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By C. C. Singleterry, D. L. Katz

The critical phenomena have been studied during the past century but our knowledge of the critical temperatures and pressures of complex hydrocarbon mixtures still is very limited. The critical temperatures and pressures of pure substances have been examined in large numbers120 and in great detail.11.17 No experimental determinations of the critical phenomena have been reported on such complex hydrocarbon systems as a reservoir fluid. The critical temperature is defined by Taylor18 as follows: "there is some temperature for each gas above which the gas cannot be liquefied. This temperature is called the critical temperature." The critical pressure of a pure substance is the vapor pressure at the critical temperature. It should be noted that these definitions refer to a given substance in the pure state and do not mean that the pure substance cannot be liquefied in the presence of a second constituent. The normal procedure for obtaining the critical temperature of a substance is to heat it in a glass tube 1,20 under pressure until the meniscus between the liquid and vapor phase disappears, although other methods, especially for mixtures, have been used.13,14 However, when considering oil and gas reservoirs, it is more enlightening to consider a critical phenomenon that occurs when a mixture of oil and gas are compressed at a reservoir temperature until the meniscus disappears because the two phases become equal in composition. This conception, along with erroneous applications of the definition of the critical phenomena of a pure substance to that pure substance when it is part of a complex mixture, has caused confusion even among persons familiar with the classical theories. The purpose of this paper is to discuss the critical phenomena of pure substances and mixtures and to report experimental data on a mixture of

Jan 1, 1939

By C. C. Singleterry, D. L. Katz

The critical phenomena have been studied during the past century but our knowledge of the critical temperatures and pressures of complex hydrocarbon mixtures still is very limited. The critical temperatures and pressures of pure substances have been examined in large numbers120 and in great detail.11.17 No experimental determinations of the critical phenomena have been reported on such complex hydrocarbon systems as a reservoir fluid. The critical temperature is defined by Taylor18 as follows: "there is some temperature for each gas above which the gas cannot be liquefied. This temperature is called the critical temperature." The critical pressure of a pure substance is the vapor pressure at the critical temperature. It should be noted that these definitions refer to a given substance in the pure state and do not mean that the pure substance cannot be liquefied in the presence of a second constituent. The normal procedure for obtaining the critical temperature of a substance is to heat it in a glass tube 1,20 under pressure until the meniscus between the liquid and vapor phase disappears, although other methods, especially for mixtures, have been used.13,14 However, when considering oil and gas reservoirs, it is more enlightening to consider a critical phenomenon that occurs when a mixture of oil and gas are compressed at a reservoir temperature until the meniscus disappears because the two phases become equal in composition. This conception, along with erroneous applications of the definition of the critical phenomena of a pure substance to that pure substance when it is part of a complex mixture, has caused confusion even among persons familiar with the classical theories. The purpose of this paper is to discuss the critical phenomena of pure substances and mixtures and to report experimental data on a mixture of

Jan 1, 1939

By Ramesh Malhotra, Hubert E. (Deceased) Risser

THE WORLD Coal, as a source of energy and as a source of coke for the smelting of iron ore, has contributed significantly to the development of every major industrial nation of the world A number of other materials-oil, natural gas, wood, waste materials, water, and, in some applications, nuclear materials -can be used satisfactorily for the generation of heat and energy, but no generally acceptable and economic substitute has been found to supplant coke in iron ore smelting in conventional blast furnaces. In the development of many nations, coal provided the initial source of energy for industrialization Although coal provided more than 60% of the world's energy each year between 1902 and 1929, oil and natural gas have surpassed it as a source of energy in more recent years (Ref. 38, pp. 439, 441). Despite the rapid rise in importance of other fuels, a considerable amount of the total energy consumed is still supplied by coal. In 1972, coal supplied 32.1 % of the total world energy (Ref. 49, pp. 2-3). To produce this energy, 2.4 billion metric tons of coal were consumed-a 16.0% increase over the amount consumed in 1962. A further worldwide increase in the amount of coal used to supply energy is projected. According to Dr. Karlheinz Bund (Ref. 37, p 145), by the year 2000 world coal consumption could amount to 5 billion mt. Coal Resources and Production The world's coal resources are estimated to be about 10,872 billion mt. Of this amount, 1,297 billion mt are classified as measured reserves (Ref. 50, p. 57). In Table 13.A.1 the estimates of measured reserves and total resources, recent production, and the ratio of measured reserves to production of major coal-producing countries are shown. About 90% of the world's total coal resources are estimated to be in the USSR, the United States, and China. The United States ranks second in the world in coal resources, but in measured reserves, it ranks first. Because of the difference in rate at which available coal resources are being exploited, the ratio of measured reserves to actual production varies widely among areas and countries. France and East Germany have the lowest reserve to production ratios, 49.5 and 60.1, respectively. In Mexico, where currently less than 5 million mtpy of coal are produced, the ratio is 1257 For all countries producing more than 200 million mtpy of coal (except East Germany), the ratio ranges from 350 to 670. For the United States, the ratio is 669.7. In Table 13.A.2, distribution of the world's coal resources by area is shown. More than 97% of the total resources lie in the northern hemisphere, with Asia, including European USSR, having 63.4%. Only 1.9% of the total coal resources are estimat-

Jan 1, 1976

By Rudolph G. Wuerker

The progress made in testing the strength of rocks and minerals as they are encountered in mine operation is reviewed. An attempt is made to correlate these physical measurements with abrasive hardness, grindability, and behavior in comminution on one hand and fracture of rocks in pillars and roof control on the other. THIS paper reviews the progress made in testing the strength of rocks, ores, coal, salts, and other minerals as they are encountered in mine operations. It attempts to correlate the results of these physical measurements with technological properties more useful to the mining engineer: abrasive hardness, grindability, and behavior in comminution on one hand, and roof control, fracture of rocks in pillars, and mining methods with controlled caving on the other. In the following pages, the materials discussed will be referred to as rocks. Basic to rock mechanics and comminution are the problems of strength, elastic behavior, and failure, common to all brittle materials. A distinction will be drawn as to theoretical and applied research, and discussion of the progress made in each field will include test data obtained by the U.S. Bureau of Standards,1-1 the U.S. Bureau of Mines," the Iowa Engineering Experiment Station,"." the Committee on Geophysical Research at Harvard University,'" Basic Industries Research of the Allis-Chalmers Manufacturing Co.,11,12 by Philipps,13 and by Mueller," to name only a few. With refinements of testing methods and increased standardization. more useful and more comparable results have been achieved. This is especially important in testing a material like rock, as the inherent heterogeneity demands careful and exacting procedures. New measuring procedures that appear to supersede well known standard methods have contributed to faster and less costly testing yet have introduced new concepts, with implications as to comparability of results which must be watched. Reference is made to the sonic method for determining elastic properties," to be discussed in detail below. Basic Investigations Historically, all work in the field has started with the simplest determinations such as those for crushing strength, abrasive hardness, and grindability. These serve the limited objectives in the researcher's field of specialization: building construction, road ballast, roof control in mines, comminution, and seismic prospecting. Occasionally, fundamental properties like the modulus of elasticity E and Poisson's ratio v have been determined with the idea that they might have some bearing on the technological properties of the material under investigation. But it was not until the work of Philipps,13 of Harvard University,'" and of the U.S. Bureau of Mines"' that sufficient basic data were collected to allow researchers to go beyond the technological test and find the fundamental laws behind the behavior of rocks in mine and mill operations. The properties to be looked for are those that describe the elastic behavior of any material, the modulus of elasticity E and Poisson's ratio v being the ones determinable with least difficulties. Only two such properties are required to compute any other property such as the shear modulus, the modulus of rigidity, and the bulk modulus, all of which are related to each other according to well known equations of the theory of elasticity." In spite of their heterogeneous character, all rocks tested have possessed elastic properties. This does not mean that rocks of the same type always have the same modulus of elasticity, which varies exactly as the crushing strength or any other physical property of a rock can spread over a wide range. This has been explained by imperfections of the material always found in rocks, but to some extent this scattering of data is caused by inaccuracies inherent in the testing methods. Modulus of Resilience, a Criterion of Failure Increased availability of E values should allow us to test the validity of the quantity of strain energy theory which has been used in the solution of roof control problems by Philipps13 and by Holland.'" Recently Bond and Wang12 have applied this theory to explain the failure of an elastic material in comminution. Actually it is a very old theory, proposed as far back as 1885 by Beltrami.16 By its assumption the condition of yielding is determined by the term S2 M, = — x volume. Here M, is the modulus of 2E resilience, and its dimension is inch-pounds per cubic inch, that is, work per unit volume. Its numerical value is equal to the area under the stress-strain diagram. In the foregoing equation S is the yield stress (in psi) in tension or compression, whatever the case may be. E, the modulus of elasticity, is in psi. The great appeal of Beltrami's concept of stored energy lies in the fact that the two properties which seem to influence failure most, strength and elasticity, occur in the formula for the modulus of resilience. As an illustration of this, the moduli of resilience in compression of some typical materials tested by the U.S. Bureau of Mines" have been plotted in Fig. 1. The sample of concrete of conventional mix is shown only for the sake of comparison. Its determination was made in the Department of Mining and Metallurgical Engineering, University of Illinois. The values of the moduli of resilience of the various specimens in the plot are:

Jan 1, 1954

By D. M. Dunbar

LONG before Columbus discovered America the original inhabitants toiled in the copper workings of the Andean Cordillera. Their best diggings appear to have been at Chuquicamata, site of the huge present-day open pit owned by the Chile Exploration Co., subsidiary of Anaconda Copper Mining Co. Located in Antofagasta Province of northern Chile, Chuquicamata is in the Atacama desert, high on the western slope of the Andes at 9500-ft elevation. In the Chuquicamata area the Atacama desert merges into the Cordillera. The climate is extremely arid and precipitation, either in the form of rain or snow, is very infrequent. The temperature varies from 50° to 85°F during the day, and drops to 20° to 40° at night. The Antofagasta and Bolivia Railroad, which connects the Chilean Port of Antofagasta with La Paz, Bolivia, passes within approximately 6 miles of the plant. A branch from the main line to Chuquicamata serves the property for outgoing copper and incoming freight. The distance to Antofagasta by rail is 163 miles. Previous to the Inca conquest, this region was inhabited by the Chuco Indians, a small tribe, descendants of the Aymaras and Quechuas. The Incas, whose capital was located in Cuzco, Peru, gradually extended their empire to the south, reaching at one time to what is now central Chile. It is believed that they built crude primitive furnaces on the banks of the Rio Salado where on a small scale they smelted copper ore from Chuquicamata. At the time of the subsequent Spanish conquest, legend has it that Diego de Almagro, on his return to Cuzco in 1536 after his invasion of Chile, obtained from these furnaces metallic copper for horseshoes. During the period from 1560 to 1879 the high grade veins of the Chuquicamata deposit were worked superficially by the Spaniards and Bolivians. The treaty signed after the war of 1879 recognized the sovereignty of Chile over this territory and Chile, realizing the importance of the district, started to develop it in an orderly manner, although only high grade veins were worked. New Process Is Key Reports on the deposit were brought to the attention of Albert C. Burrage, a Boston lawyer and financier, in 1910. Chuquicamata was described as a huge deposit of ore that was not amenable to the usual treatment by concentrating and smelting since much of the copper occurred as oxides. He had been working on a process for the recovery of copper from sulphide ore which involved a sulphating roast, leaching of the roasted product, and pre-

Jan 1, 1952

By Richard Franchot

IN the inevitable conquest of the blast furnace by metallurgical science in the solution of the problem of how to make more and better iron or to burn less coke, or both, it is highly desirable first to find out why the efficiency of the furnace generally is no better than it is. The immediate need would seem to be a theory to account for the existing facts. Explanation for the quantitative results obtained in current practice has been strangely lacking. One reason for this may be found perhaps in the custom of think-ing of efficiency in terms of coke consumption. Before efficiency can be explained there should be a fairly exact knowledge of what it is. A statement of the pounds of coke used per ton of iron made may have value in indicating comparative results in smelting similar ores with similar cokes, but it tells very little of the efficiency of the operation. When the materials are different, one practice burning 1800 lb. may be less efficient than another using 2000 lb. A better measure is the pig and slag per unit of coke. What is needed is a specific description of efficiency as a' definite quantity having an exact meaning. Such description is afforded by expressing efficiencies in terms of the respective proportions of the fuel energy absorbed in and chargeable to the various actions known to be -taking place in the furnace. Concretely, the energy value of a pound of coke having 85 per cent carbon blown with air heated to 1200° F. is about 7650 lb.-cal. (13,770 B.t.u.). And the work done in smelting a pound of average iron from hematite, comprising reduction and melting with production of a half pound of free running slag from an equal weight of limestone,

Jan 9, 1926

By Ole Singstad

THE legislatures of New York and New Jersey, determined in 1919 that a vehicular tunnel should be built under the Hudson River. On July 1, 1919, an engineering staff was organized with the late Clifford M. Holland as chief engineer, and this staff was given a number of problems to solve, such as location, size, type of tunnel, method of construction, method of ventilation and cost. After a period of preliminary investigations and studies it was decided to build the tunnel at Canal St., New York, connecting 12th St., Jersey City. This is the center of the heaviest traffic across the Hudson River. It was also decided to build two tunnels-one for west-bound traffic and one for east-bound traffic-the tunnels to be of cast iron, built up of segments and bolted together, each tunnel to have a roadway 20 ft. wide and a clear heat room of 13 ft., 6 in. This is to provide for two lines of vehicles in each direction. The tunnels have an exterior diameter of 29 ft., 6 in. The interior lining is of concrete, the sidewalls tiled with a vitreous white tile and the roadways paved with granite block. The entrances and exits at both ends are separated by two blocks so as to reduce traffic congestion. BASIS OF VENTILATION It was recognized very early that one of the most important problems confronting the engineers was a proper ventilation system. It was estimated that each tunnel as planned would have a traffic capacity of 1900 vehicles per hr. The tunnels are 8500 ft. long between portals, and it was considered that the ventilation should be based on all of these vehicles being operated by gasoline engines. That presented a problem in ventilation unlike any other either in magnitude or character.

Jan 8, 1926

By Donald M. Hausen

Microscopic evaluation of trace quantities of metalliferous phases in flotation products requires counting large numbers of particles. Particle counts of many thousands may be required for precision, but cannot be obtained practically by conventional microscopic techniques. A less tedious microscopic method for evaluating trace sulfides in mill tailings was developed for the O'okiep Mining Co. in South Africa. Hundreds of thousands of particles were evaluated by this method called "gross-counting." Gross-counting consists of counting microscopic fields rather than point-counting individual particles. Total counts are calculated by multiplying the average number of particles per field by the total number of fields examined over the entire mount. Total gross-counts range from about 20,000 particles for +200 to 100,000 or more for -400 mesh size material in lucite mounts. Sulfides and metallic particles in each field are identified and tallied along with field counts. Totals for each type of metallic particle are divided by the total gross-count to give volume percent which is corrected to weight percent by specific gravity factors.

Jan 1, 1973

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By AIME

TITANIUM-RICH ilmenite deposits, situated in the Allard Lake area in Quebec some 400 miles down the St. Lawrence River from Quebec City and 28 miles north of Havre St. Pierre on the north shore of the Gulf of St. Lawrence, are undergoing an intensive development program by the joint efforts of the Kennecott Copper Corp. and The New Jersey Zinc Co. Easily accessible ore, amounting to about 125 million long tons and carrying from thirty to forty per cent titanium oxide, has been delimited. Plans are being made for construction of an electric smelter at Sorel, on the south bank of the St. Lawrence midway beween Montreal and Three Rivers, which will produce 650 long tons of high-grade titanium slag and 500 long tons of iron per day from 1500 long tons of ore. Occurrence of ilmenite ore in this area has been known since J. A. Retty reported his geological work in the lower Romaine River area for the Quebec Bureau of Mines in 1941. In this report Dr. Retty mentions the presence of anorthosite rocks, some of which were rich in ilmenite. Claims were staked by several interests but the small showings and complex metallurgy were too formidable for any organization not adequately equipped with capital, metallurgical knowhow, and market outlets. However, Kennecott became interested and through a newly formed Canadian subsidiary, Kennco Explorations Ltd., options were taken up under the direction of A. H. Robertson. An area of 300 square miles was traversed in the summers of 1945 and 1946. During 1946 and 1947 geophysical and diamond-drill prospecting disclosed a num-

Jan 1, 1948

By Russell G. Wayland

THIS paper gives the author's personal idea of the general viewpoint of the world's largest mica consumer, the U. S. Army, toward the supply, uses, and conservation of mica. However, to cover so broad a subject in a brief paper will require the dismissal of many phases with little or no mention. For example, it will be necessary to omit further reference to phlogopite or amber mica, even though amber block and splittings for certain spark plugs and commutator segments present some supply problems. This paper will deal entirely with muscovite, or white mica. MUSCOVITE MICA Muscovite mica is available commercially in four general forms; namely, as block mica, as splittings, as washer punch, and as scrap mica.1 No strategic importance is attached to washer punch and scrap mica, even though scrap has found some use in military construction and in electrical ceramics. The use of washer punch as such has fallen off with the non-manufacture of household electrical appliances. Some qualities of block mica are also of little or no interest, but other qualities of block mica and all splittings are considered of vital importance. Army equipment requires large amounts of muscovite mica splittings in the form of built-up mica commutator segments and coil insulation in motors and generators. Other military items using significant amounts of muscovite splittings are transformers, switchboards, and blasting apparatus. Flexible mica tape, made from bookform or loose-dusted splittings cemented to paper, linen, glass cloth, and other backing, is widely used in coil insulation in heavy electrical equipment and in aircraft generators. All muscovite mica splittings come from India, principally because of the enormous amount of hand labor required in their preparation. In this emergency, the need for them was anticipated and large industry and government stocks were on hand, while shipments have continued to come by sea in spite of wartime hazards. With the possible exception of certain bookform splittings, no trouble is anticipated in supply. Accordingly, the remainder of this paper is devoted to block (or sheet) muscovite mica, including condenser film that is split from block. THE MICA PROBLEM Block muscovite mica is commercially classified into the following general qualities, beginning with the best quality: I. Clear and Slightly Stained (C & SS). 2. Fair Stained (FS). 3. Good Stained (GS). 4. Stained (S). 5. Heavy Stained (HS). 6. Black Spotted. The ratio of relative commercial abundance in the present new supply of these micas is approximately I C & SS to 4 FS to 10 GS to 14 S to whatever the

Jan 1, 1944

By Geo. H. Ashley

The following paper is intended to be suggestive only, and to open the way for discussion and further observation. Its preparation was requested only two days before the time limit set for the submission of the papers comprising this symposium. Thus no time existed for detailed studies, so it is largely a memorandum of such facts as have come incidentally to the notice of the writer in the study of coal in the field. The field study of sulfur in coal has received very little special attention or description from coal student's. The presence of sulfur concretions is noted in hundreds of descriptions, and certain benches of a coal bed may be described as "sulfury" or the presence and position of sulfur bands may be noted in coal sections in connection with sampling. It may be accepted that some sulfur is present in all coal. The amount varies greatly in different regions, in different beds, and in the same bed in different areas. The anthracite of Rhode Island comes the nearest of any coal known to the writer of being free from sulfur, several analyses of that coal showing less than 0.1 per cent. Subbitumi-nous coals in Colorado in a few places have close to 0.2 per cent. of sulfur on the dry-coal basis and in other states subbituminous coals approach this lower limit. Bituminous coals seldom run under 0.4 per cent. of sulfur on the dry basis, though in a few places dry bituminous coals in Colorado and Washington have between 0.3 and 0.4 per cent. The better known bituminous coals have almost everywhere over 0.4 per cent. The best of the Pocahontas and New River coals run close to 0.4 per cent., but there is very little commercial coal in Pennsylvania, Ohio, Indiana, Illinois, Kentucky, or the other states, that runs under 0.5 per cent. on the dry basis. From these minimum figures, the amount will range up to 5 or 6 per cent. or higher if visible sulfur is not excluded. It must be remembered that the usual analysis of a coal bed is not intended to give the total proportion of sulfur in the bed but the amount in the coal after the removal of the more obvious and larger sulfur masses. Professor Parr has already pointed out that, chemically, sulfur occurs in several forms: as pyrite, organic sulfur, sulfates, and possibly as un-combined sulfur. Sulfur in the form of sulfates is commonly the obvious result of the weathering of pyrite and may be found in the coal within .

Jan 1, 1920

By M. A. Grossmann

THE hardenability of most steels can be predicted within 10 to 15 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a ''pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain sue may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter"; namely, the diameter of bar, in inches, that will just harden all the way through (absence of un- hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test. The data bring out certain features rather clearly. For example: I. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals," are known; thus an "incidental" chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybde- num when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful as wouldappear to be common experience; observe that an increase from no manganese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added " 20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the first small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using 1.0 per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost lo per cent in hardenability (in these units); this, however, does not apply to certain steels of high hardenability. It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome- molybdenum and chrome-vanadium steels, undissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum possible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the absence of Cr, and V up to 0.04 per cent), the charts provide reasonable approximations. The precise figures on the charts are suggested as tentative, subject to some modification as more data accumulate, but the fundamental concept appears to be supported by tests made on a wide variety of steels, a few of the correlations being shown in Fig. I.

Jan 1, 1942

By R. F. Hehemann, D. J. Cometto, G. L. Houze

The w transformation in the Zr-Nb system was studied using X-ray diffraction, dilatometric, re-sistornetric, hardness, and metallographic techniques. w forms in a diffusionless, completely reaersible manner on quenching and in a diffusion-controlled manner- on aging. The temperature at which w begins to form on quenching was determined as a Junction of composition and was found to decrease with increasing solute content. w formed bv aging establishes a metastable equilibrium with an enriched ß phase. The ß/w + ß transus has been determined for this metastable equilibrium and employed to rationalize retrogression and reversion phenomena observed in these alloys. The decomposition mechanism is discussed in terms of a gradual or continuous transformation from ß to the w state. BETA- stabilizing alloying elements lower the MS temperature of the martensitic bcc (ß) to hcp (a') transformation in zirconium and titanium alloys. In certain titanium alloys, a lower symmetry modification of the martensitic structure, termed (a"), also has been reported.1,2 These martensitic transformations are suppressed when the amount of the ß-stabilizing element exceeds a critical level. However, the high-temperature ß phase cannot be quenched to room temperature without change. At alloy contents just above the critical level, |ß trans-forms to the w phase when cooled rapidly.3-6 The amount of w in quenched alloys is reduced by increasing alloy content, and this phase virtually disappears above a critical composition.5 In addition to the transformation during cooling, w also can be formed by aging ß at temperatures below approximately 500°C, and significant alloy enrichment of retained 13 accompanies the isothermal transformation.1-8 The structure of LC is closely related to that of the ß from which it forms.9-15 The bcc (ß) lattice can be generated using a hexagonal cell with three atoms located at (000) and ±(2/3, 1/3, 1/3). This cell has an axial ratio of 0.612 and is oriented with respect to the cubic cell such that (0001)H (111)C and [1120]H [101]C. Consequently, there are four possible orientations of the hexagonal cell, associated with the four (111) planes of the bee lattice. Formally w can be obtained from 0 by allowing the two atoms at the ±(2/3, 1/3, 1/3) positions to approach the coordinates ±(2/3, 1/3, 1/2) and there are four equally probable orientations of w for each 0 grain. In titanium alloys w retains the cubic axial ratio of 0.612" and hence also can be indexed as triply cubic, but this is not the case for aged Zr-Nb alloys where w is clearly hexagonal with an axial ratio of 0.622." The lattice parameters and atomic positions of w depend on thermal history and alloy content. The atomic positions (000), ±(2/3, 1/3, 1/2) provide reasonable agreement between calculated and observed diffracted intensities for w in the fully aged condition.10,14 In the quenched condition, on the other hand, the atoms appear to be displaced from the central plane12,13,15 and assume positions ±(2/3, 1/3, Z = 0.42-0.48) rather than ±(2/3, 1/3, 1/2). This results in a structure with trigonal rather than hexagonal symmetry. The readily detectable parameter and axial-ratio changes of w in Zr-Nb alloys make this system especially attractive for studying the structural changes that occur in the formation and aging of w. Particular attention in this investigation has been directed to the relationship between the structure of w in the quenched and aged conditions, and to certain aspects of the reaction kinetics. MATERIALS AND PROCEDURE Zr-5, 12, 17.5, and 25 pct Nb alloys were prepared by a double arc-melting practice, encased in stainless-steel cans and hot-rolled to 1/8-in.-thick sheet.* Charged weights have been employed for the niobium contents and interstitial analyses are reported in Table I. Dilatometric, X-ray diffraction (filtered CuK, and MoK, radiation), metallographic, and hardness techniques have been employed to follow the transformations during isothermal and quench-aging heat treatments. In quenched specimens, the electrical resistivity also was studied. Betatizing was conducted for 1 hr at 900°C. With the exception of the isothermal dilatometric studies, samples were

Jan 1, 1965

By Russell G. Wayland

This paper gives the author's personal idea of the general viewpoint of the world's largest mica consumer, the U. S. Army, toward the supply, uses, and conservation of mica. However, to cover so broad a subject in a brief paper will require the dismissal of many phases with little or no mention. For example, it will be necessary to omit further reference to phlogopite or amber mica, even though amber block and splittings for certain spark plugs and commutator segments present some supply problems. This paper will deal entirely with muscovite, or white mica. Muscovite Mica Muscovite mica is available commercially in four general forms; namely, as block mica, as splittings, as washer punch, and as scrap mica.1 No strategic importance is attached to washer punch and scrap mica, even though scrap has found some use in military construction and in electrical ceramics. The use of washer punch as such has fallen off with the non-manufacture of household electrical appliances. Some qualities of block mica are also of little or no interest, but other qualities of block mica and all splittings are considered of vital importance. Army equipment requires large amounts of muscovite mica splittings in the form of built-up mica commutator segments and coil insulation in motors and generators. Other military items using significant amounts of muscovite splittings are transformers, switchboards, and blasting apparatus. Flexible mica tape, made from bookform or loose-dusted splittings cemented to paper, linen, glass cloth, and other backing, is widely used in coil insulation in heavy electrical equipment and in aircraft generators. All muscovite mica splittings come from India, principally because of the enormous amount of hand labor required in their preparation. In this emergency, the need for them was anticipated and large industry and government stocks were on hand, while shipments have continued to come by sea in spite of wartime hazards. With the possible exception of certain bookform splittings, no trouble is anticipated in supply. Accordingly, the remainder of this paper is devoted to block (or sheet) muscovite mica, including condenser film that is split from block. The Mica Problem Block muscovite mica is commercially classified into the following general qualitie3, beginning with the best quality: 1. Clear and Slightly Stained (C & SS). 2. Fair stained (FS). 3. Good stained (GS). 4. stained (s). 5. Heavy Stained (HS). 6. Black spotted. The ratio of relative commercial abundance in the present new supply of these micas is approximately 1 C & SS to 4 FS to ro GS to 14 S to whatever the

Jan 1, 1948

By Russell G. Wayland

This paper gives the author's personal idea of the general viewpoint of the world's largest mica consumer, the U. S. Army, toward the supply, uses, and conservation of mica. However, to cover so broad a subject in a brief paper will require the dismissal of many phases with little or no mention. For example, it will be necessary to omit further reference to phlogopite or amber mica, even though amber block and splittings for certain spark plugs and commutator segments present some supply problems. This paper will deal entirely with muscovite, or white mica. Muscovite Mica Muscovite mica is available commercially in four general forms; namely, as block mica, as splittings, as washer punch, and as scrap mica.1 No strategic importance is attached to washer punch and scrap mica, even though scrap has found some use in military construction and in electrical ceramics. The use of washer punch as such has fallen off with the non-manufacture of household electrical appliances. Some qualities of block mica are also of little or no interest, but other qualities of block mica and all splittings are considered of vital importance. Army equipment requires large amounts of muscovite mica splittings in the form of built-up mica commutator segments and coil insulation in motors and generators. Other military items using significant amounts of muscovite splittings are transformers, switchboards, and blasting apparatus. Flexible mica tape, made from bookform or loose-dusted splittings cemented to paper, linen, glass cloth, and other backing, is widely used in coil insulation in heavy electrical equipment and in aircraft generators. All muscovite mica splittings come from India, principally because of the enormous amount of hand labor required in their preparation. In this emergency, the need for them was anticipated and large industry and government stocks were on hand, while shipments have continued to come by sea in spite of wartime hazards. With the possible exception of certain bookform splittings, no trouble is anticipated in supply. Accordingly, the remainder of this paper is devoted to block (or sheet) muscovite mica, including condenser film that is split from block. The Mica Problem Block muscovite mica is commercially classified into the following general qualitie3, beginning with the best quality: 1. Clear and Slightly Stained (C & SS). 2. Fair stained (FS). 3. Good stained (GS). 4. stained (s). 5. Heavy Stained (HS). 6. Black spotted. The ratio of relative commercial abundance in the present new supply of these micas is approximately 1 C & SS to 4 FS to ro GS to 14 S to whatever the

Jan 1, 1948

By J. A. Coll, R. W. Cahn, A. Lawley

WHILE the creep properties of pure face-centered-cubic and close-packed-hexagonal metals have been thoroughly investigated and are well established, body-centered-cubic metals have been studied less extensively. Moreover, very few fundamental studies on the creep of solid solutions, irrespective of crystal structure, have been reported. The present study is concerned with the creep of a series of body-centered-cubic solid solutions. The present position concerning creep of pure metals is, briefly, as follows.1"3 Creep at first takes place at a steadily decreasing rate; this is the stage termed primary or transient creep. Except at the lowest temperatures this is succeeded by a stage of secondary or steady-state creep. At high temperatures and stresses, this may be succeeded by an accelerating stage, termed tertiary creep, with which we shall not here be concerned. There is no well-defined physical model at present for the transient stage; in general terms, transient creep is best regarded simply as a manifestation of work-harden ing. Steady-stage creep can certainly take place by several different mechanisms: the choice of dominant mechanism depends primarily on temperature. We shall here be concerned only with high-temperature steady-state creep, a term usually reserved for creep at absolute temperatures higher than 0.5 Tm, where T, is the melting point. In this range, the activation energy for creep is, for many metals, equal to the activation energy for self-diffusion, and this is generally interpreted in terms of a "climb mechanism.1-4 The creep rate is determined by the speed at which dislocations, impeded by obstacles the nature of which is disputed but which are probably established during transient creep, can climb by means of a diffusion process, until they are able to by-pass the obstacle. In solid solutions, the intrinsic resistance to the slip motion of dislocations may be much larger than in the solvent, to the extent that the motion of dislocations in the glide plane, rather than their escape by climb out of this plane, may become the rate-controlling factor. weertman5 has considered this possibility from a theoretical point of view, and concluded that some form of "viscous slip" is likely to be rate-controlling at comparatively low stresses. The resistance to slip may arise from "atmospheres" of impurities forming around dislocations; a high Peierls force in materials of high cohesion; or some structural peculiarity such as clustering or ordering of solute atoms.= We shall be concerned here with the case of ordering. The only published investigations concerned explicitly with the effect of order on creep refer to creep in ß-brass by Herman and Brown,7 and in Ni-Fe alloys, by Kornilov and panasyuk8 and by Suzuki and Yamamoto.9 Recently, Herman and Brown's paper has been supplemented by a determination of the tensile yield point of ß-brass as a function of temperature.10 Both studies showed a sharp drop in resistance to deformation of ß-brass over a range of a few degrees just above the critical temperature Tc at which order finally disappears. These observations are especially noteworthy, because in ß brass the degree of order diminishes steadzly to zero as the temperature approaches Tc. It is, therefore, the disappearance of the last traces of long-range order which has the largest effect on the resistance of the alloy to plastic deformation. In the Ni/Fe alloys of various compositions, resistance to creep at a given temperature and stress is maximum at the stoichiometric composition, both below Tc, (long-range order), and above T,. (short-range order).' Near Tc, the creep resistance of an ordered alloy is much higher than that of the same alloy in the disordered condition.9 The aim of the present investigation was to study the creep behavior in the neighborhood of Tc, of another system of ordering alloys. The iron-aluminum alloys were considered the most suitable. because: i) The order again diminishes steadily to zero as the temperature approaches Tc; there is no sudden drop in order at Tc, and it therefore is

Jan 1, 1961

By M. A. Grossman

THE hardenability of most steels can be predicted within 10 to 15 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter"; namely, the diameter of bar, in inches, that will just harden all the way through (absence of unhardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test. The data bring out certain features rather clearly. For example: I. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals," are known; thus an "incidental" chromium content of o.-2o per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful as would appear to be common experience; observe that an increase from no manganese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.2o per cent Mo provides a factor of 1.63, an increase of over 6o per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the first small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater harden ability will be obtained by using, for example, o.5 per cent of each than by using 1.0 per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain steels of high hardenability. It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, undissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum possible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the absence of Cr, and V up to 0.04 per cent), the charts provide reasonable approximations. The precise figures on the charts are suggested as tentative, subject to some modification as more data accumulate, but the fundamental concept appears to be supported by tests made on a wide variety of steels, a few of the correlations being shown in Fig. I.

Jan 1, 1942

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnxTe have been grown from nonstoichiometric, cation-rich melts with the objective of producing as-grown, bulk material containing carrier concentrations ranging from 1016 per cu cm to 1018 per cu cm. Three specific crystal composi-tions were investigated in detail; x = 0.00, 0.10, and 0.17. Pull rates of from I to 3 mm per hr were used. Single crystals were successfully pulled from melts containing as little as 30 at. pct Te. Hall coefficients, resistivities, and carrier mobilities of these materials were determined. The relationship between the composition of the melt and the carrier concentration in the as-grown crystal has been studied for the three crystal compositions of interest. BULK single crystals of Pb,-,Sn,Te have previously been grown from stoichiometric melts.1,2 Such crystals are p-type and have relatively high carrier concentrations ranging from -9 x 1018 per cu cm for PbTe to -8 x l020 per cu cm for SnTe at 77°K. These carrier concentrations result from deviations from stoichiometry (lead vacancies) in the as-grown crystals. Since lower carrier concentrations are desirable for electrooptic device applications, these crystals are usually subjected to long-term, isothermal anneals.' This paper reports on the growth of Pbl-xSnxTe single crystals from nonstoichiometric melts with the primary objective of producing as-grown material containing relatively low (1016 to 1018 per cu cm) carrier concentrations and also reports on the general characteristics of these crystals. The phase relationships in the Pbl-xSnxTe systems are such that materials solidifying from nonstoichiometric, cation-rich melts will have smaller deviations from stoichiometry than materials grown from stoichiometric melts. Fig. 1 is the T-x phase diagram for PbTe in the vicinity of the stoichiometric composition.3 A crystal grown from a stoichiometric melt will solidify at a melting point maximum at which the solid will contain -0.5002 atom fraction of tellurium. PbTe single crystals grown in our laboratories from stoichiometric melts have carrier concentrations of 9 x 10" per cu cm, indicating that the excess tellurium in the crystals is as expected from this phase diagram. However, growth of PbTe from a lead-rich melt will result in material having a more nearly stoichiometric composition. Although the addition of Sn to the melt shifts the solidus curve further toward the tellurium-rich side,4 the general discussion given for PbTe applies to the Pbl-xSnxTe systems as well. EXPERIMENTAL Single crystals of Pb1-xSnxTe have been grown in our laboratories from nonstoichiometric, cation-rich melts using the Czochralski technique and boric oxide liquid encapsulation. The details of the growth apparatus and growth technique have been reported in a previous paper on growth of these alloys from stoichiometric melts.2 In the present study, three specific crystal compositions were investigated in detail; x = 0.00, 0.10, and 0.17. Growth of alloy crystals from nonstoichiometric melts requires considerable care, and good quality single crystals were obtained in this study only by optimizing the mechanical and thermal stability of the growth system and by using pull rates of from 1 to 3 mm per hr (Pbl-xSnxTe crystals are easily pulled from stoichiometric melts at rates of from 5 to 10 mm per hr). The liquid encapsulation technique was found to yield near-ideal conditions, since the B2O3 layer increased the thermal stability at the growth interface, permitted easy attainment of near-ideal thermal gradients, and dampened vibrations at the melt surface. The hygroscopic character of the B2O3 was a slight problem and vacuum heat treating was necessary to completely remove the water from the boric oxide. During initial growth, the seed diameter was reduced and a narrow neck (1 to 2 mm diam) of several millimeters length was grown. The latter steps were found to be necessary for the growth of single crystals, i.e., if either of these two requirements were

Jan 1, 1970