of heating the feed is a reduction in thermal requirements because of the lower evaporated load on the dryer. The flowsheet comparison on this, however, was not completely correct. Disc filters do not generally utilize enhanced mechanical dewatering through increased temperature. Horizontal belt filters, through the optimal use of steam heating of the filter cake, have shown significant cost reductions over disc filters where steam is not used. In addition, the authors forgot to mention that there is a certain fraction of the feed that is so fine that it cannot be recovered by the centrifuge economically. That is the function of the filtration device shown in [Fig. 4]. In subbituminous pipeline coals, this fraction represents more than 10% of the feed. Even after flocculation and belt pressing, the moisture content in the fine fraction is 30%-40. Recent tests on a subbituminous pipeline coal slurry, compared an Eimco-Extractor horizontal belt filter with the screen bowl centrifuge flowsheet shown in [Fig. 4]. Mechanical dewatering was enhanced through the use of a steam dry zone after the initial dewatering zone. Vacuum pump horsepower was reduced by more than 50% through the use of condensers, and heat recovery was utilized to minimize thermal costs. Thermal drying to 10% moisture by weight was required in both flowsheets. The 0.5 wt% fines in the filtrate were flocculated and recycled to the filter, thus eliminating the belt press and solids mixers. When the three major operating costs (which normally account for 50%-75% of the coal operating costs) of steam, electricity, and flocculants at current prices were calculated, the flowsheets utilizing the Eimco-Extractor had cost savings vs the centrifuge flowsheet of 89c/t (81c per st) of surface dry coal. This advantage increases with increasing thermal and electricity prices. I congratulate the authors for the strides made with the screen bowl centrifuge. However, filtration flowsheets continue to be improved and their simplicity and low thermal and electrical requirements should not be so quickly dismissed.

Jan 1, 1984

By Hugh Douglas

ANTIMONY Antimony (Sb) has been used since the early Egyptian dynasties. Prior to World War I, total demand amounted to only 6000 to 7000 tons per year (tpy). Wartime uses and rapid rise of industrialization in the Northern Hemisphere nations have pushed world antimony use to the 78,000-tpy level. An overwhelming supply of low-cost antimonial resources in the Sino-Russian bloc countries has and will continue to have a major impact on availability and price to users outside the bloc. Table 14.4.1 shows trends in world production, United States production and consumption, and prices. Demand Antimony is used principally as an alloy in lead-based metals and other alloys. Pure metallic antimony usage is small and is confined to such areas as laboratory and electronic applications. Lead-antimony alloys are used in automobile storage batteries, chemical pumps, and pipes, tank linings, roofing material, and cable sheaths. The metal increases the hardness of lead, and, for such uses as foundry printing type, reduces shrinkage for casting and lowers the melting point. Antimonial oxides are used for ceramic purposes, white paint pigments, glass forming, textile finishing, fire retardants in military clothing, matches, and solder. Wartime applications include use as hardener for bullets, an element for tracer bullets, and ingredient for producing dense white smoke for visual markers. A small but rapidly growing use for antimony is for metallic compounds in semiconductors and thermoelectric devices. In the United States demand for antimony is about evenly divided between metallic end-use markets and nonmetallic markets. In metallic end uses, antimonial lead accounts for 27% of total metallic and nonmetallic use; in nonmetallic areas major uses are flame retardants (15%) which is the fastest growing market, plastics (13 % ), and ceramics and glass (11%). While antimony has advantages in most of its applications, there are uses in which other materials can be substituted, including: mercury, titanium, lead, zinc, chromium, tin, and zirconium in paints and pigments; tin in sheathings; calcium in battery plates; and bismuth in type metal. Supply Antimony is produced from both antimony ores and as a byproduct of smelting other ores. The principal ore mineral is stibnite (Sb2S3), along with its oxidized antimonial minerals and derivatives which occur in small discontinuous replacement veins or fissure vein implacements. Stibnite occurs in quartz-gold veins and copper-lead-zinc

Jan 1, 1976

By P. R. Martin, R. B. Kelly

Drilling in Central Texas during 1933 was confined, for the most part, to the search for new serpentine plugs. Bastrop County led in this particular activity, with 50 completions during the 12 months' period, 12 of which were productive. Only one new field was opened in Central Texas during the year, it being known as "Hilbig" (Bastrop County) and was discovered by the Humble Oil & Refining Co. The finding of commercial production in the serpentine at 2500 ft. led to further search in this and surrounding counties, but without success. Bexar County actually provided the greatest amount of drilling but the activity was limited to shallow development from 400 to 2000 ft. The Edwards limestone pay, which has been such a factor in past years, received but slight attention during 1933. Unsuccessful exploration was carried on in Lee and Burleson counties. With the exception of Freestone County, the Woodbine sand area was given even less consideration. This county, because of its close proximity to Anderson and Leon counties, saw a very active leasing campaign and several important tests drilled. In Central Texas, 252 wells were completed in 1933, and of this number 52, or 21 per cent, were productive. Hilbig Field The discovery well, Humble Oil & Refining Company's Annie Hassler No. 1, was completed Feb. 16, 1933, for an initial production of 65 bbl. the first hour, through tubing and 1/2-in. choke. The production was found in serpentine at 2468 ft. and tested 37.2" A.P.I. gravity. Twelve producing wells were drilled during the year and served to indicate that not more than 300 acres would comprise the entire field. Daily production at the end of the year was 775 bbl., although the field potential was 18,240 bbl. daily through 1-in. choke. The field adapts itself to pressure maintenance, and this scientific handling is being undertaken by the Humble Oil & Refining Co. through one injection well. It is the only area in the district where work of this nature is under way. Proration of Oil The more stringent application of proration in 1933 did not affect materially the producing fields in Central Texas. This is accounted for

Jan 1, 1934

By Henry M. Otte, Ralph P. I. Adler

The changes of line position and integral line breadth in the X-ray diffraction pattern of a polycvys-talline Cu-30Zn tensile test piece, incrementally loaded (and unloaded) up to fracture, have been an-alyzed in detail. The stacking-fault probahility, cv, increased linearly with increasing strain, E, wheveas the effective domain size, De(hkl), decreased with decreasing E-1 Over the greater part of the stress-strain curve the rate of work hardening was essentially constant (about 86 kg per sq mwz), and could be correlated with the slope of stage II of the single-crystal stress-strain curve. Consequently the theories of work hal-dening (particularly those parts relating to stage 11) as developed by Mott and Hivsch and others could be applied to the observations made on the polycrystalline brass. A relationship of the form Aa = Aao - MhklEhkl between the change, Aa, in the extrapolated lattice pararneter and the rvns strain, Ehkl, was derived and found to fit the results acceptably well. From this and other relationships developed in the papev it was estimated that the equilibrium stacking-fault energy of Cu-30Zn was between 8.4 and 12.5 ergs per sq cm, in fuirly close agreement with the (corvected) value obtained by Howie and Swann (1961)43 using transmission electron microscopy. The theory of work hardening in the jorm developed and recently presented by Hirsch (1964)3 successfully described all the pvesent observations. In order to test certain aspects of the theories of work hardening, as developed by Mott,1 Hirsch,2,3 Seeger et el,4-7 and others (for review see Nabarro, Basinski, and Holt8), several recent investigations have been concerned with relating the dislocation density, p, with the shear stress, 7 (and strain, y), applied to the specimen. The results of these investigations have shown that the square root of the dislocation density appears to be linearly related to the applied shear (or flow) stress for fcc as well as bcc metals and alloys. Furthermore, the relationship appeared to apply not only to the deformation of poly-crystalline specimens, but also to stages I and I1 of the deformation of single crystals. An expression of the form has thus come into wide use. Here b is the Burgers vector for a total dislocation, G is the shear modulus, and 70 and q are constants. A review9 of available values of q shows it to have values (at room temperature) in general between 0.3 and 0.6. Forms of Eq. [1] can be deduced from, or predicted by, the current theories, and the various constants adjusted so that they are compatible with the experimentally found value of q . No unique relationship has yet been found between the dislocation density and the applied shear strain. There are several serious objections to the use of Eq. 11]. In the first place, it relates the shear stress to the density of the dislocations without regard to their arrangement, type, or distribution; the significance of the relation may therefore be justly questioned.5 In the second place, the values of the experimental quantities usually substituted into Eq. [11 are those of the applied shear stress and the total dislocation density measured after unloaditzg. The dislocation density value that should in fact be used is that for the mobile dislocations present in the specimen when under the applied load.* Finally, in cases where the values used for p, the dislocation density, are those obtained by electron microscopy, p is subject to considerable error,' both systematic and random. The corrections to be applied are still controversial. Dislocation densities can also be measured by etch-pit and other techniques,'' each having their specific limitations. An objective of the present investigation has been to obtain information about the dislocation configyration and distribution by analyzing the changes in the position and shape of X-ray diffraction profiles as a function of deformation. The X-ray techniques employed, also open to criticism, have certain advantages, however. Thus, although the X-rays diffract only from the surface layers to an effective depth of about 20 p, the measurements can be made while the specimen is under load. The value of the dislocation density obtained by the X-ray method is also subject to errors, which are different from those of the electron microscope. Though a considerably larger volume of material is sampled by the X-rays, thereby reducing some of the statistical errors inherent in the electron microscope data, the information obtained is less detailed and is dependent on the method of analysis used to obtain a value for the dislocation density. Nevertheless, important observations can be made because the aforementioned advantages outweigh some of the limitations. In the present paper the X-ray method is briefly described and applied to a brass specimens deformed in tension. The results are then discussed in terms of some of the current concepts of work hardening. 1) EXPERIMENTAL PROCEDURE Details have already been extensively published elsewhere11-14 and therefore will only be dealt with briefly here. 1.1) Materials and Specimen Preparation. Commer-

Jan 1, 1968

By A. L. Holley

Those who are familiar with working gas furnaces will perhaps admit that the ordinary producer is the least satisfactory feature of the- whole system, chiefly by reason of its great waste of fuel, both above and below the fire. The waste of fuel in cleaning the fire has not, as fdr as I am aware, been carefully measured ; it has been roughly estimated at various works as averaging twenty per cent. to twenty-five per cent. The coke that falls into the ash-pit is largely mixed, if not stuck together with clinker; when this coke is not recovered and utilized (and where coal is cheap it does not pay to recover it), the waste is certainly as high as above estimated. Cleaning a fire on a grate (especially a fire of dirty coal, like much of our Western coal), by inserting a few temporary grate-bars, then withdrawing the regular grate-bars and letting the whole lower part of the fire tumble into the ash-pit, must necessarily be wasteful of fuel, but it has been found to be the most practical system. The fire under a boiler should be thin, to insure perfect combustion; hence it may be moved from one side to the other, so that .the clinker and ashes may be uncovered and removed. But a producer fire should be so thick that carbonic oxide only shall rise from it; a thick fire cannot be thus manipulated. In several of the French works the ordinary producer without grates is employed ; the whole body of the fire rests on the floor of the ash-pit. It did not seem to me that less fuel was wasted here than with grates in cleaning fires. The bottom layer of the fire had to be drawn out with hooks, and there was nothing to prevent much coke from coming away with the clinker and ash. A producer shaped like a cupola furnace has many advantages, but if grates are employed the waste of coke in cleaning is not lessened. But the waste at the bottom of the fire is only a part of the waste in the ordinary producer. Mr. Emmerton, chemist to the Juliet Iron and Steel Company, has lately made a number of gas analyses from the producers of that company, worked with impure Illinois

Jan 1, 1880

By M. J. Pool

The partial molar heats of solution in liquid tin of cadmium, silver, tellurium, and zinc have been measured at 655°. 700°, and 750°K by liquid-metal solution calorimetry. Silver, cadmium, and zinc are endothermic at these temperatures while tellurium is exothermic. Only the heat of solution of silver depends on composition while all four elements show a temperature-de pendent heat of solution. The heat of solution of tellurium is constant up to 0.6 g-at. pct, becomes increasingly more exothermic, and reaches a limiting value at 1 g-at. pct Te. The limiting value has been used to calculate the heat of formation of SnTe at 750°K. The heat effects associated with the dissolution of the compounds Ag2 Te, CdTe, and ZnTe in liquid tin were measured at 750°K. These values are cotnOined with the measured hat effects at 750°Kfor silver, cadmium, tellurium, and zinc to detertrline the heats of formation of the telluride compounds. Cadmium lelluride exhibits a heat of dissolution which has a compositional dependence. THERE is a considerable amount of interest in the compounds of tellurium because of their electronic properties. Both cadmium and zinc tellurides are thermoelectric materials and considerable work has been done on their electronic properties but a limited amount of data is available on their ther-modynamic properties. This work was undertaken to elucidate the heat of formation data on cadmium and zinc telluride. Since both cadmium and zinc are in Group II it seemed to be of interest to compare the values obtained for them with the heat of formation of a Group I telluride. Silver telluride was selected for this comparison. In the course of the work it was also possible to determine the heat of formation of tin telluride and therefore to make a comparison of some of the Group I, 11, and lV tellurides with the metallic elements silver, cadmium, and tin being in the same period. There is also a great deal of interest in the energetic changes which occur upon addition of solute elements to a common solvent. This investigation provided an opportunity to study the partial molar heats of solution of silver, cadmium, tellurium, and zinc in liquid tin. The partial molar heats of solution are of theoretical interest because solute-solute interactions are a minimum in dilute solutions and application of solution models is simpli- fied. In order to complete the analysis of solute-solute and solute-solvent interactions the temperature dependence of the partial molar heats of solution was also measured. MATERIALS AND EXPERIMENTAL PROCEDURE All materials were of the highest purity available. The silver, zinc, cadmium, and tellurium were obtained from American Smelting and Refining Co. and were reported to be 99.999 pct pure. The silver telluride, zinc telluride, and cadmium telluride were obtained from Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp., and were electronic-grade material of 99.999 pct purity. Tin used for the solvent bath and for calibration was obtained from the Vulcan Manufacturing Co. and was reported as being 99.99 pct pure. The liquid-tin solution calorimeter used in this work is similar in principle to the differential twin-type calorimeter described by K1eppa.l Two of three identical calorimeter wells are used together during any set of experiments, one well being active and the other being passive. The wells are positioned 120 deg apart in an aluminum calorimeter block. Each well contains a multijunction thermopile and a Pyrex test tube to hold the liquid metal bath. Forty-eight of the thermopile junctions are distributed over the surface of each calorimeter well adjacent to the test tube and serve to integrate the heat effects occurring. The other forty-eight are next to the aluminum calorimeter block. The thermopiles for the three wells are connected differentially so that any change in temperature at the outer junctions (which will be the same for both wells because of the high conductivity of the aluminum block) will oppose for the two wells and result in no shift of the zero. The electrical output represents the true temperature difference between the two reaction vessels. A reaction occurring in the active well gives a comparison with another body of very similar thermal properties. In this way, any spurious heat effects due to slight temperature drifts within the entire calorimeter block are eliminated. The output of the differential thermopile goes to a dc amplifier with multiple ranges of from * 10 pv to 1 30 mv. The output of the amplifier is then fed into a Leeds and Northrup strip-chart recorder. The adiabatic temperature change is then calculated using the technique of Howlett, Leach, Ticknor, and ever.' The aluminum calorimeter block is contained in a cylindrical furnace with main and control heaters

Jan 1, 1965

By M. I. Jacobson, A. S. Yue, A. E. Vidoz, F. W. Crossman

An equation governing the concept of constitutional supercooling under the combined effect of concentration and temperature gradients was used to produce platelike Al-CuAl2 eutectic composites for mechanical properties studies. Compression specimens were prepared from a single-colony Al-CuA12 eutectic composite ingot, 2 in. in diam and 12 in. long. The specirrzens were cut such that the platelets were oriented parallel, 45 deg, and perpendicular to the compression direction. Since the ingot was of eutectic composition, The aluminum-rich matrix could dissolve 5. 7 wt pct Cu in solid solution, and therefore could be strengthened by precipitation hardening. Specimens were tested at room temperature and elevated temperatures in the unidirectionally solidified, solution-treated, and solution-treated plus aged conditions. The results were compared with those for the conventionally cast and extruded specimens. For the controlled material, the highest strengths were obtained with platelets oriented parallel to the compression axis. In the unidirectionally solidified condition, 0.2 pct offset yield strength was 32,000 psi; however, this was increased to 59,000 psi by solution treatment, and further increased to 90,500 psi by solution treatment and aging. The attainment of high compressive strengths in the Al-CuAl2 eutectic composites was interpreted in terms of the buckling of elastic CuAl2 platelets in the plastically deformed a aluminum matrix. SINCE the discovery of high-strength whiskers,' scientists and engineers have made significant progress toward incorporating these whiskers into metallic matrices, forming composites for basic studies and structural application. The general procedure is to produce the whiskers first and then to bind them together with a ductile matrix. The production of whisker-reinforced composites requires tedious handling techniques,, particularly when it is desired to align the whiskers unidirectionally. Furthermore, the interfacial bond between the whisker and the matrix is frequently poor3 so that the resulting composite has strengths lower than expected. These disadvantages are generally true for any metallic composite produced by physically mixing the components. It is possible to eliminate these shortcomings by growing whiskers directly in the matrix material by eutectic solidification.4-8 In eutectic solidification, the matrix phase and a whisker phase are grown approximately simultaneously from a liquid of the same overall composition at the eutectic temperature. If the solidification process is controlled by varying the freezing rate, the temperature gradient, and the impurity content, platelike or filamentlike whiskers are produced parallel to the growth direction. The morphology of the grown-in reinforcement, i.e.. plates or rods, generally depends on the volume fraction9 of the dispersed phase present in the eutectic mixture. Since the unidirectional eutectic solidification is a one-step process, i.e., the liquid-solid transformation process, an excellent interfacial bond between the matrix and whisker is obtained. An additional advantage is that no special handling technique for whiskers is needed. In recent years, many investigators10-13 have studied the effects of growth variables on the micromorpholo-gies of binary eutectic alloys produced by controlled solidification. The study of their mechanical properties was initiated by Kraft and coworkers14-16 who found that the strength of cast A1-CuA12 eutectic alloy can be increased threefold by unidirectional solidification. In the A1-AL3Ni system, a strength of 50,000 lb per sq in, was reported for the unidirectionally solidified eutectic alloy, a value five times higher than for conventionally cast material. Thus, the unidirectionally solidified eutectics can be used as fiber-reinforced composite materials. In this paper, we shall first use an equation17 as a guide for the production of eutectic composites in general and the Al-33 wt pct Cu eutectic in particular. Experimental data supporting the theoretical prediction are given. Second, the compressive properties of the grown A1-33 wt pct Cu eutectic were thoroughly investigated in terms of platelet orientations, thermo-mechanical treatment, and temperature. The experimental data are interpreted in terms of a buckling model of fibers in elastic fiber-plastic matrix metallic composites. EXPERIMENTAL PROCEDURE Crystal Growth. The following experimental procedure was adopted for the production of controlled microstructures in the A1-33 wt pct Cu eutectic alloy. The controlled solidification was accomplished with a movable resistance-wound radiation furnace. Fig. 1 is a schematic drawing of the solidification apparatus. A water-cooled chiller was placed into a degassed high-purity graphite crucible containing the charge. Rubber stoppers wrapped with aluminum foil were used to seal both ends of the quartz tube through which a dried argon atmosphere was passed under a slight positive pressure. At both ends of the quartz tube, radiation shields were used to minimize heat loss. The quartz tube was held in place by two steel clamps and the furnace was drawn vertically by means of a steel cable against the steel truss which permits the furnace to move without touching the tube. The drive mechanism consisted of two pulleys, a counter weight.

Jan 1, 1969

By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.''2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3'4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970