Search Documents

By L. L. Melton, W. T. Malone

Fluid mechanics research conducted with non-Newtonian fluid systems now permits prediction of the behavior of these fluid systems in both laminar and turbulent modes of flow through circular pipes. Present work concerns non-Newtonian fluid systems currently used in the hydraulic fracturing process. During fracturing treatments, an unsteady-state condition may frequently be encountered arising from. the reaction rate of a chemical additive. This condition must be evaluated in order to predict the actual behavior of a particular fluid during field application. Design and operation of the apparatus used to determine fluid-flow behavior permit obtaining data under such non-equilibrium conditions. This paper shows methods used to obtain rheology measurements, develop hydraulic relationships and evaluate chemical reactions producing unsteady-state conditions. Engineering application of this research is illustrated by employing measured rheological values and developed hydraulic retationships to produce frictional pressure loss (psi/100 ft) us flow rate (bbl/min) charts of common tubing and casing sizes for an example fracturing fluid. How these charts and chemical reaction rate information are then combined to predict actual turbulent hydraulic behavior during unsteady-state field conditions is also discussed INTRODUCTION Many fluids used in hydraulic fracturing contain chemical additives which impart non-Newtonian fluid properties that may drastically alter their hydraulic behavior. Equally drastic alteration in wellhead pressure, injection rate and hydraulic horsepower requirement may result from these fluid properties. Prior research conducted to relate non-Newtonian fluid properties with hydraulic behavior has not as yet produced a universal relationship, particularly for the turbulent flow region. which of the many Possible non-Newtonian fluid properties is responsible has not been conclusively established. A systematic description, suggested by Metzner, of the many possible non-Newtonian fluid properties exhibited by real-fluid behavior, and a current discussion of theoretical and applied aspects of non-Newtonian fluid technoloy can be found in Handbook of Fluid Dynamics. f Little or no research has previously been attempted with fluids exhibiting time - dependent properties. Addition of chemicals during a fracturing treatment is often accomplished by continuously mixing and displacing the fluid. This produces a time-dependent effect or unsteady-state condition while the fluid is progressing through surface and wellbore conductors. This condition is due to solution or chemical reaction of the additive. Considerable departure from conventional methods of obtaining and interpreting data was found necessary to consider these conditions. Therefore methods were developed to obtain hydraulic behavior information under these complex, unsteady-state conditions. Relationships presented in this paper to predict hydraulic behavior of non-Newtonian fluids in circular pipes were obtained by constructing and operating a small pipeline apparatus in the manner of a pilot-plant study. These relationships are suggested as scaleup equations and are not proposed as fundamental rheological parameters. While perhaps deficient from a fundamental research viewpoint, a pilot-plant study does permit the determination and convenient evaluation of variables pertinent to a process. A pilot-plant study can result in a valid engineering application procedure even when fundamental relationships are still undefined. An excellent series of articles by Bowen has appeared in the chemical engineering literature.2-8 These give a thorough review of proposed hydraulic relationships and their limitations for non-Newtonian fluid behavior in circular pipes. A graphical method is presented to scale up data for a fluid exhibiting an anomalous hydrau1ic behavior in the turbulent flow region. Considerable assistance has been obtained from these articles to interpret the anomalous behavior noted during this investigation. These articles also provided assurance that a pilot plant is a practical approach to evaluate the hydraulic behavior of non-Newtonian fracturing fluids. _____________

Jan 1, 1965

By F. F. Aplan

The past year has been another year of vigorous fundamental research in mineral processing as evidenced by the active publication of results, particularly in Germany, Japan, United Kingdom, United States and USSR. It was also noteworthy for several significant meetings and conferences. The Basic Science sessions at the AIME Annual Meeting continued to attract an increasing audience and the sessions were especially notable for the active discussion of papers. The third Engineering Foundation Conference on Particulate Matter Systems,1 chaired by F. F. Aplan, was held in Milwaukee in August and attracted over 100 experts from five continents. Sessions at this week-long conference covered comminution, particle characterization, separation of fine particles, fluid-solid separations as applied to pollution control, flotation kinetics, particle-particle interactions and particle agglomeration. This popular conference will be continued under John Karpinski of Bethlehem Steel Corp. as 1968 chairman.

Jan 2, 1968

By Ferid Kromer

This paper is the first in a series which will describe geology, mining methods, and production costs of some, of Turkey's more important minerals. In this paper the economically significant minerals-chromite, meerschaum, and magnesite-of the Tagtepe district are described. The cost data presented are believed by the author to be the first made public on Turkish chromite mining.

Jan 1, 1950

By S. F. Shaw

In 1913, the Tiro General mine, at Charcas, S.L.P., Mexico, which had been making from 125 to 150 gal. of water per min., was allowed to become flooded, after all the pumps had been removed, and in 1918 the problem of unwatering it came up for solution. There are two vertical shafts, the Tiro General, 1390 ft., and the San Fernando, 1225 ft. in depth, with five connecting levels between them. The San Fernando shaft had been partly retimbered, while the Tiro General had been newly timbered from the collar to 1090 ft. in depth. It had been possible to place guides in only one compartment of the Tiro General, from the collar to the seventh or 850-ft. level, to which it was necessary to lower the water before station pumps could be installed. Soundings indicated that compartments in the Tiro General were open to 1082 and 428 ft., and in the San Fernando shaft to 471, 488, and 586 ft. The water had risen to a point 140 ft. below the collar of the Tiro General shaft.. Pumping Equipment The steam plant at the Tiro General shaft includes one 300-hp., one 150-hp. and one 100-hp. Erie City water-tube boiler, and two 160-hp. Heine water-tube boilers. All but one of these boilers were supposed to be in good shape, but it was soon discovered that six years of idleness in a climate that is foggy for several months of the year had left them in poor condition. The compressed-air plant comprises one Nordberg cross-compound compressor with piston displacement of approximately 2500 cu. ft.of free air compressed to 96 Ib. per sq. in.; and another Nordberg cross-compound with piston displacement of 1235 cu. ft. of free air, to the same pressure. The main pump station is on the seventh level where had been installed a Prescott pot-valve plunger pump with capacity of 200 gal. per min.; also a Gould triplex plunger pump with capacity of 135 gal. per min., driven by a 6 1/2 by 10 by 12 in. steam engine. From the lower levels, the water had been raised to the seventh level by small station pumps and sinking pumps.

Jan 1, 1920

By R. K. Hopkins

Fox a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not withstand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950° to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as -75° F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these requirements, but as a result of the extensive research carried on by steel manufacturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service.

Jan 1, 1935

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By S. R. Mitchell, M. C. Fuerstenau, A. M. Gaudin

The two principal attributes of a thickener pulp are its settling rate and the ultimate pulp density of the thickened mud. Testing for evaluation of thickening attributes of a pulp has usually been done batch-wise by placing the pulp in a one-liter glass graduated cylinder and noting the position of the boundary between clear liquor and mud as a function of time. Refinements in testing have included repulping a thickened mud to various dilutions and evaluating the settling rate on these various repulped muds. This is considered to make possible an estimate of the settling rate as a function of pulp density and therefore to pinpoint the slowest settling pulp which ought to be critical from the standpoint of thickener plant design. Finally, tests are sometimes made with model-size continuous thickeners of arbitrary size. In batch tests it is generally accepted that the behavior of a pulp is described by a curve such as the one shown in Fig. 1, in which the position of the boundary between clear liquor and mud (the mudline) is plotted against time. It has also been assumed that the initial settling rate (the slope of the line segment AB) is descriptive of the pulp and independent of the size and shape of the container. Where the settling rate is slower and clearly a function of time (portion CD of the settling curve), it has been assumed that the data are not of much use because of the intrusion of compacting phenomena. The next important datum is the height, PE, which is a measure of the so-called ultimate pulp density. This quantity is assumed to be characteristic of the pulp and independent of the container.

Jan 6, 1959

By C. M. Brinckerhoff

Safety work in mining at the Andes Copper Mining Company, Potrerillos, Chile, is divided into three parts: (1) accident prevention, (2) fire prevention and protection, and (3) silicosis prevention and control. In the company's operations a steady campaign has been waged to reduce accidents and silicosis, and to prevent fires. In the following pages the safety record for the past twelve years will be examined and the methods explained by which the accident rate was reduced. Table 1 contains yearly data pertaining to the scale of the mining operations and the accident record. Block caving is used for all ore production and the tonnage mined has averaged 30,000 short tons per day for the past seven years. Table 2 classifies 44 fatal accidents which have occurred since 1935. The leading causes of accidental death are transportation of ore and use of explosives, followed in order by persons falling, falls of ground, and by asphyxiation. In the case of serious accidents, however, the greatest cause is falls of ground, followed, in turn, by ore transportation, persons falling, explosives, and asphyxiation. Accident Prevention The improvement of the safety record was obtained by a combination of many factors. In surveying the results at Andes for the past twelve years, it is possible to select some features of the present operation which have contributed to the accident record. The most important of these are: (1) good staff planning, (2) good equipment, (3) an alert safety organization, and (4) education and selection of the workmen. GOOD STAFF PLANNING As a result of good staff planning, the mine has good working conditions, namely, good ventilation, moderate temperatures and humidity, and good lighting. These factors not only reduce accidents but also improve efficiency. In haulage work, accidents have been reduced by having traffic move in a forward direction only. The latter makes possible a one-man train crew. Trains are centrally dispatched from loading drifts which are interconnected by signal lights, so that when a train in a lateral drift is given permission to move into a main line drift, a red light signals in all other lateral drifts in that area. Good track is maintained, and safety niches are required at all switch throws. Since safety niches were provided there have been no fatal or serious accidents at such points. All main line haulage drifts are illuminated by electric lights. Haulage drifts are kept clean. Adequate clearance has been provided between cars and between cars and the sides of the haulage drifts. The 4 1/2 ton Cranby type cars are equipped with roller bearings, and the 10 ton loconlotives with trolley shoes instead of wheels. These two features are responsible for improved ore haulage conditions and contribute to greater efficiency and safety.

Jan 1, 1950

By R. W. Newcomb

THE constancy of calibration, and to a great extent the life, of a thermoelement is dependent on the suitability of the primary protecting tube in which the wires are mounted, particularly when used at high temperatures. An ideal thermocouple protecting tube would be com-posed of materials that would not contaminate the thermoelement wires contained in it-one that would remain absolutely gas-tight ,it all temperatures of usage, that will not be attacked by gases, or other surrounding agencies, that is not destroyed by heat, that withstands sudden and extreme temperature changes, that affords a high degree of mechanical protection and does not deform at high temperatures, that is a good heat conductor and obtainable in small diameters so as to keep down lag factors. It has not yet been possible to produce tubes of any known mate-rials that will meet all of these conditions. In selecting protecting tubes, therefore, one should be chosen the characteristics of which best fit it to the particular conditions of usage. Frequently conditions are such that two tubes have to be used, a primary gas-tight protecting tube inside of a secondary protecting tube, because certain agencies will attack the primary gas-tight tube unless it is guarded by the outside tube.

Jan 9, 1919

New Products Equipment

Jan 4, 1953

By Morris M. Fine, Norwood B. Melcher

As a raw material, prereduced pellets can be considered symptomatic of the quiet revolution taking place in the quality and grade of blast furnace burdens for the past decade. In 1954, the average analysis of ores from U.S. ranges in the Great Lakes area was 50.86% Fe (natural), 10.22% SiO2, and 10.90% moisture; ten years later, the average was 56.67% Fe (natural), 8.13% SiO2, and 6.17% moisture. The advance in Canada was even more pronounced in a lesser number of years. In 1957 the average product of Canadian ore-producing areas was 51.62% Fe (natural), 8.59% Si02, and 8.02% moisture; in 1964, the average grade was 59.59% Fe (natural), 6.27% SiO2, and 3.94% moisture.2 These dramatic data are testimony to the giant strides made in iron ore improvement, and the next logical step is prereduction. Prereduction can well be considered as a beneficiation step in which oxygen is the gangue. Since the ultimate objective of milling and smelting is iron metal, non-metallic constitutents in general, whether oxygen or silica, are contaminants. The past and continuing attack aimed at lowering the silica content of concentrates is succeeding. One need only thumb through the Grade Name listings of the American Iron Ore AssociationVo note that virtually all commercial pellets contain less than 8% silica, many are lower than 6%, and a few below 45%. With natural technical evolution, it is expected "many" rather than "few" will ultimately be in the last category and further mechanical concentration will have reached the point of diminishing returns. At this level, oxygen would constitute the only major diluent worthy of attack.

Jan 7, 1966

By W. A. Schaeffer, Sidney A. Justin, Jr. H. D. Easton

Restriction and proration of petroleum production have increased materially the difficulties attendant upon the estimation of reserves, particularly in large, "flush" fields. Such practices preclude the use of decline or other curves, from which, under capacity production conditions formerly prevalent, much could be learned as to the ultimate recovery to be expected from a given field or lcase therein. In restricted fields that would produce at many times the low rate allowed by the regulations in force if allowed to flow without restraint, one is forced to use other information than production performance to predict the volume of oil recoverable. Examples are: at Kettleman Hills, California; the Conroc, Van and East Texas fields, Texas; the Iowa field, Louisiana. It is beyond the scope of this paper to apply a definite method to the determination of the reserves in any actual field, therefore the discussion will be limited to a consideration of available methods and an enumeration of important factors governing the accuracy of such estimates. The problem is to determine not only oil in place but recoverable oil in place, for a given field or tract, which is complex and depends not only on the characteristics of the reservoir but also on the plan of development, the production allocation scheme, the rate of production and many other factors. Many data must necessarily be considered, weighed as to inportance, and assigned quantitative values. Estimates of recovery in prorated fields have been discussed by Brace', Shaw2, Snider3 and others. The wide difference in estimates of ultimate recovery from a number of important recently developed fields demonstrates the inadequacy of

Jan 1, 1935

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young's modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young's modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman' noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig' observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity' or the paramagnetic susceptibility.' Likewise, no one has noted a change in crystal symmetry. In the present investigation Young's modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,' and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.' The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder' the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young's Modulus: For measurement of Young's modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young's modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young's modulus at 25°C, Fig. la, is 28.2~10" dynes per cm' (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;' the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By Robert Pring

IN addition to the humanitarian aspects of a dust-control program, certain economic benefits are becoming more fully recognized and now furnish a greater incentive to the mill operator to eliminate the dust from his plant. It is well known that a favorable working environment promotes increased efficiency and improves the morale of em-ployees, with a consequent decrease in labor turnover rates. One progressive mining company estimates its direct and indirect labor turnover costs at from $40 to $50 per man; for skilled labor, such as machine operators, the cost may approach $100 per man. While these figures may not be typical of every plant, they do indicate a potential savings in operating costs. Dust signifies waste; its elimination de-creases maintenance costs of mechanical and electrical equipment; its recovery is often justified from the standpoint of values contained in the collected material, although in large-scale milling operations handling low-grade ore this may not be an important factor. Perhaps the most significant trend in industrial sanitation is that dust-control equipment and procedures are becoming recognized as integral parts of the mill flow-sheet. Exhaust ventilating systems are now afforded equal care in design and mainte-nance to that given other machinery more closely related to the process,

Jan 1, 1940

By Clarence A. Seyler

The object of all classification is to group together things which are alike, and separate those which are unlike. This object is essentially a practical one, enabling us to apply past experience to new conditions. Many costly large-scale experiments lose half their importance for want of proper description of the coal used, and the consequent impossibility of predicting that other coals will behave in the same way. I do not, therefore, make a fundamental distinction between "scientific'' and "use" classifications, except in so far as use depends on conditions, such as size or impurities which are not related to the nature of the coal substance itself. The characters chosen to define the classes of coal must be such as are accompanied by as many other properties as possible. It is not to be expected that any system of classification will enable us to predict every property of coal, since all specimens have an individuality of their own. But specimens can be grouped by a number of resemblances into species. Further, species which resemble each other can be grouped into genera. Elementary Composition as a Basis of Classification There can be little doubt that the ultimate or elementary composition of "pure coal" is the best basis of classification. It was soon after the perfection of the method of elementary analysis of organic substances by Liebig that Regnault, the distinguished chemist and physicist, laid down the principle that coals of the same kind vary only between narrow limits of elementary composition. This is still the widest generalization that can be made about coal. Upon it the metallurgist Gruner based his classification. In some quarters the value of the ultimate composition was denied, Stein going so far as to say that it teaches us nothing of importance about coal. One still hears statements that it is like crushing a work of art in a mortar and analyzing the powder, or like counting the number of times a given letter occurs in a sentence. Such comparisons are misleading, and the criticism might be applied to organic chemistry as a whole. Nor is the existence of isomerism, or of entirely different substances which

Jan 1, 1928

By Joseph D. Weeks

NOTE BY THE SECRETARY.—This address having been made the object of much hostile comment, arising, as Mr. Weeks believed, in large part from misunderstanding of its purpose and meaning, was, by his express direction, withheld from official publication in the Transactions until he should have so modified or added to it as to make such misunderstanding impossible. His illness and death prevented him from executing this intention; and, consequently, the only version of the address now in the Secretary's hands is one of which the author had forbidden the publication. Under the circumstances, therefore, it seems best to publish, in this place, only some portions of the address and its appendixes which have a historical value and are beyond controversy, giving at the same time a summary of its general nature, based upon the original manuscript and upon correspondence with Mr. Weeks. For this summary, the Secretary is alone responsible. The address was essentially a restatement of well-known and established facts, which it interpreted as proving that, of the three elements of the Bessemer process (namely, the pneumatic principle, the successful mechanical application of that principle, and the recarburization with spiegeleisen), William Kelly was the first inventor of the first, Bessemer of the second, and Mushet of the third. Mr. Weeks used the words " original inventor " in the sense (as he explained in one place) of first inventor, and neither asserted nor believed that Bessemer's con-

Jan 1, 1897

By Gerhard Bockstiegel

Kuczynski's formula has been derived for the case of nonspherical particles. TWO formulae of Kuczynski's type have been derived, one describing the increase in tensile strength, the other describing the progress of shrinkage of a powder compact. It has been strength,shown that the exponents of all three formulae each contain two magnitudes of different physical characters, viz, the geometrical factor a and the kinetic factor ß. The interrelationships between the three exponents are stated. SOME years ago Kuczynski1 experimentally showed that the radius, x, of the area of contact between very small spherical metal particles and a metallic block is related to the time of sintering, t, by the following equation x = constant tk [11 where k has the value 1/5 or 1/7. Assuming that the metal particles were perfect spheres and the metallic block was perfectly flat, he derived the foregoing equation from theoretical considerations of the process of material transport in metals, and he showed that exponent k is different for different mechanisms of transport, e.g., k = 1/2 for viscous flow (according to Frenkel2), k = 1/3 for evaporation and condensation, k = 1/5 for volume diffusion, and k = 1/7 for surface diffusion. From this Kuczynski concluded that the mechanism of transport was either volume diffusion or surface diffusion, depending on whether the value of k, as found in his experiments, was 1/5 or 1/7. Subsequently. Cabrera8 corrected Kuczynski's calculations with regard to surface diffusion, showing that the theoretical value of exponent k is 1/5 for both volume and surface diffusion. He supposed that the different experimental values of k were due to slight differences in the shape of the metal particles. An exponential relationship similar to the aforementioned was found by Okamura, Masuda, and Kikuta,4 Masuda and Kikuta, and Takasaki8 when studying the rate of shrinkage on powder compacts during sintering. The authors measured the shrinkage by means of the fraction w = Vp — V./Vp — V,,,, where V,, is the volume of the green compact, V, is the volume of the sintered compact, and V,,, is the volume of the compact in its densest state. This fraction, w, they found, is related to the time of sintering, t, by the equation w == constant tm. [21 Further, Bockstiegel, Masing, and Zapf7 observed that the tensile strength, s, of sintering iron powder compacts can also be related to the time of sintering, t, by an equation of the foregoing type, i.e., s = constant tn. [3] For exponent n the values 0.28 (S=2/7) and 0.35 ( 2/5) were obtained, and the authors pointed out that there might exist a simple interrelation between exponent n as found in their experiments and exponent k in Kuczynski's equation. The authors supposed that 2k = n, since the strength of adhesion between a metal sphere and a block (as in Kuczyn-ski's experiments) must approximately be proportional to their contact area, p. x2. Theoretical Considerations This paper is an attempt to correlate the fundamental experiments of Kuczynski's type with the results obtained with powder compacts as represented by Egs. 2 and 3. In particular, the paper is to show how the rate of sintering is influenced by the geometry of the sintering particles and by the type of material transport. As the geometry of particles conglomerating in a powder compact is very complex, some simplifying assumption has to be made, of course, in order to adapt the problem to mathematical treatment. In the following paragraph a suitable simplification is introduced, and Kuczynski's formula is derived for the case of nonsphcrical particles. Relation Between Area of Contact and Sintering Time—As the face of contact between two particles in a sintering powder compact is not necessarily a circle (as in the case of spheres sintering to a block), Kuczynski's formula is modified as follows: Let the perimeter of the face of contact be described by means of polar coordinates R, 4, as shown in Fig. la, so the area of contact, f, is determined by f= 1/2 . S112p[R(Æ) ]2 dÆ [4] Then, let the two particles be intersected by a plane perpendicular to area f. The intersection is shown in Fig. lb. According to the nomenclature in this figure, the distance, h, between the surfaces of the two particles is a function of T and Æ: h = h(r,Æ). For the particular case of spherical particles, as in Kuczynski's theory, this function becomes: h = constant r2. It shall be assumed here that in the close neighborhood of their

Jan 1, 1957

By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

FEW whose good fortune it has been to gaze on the Utah Copper mine but will agree that it is one of the two or three most magnificent man-made spectacles in the world. Skyscrapered Manhattan Island perhaps is more inspiring; but there the effect is obtained by aggregating a thousand separate units. The Utah mine is a single thing- the biggest thing that men have made. By the end of 1931 there had been moved at Utah 222,000,000 cu. yd. of material, including ore and the waste rock that overlay it. This figure will be increased at an average rate of nearly 20,000,000 yd. per year. Excavations for the Panama Canal are estimated at 232,300,000 cu. yd., but the Canal is 50 miles long, and it is impossible to obtain a comprehensive view of the whole project at one time. The spectator, on the other hand, need only walk part way up the east slope of Bingham Canyon to see unfolded before him the whole panorama of the great copper mine. In the foreground is a huge pit bottomed for the time being 100 ft. below the normal floor of the canyon, which also is the elevation of the main railroad yard. Here from 500 to 800 standard steel railway cars, each of 80-ton capacity, are assembled daily to carry the ore to the concentrators. But the main part of the mine and that from which ore is now coming lies above this level. As can be seen in the accompanying photograph, a series of terraces or benches reaches to the top of the mountain that projects between the main branch of Bingham Canyon and Carr Fork. From bench A (the yard level) to bench W is a vertical distance of 1500 ft. In height the benches vary from 40 to 70 ft. and in width from 30 to 450 ft. The lower benches, as they skirt the mountain,

Jan 1, 1933

By G. W. Traer

THE distillation of bituminous coals at what is commonly termed low temperature, and the quantities, nature and adaptabilities of the products have been the subject of considerable experimentation, during recent years. Fortunately, the earlier work in this country was done by men whose scientific training qualified them properly to record and interpret the results of-their experiments. The work of Prof. Parr, of the University of Illinois, is especially notable in this respect. Prof. Parr's work, added to that of English experimenters, demonstrated certain things to a degree which is generally regarded as convincing. They have proved that a caking bituminous coal, when subjected to a temperature of not more than 1000° F. (preferably somewhat less) will yield light tar having low specific gravity (about 1.06) and high value; also, that this yield, with a given coal, will depend upon the percentage of hydrocarbons in the coal, the maximum temperature used, and the promptness with which the distillate gases are removed. It is assumed that air is excluded from the retort, and that the coal is subjected to heat for a sufficient time to drive off all of the tarry hydrocarbons. The results attained in the first, or low-temperature stage of the Carbocoal process, recently described by C. T. Malcolmson, corroborate these general principles. It is the purpose of the writer to describe other work of a practical nature, directed toward the commercial adaptation of these principles, which was begun nearly two years ago; this investigation was assisted by A. J. Sayers, of the Link-Belt Co., and Carl Scholz.

Jan 9, 1918