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By Josiah Royce

To evaluate chemically the sample of rock obtained by diamond drilling, it has long been recognized that the analyses of the two components of the sample, core and sludge, must be given appropriate influence in computing the average analysis of any unit of depth. The purpose of this investigation is to set forth what means are available for apportioning the effect of core and sludge on the final analysis, what variables affect the problem, and what combination of applied mathematics will closest approximate the truth under each condition as these variables proceed within their limitations. A drill hole is bored in iron ore exploration principally to test variations in rock composition with depth and is usually directed as nearly normal to the bedding of a horizon to be tested as possible. This practice has a tendency to minimize variation in composition laterally which in any event is not likely to be great. It is obvious that the opportunity for change in analysis of a particular rock is not statistically as great radially in a diamond drill hole where the distance in which such a change may occur is from 0.719 in. (EX bit) to 1.469 in. (NX bit) as there would be longitudinally even in a' run as short as 5 ft. Variations in composition of bedded or layered rocks are usually greater normal to the bedding than parallel thereto. Even in massive rocks, like porphyries, variations are functions of distance. Hence. in either case, variations along the hole are of greater effect than across it. Let us examine Fig 1 briefly to observe a cross section of a unit of depth of a typical diamond drill hole. If we neglect radial change in chemical composition, which we have seen is small compared to lengthwise variation, we can see that if core recovery was 100 pct, the core and its surrounding area, which would be recovered as cuttings (assuming 100 pct sludge recovery), must analyze the same if the sampling is perfect. This is the foundation of this paper, namely, that if core recovery is complete we may assume that the core constitutes as nearly as possible a perfect sample of the ground drilled. Now let us pass to the methods of weighting core and sludge in the final analysis and then develop each in turn. One might employ core analyses only, sludge analyses only, or apportion the influence of each by one of several methods. The most common apportionment is by direct proportion to relative theoretical vol- ' ume occupied by each component in the cylinder hollowed out by the drill, known as the Longyear formula. Another logical treatment would be to consider core and sludge in the final analysis according to the weight of each recovered. This procedure was elaborately set forth and refined by R. S. Moeh1man.l Then to be sure that we have embraced all the possibilities, we must admit that some other method or methods may be devised empirically or by mathematical maneuvers. Should a drill machine be capable of recovering 100 pct of the core in all types of rock, certainly core alone need be analyzed and no complicated mathematics are required; but although some companies have had fair success in obtaining high percentages of core in certain homogeneous ores on the Mar-quette Range, their same methods have proved disappointing on the Menominee, Cuyuna, and Gogebic Ranges where the iron formation often varies widely from flinty chert beds interstratified with soft hematite to wholly leached ore material composed of an unpredictable mixture of hematite and limonite with occasional zones of sugary, recrystallized chert. In spite of numerous mechanical improvements in core barrels, few drilling programs can count on complete core recovery. The sludge alone might be analyzed but for practical reasons this is inadvisable when core is obtained due to the numerous opportunities for contaminating or losing portions of the cuttings. The Longyear formula involves a weighting of the core and sludge in proportion to the theoretical volume of each, that is, where the volume of the core recovered is one-third of the total cubic volume of the cylindrical hole made by the drill, the analysis of the core is given one-third of the weight in the final analysis. This approach to

Jan 1, 1950

By S. E. Piper, E. M. Buchalter, R. P. King, E. T. Woodburn

The problems involved in an optimum decision making model for flotation circuit are, first of all, to characterize the feed material in terms of parameters which can quantitatively describe the network flotation action in terms of a feasible set of control actions. Once the characterization has been postulated, it is then necessary to devise tests relating to parameter sensitivity, in order that credibility of the model predictions can be assessed. Once a credible model is available, the optimum control set is determined by a hill climbing technique. Details will be reported as to the credibility of model predictions using the stochastic flotation model on a network and further, computational problems associated with hill climbing for a complex objective function are reviewed. Discussion is presented on use of the Rosenbrock technique with constraints and use of a modified objective function with constrained derivatives when employing Fletcher and Powell technique.

Jan 1, 1969

By D. S. Jacobus

COMPRESSED-air motors are specially desirable, if economically practicable, for underground haulage, because they require no fuel, involve no danger of fire, and not only avoid heating and fouling the atmosphere with smoke and combastion-gases, but by the emission of expanding fresh air, cool and improve it and aid ventilation. The highest developments in the use of compressed-air motors for locomotion are to be found, in the opinion of the writer, in the principles of the Mekarski car-motor as applied to street tramways, and it is thought that notes taken regarding this system, during a recent trip to Europe, where two plants are in successful operation, at Nantes and Vincennes respectively, will be interesting to mining engineers. The plant at Nantes operates a street-line 5.2 miles long, requiring about twenty motors; the one at Vincennes about 7 miles of road. Each car at Nantes carries its own motor. At Vincennes, however, the motor-car is arranged to tow a second car containing no motor. The road at Nantes is the older, having been in successful operation for ten years, during which time neither the American consul, Mr. Shackelford, who has resided at Nantes for about five years, nor the vice-consul, Mr. Bennett, who has been at Nantes ever since the road started, has ever seen anything go wrong with the motors. DESCRIPTION OF THE RAILROA at Nantes. Motor-Car.—Two small engines are connected' so as to rotate the front axle of the car, a reversing lever being used to alter the cut-

Jan 1, 1891

By C. S. Smith, Chih-Chung Wang

D. Turnbull—In the opinion of the writer the most interesting result described in this paper is that the distribution of tin with respect to solidification temperature has several fairly well-defined maxima. It appears that each peak may be associated with a catalytic impurity of some rather specific composition. Recently we have obtained some additional evidence in favor of this viewpoint in experiments on the supercooling of lead droplets coated with different surface films. The distribution of lead droplets, ostensibly coated with lead sulphate, with respect to solidification temperature exhibited two distinct and reproducible maxima, one at 20" supercooling and the other at 47". On the other hand, when the droplets were ostensibly coated with halide films, no solidification was perceptible until the aggregate was supercooled more than 55". Upon further cooling a single well-defined peak centering at 60" supercooling was observed. Since the particle size distribution was the same in these two sets of experiments it appears that the most reasonable interpretation of the results is that the sulphate surface film or its reaction products with lead are much more effective in catalyzing the nucleation of lead crystals than are lead halide films. C. S. Smith (authors' reply)—Dr. Turnbull's experiments with lead drops coated with various surface films are most interesting. However, before drawing conclusions from the cooling curves described in the paper as to the existence of a few nucleus types effective at a few different temperatures, one must consider the state of subdivision of the liquid metal. In the A1-Sn alloy used, the tin was not in uniform droplets but tended to collect in three distinct shapes—in long interconnecting prisms along grain edges, in somewhat elongated interdendritic branching pools. and in isolated droplets. A single nucleus will solidify only the metal in contact with it, and the heat evolved will be proportional to the connected volume. A uniform distribution of nuclei of random effectiveness in such an alloy will cause peaks on the specific heat curve on cooling, which correspond to the volume distribution of tin and tell nothing about the nucleus type. In any real alloy both effects will be combined, and it seems impossible at present to distinguish between them. M. B. Bever—The thesis of this interesting paper is supported by a combination of positive and negative evidence. The authors have shown that under certain conditions a liquid phase may undercool, if it is dispersed in a thoroughly discontinuous manner throughout a solid matrix. They also found that undercooling

Jan 1, 1951

By Arthur C. Simmons

The State of Pennsylvania produces approximately 60 per cent of the total production of Pennsylvania Grade oil, and naturally represents the dominant factor in the area producing that grade. The producing area comprises the states of New York, Pennsylvania, West Virginia, and a small part of Ohio. The importance of this area is too commonly neglected because it produces only 2 per cent of the total amount of crude produced in the United States. It is, of course, unimportant in its percentage of total crude production, but extremely important for its production of lubricating oil. The lubricating fraction from a barrel of Penllsylvania Grade crude oil represents about 22 per cent of the total, whereas the lubricating fraction from the total United States production represents only about 2.5 per cent of the crude oil. The Pennsylvania Grade area produces about 6,000,000 bbl. of lubricants, which is 15 to 20 per cent of the total produced in the United States. All Pennsylvania Grade lubricants are classified as "high-grade," and with a production of 15 to 20 per cent of the total lubricants, it appears probable that the Pennsylvania Grade area accounts for 25 to 50 per cent of the high-grade lubricants produccd in the United States. Production Bradford Field The production figures quoted in Table I apply only to the part of the Bradford held that lies wholly within the state of Pennsylvania; approximately 15 per cent of the Bradford field is in Cattaraugus County, New York, and 10 per cent of the production is obtained from that sector. The Bradford-field production in 1941 was 12,729,900 bbl. as compared with a production in the year 1940 of 12,748,279 bbl., or a reduction of 18,379 bbl. The year 1941 represents the fourth successive year in which production in the Bradford field has declined. All of the production from the Bradford field is obtained by water-flooding methods and increases or decreases in production are due more to economic factors than to any physical limitations of the pool, inasmuch as additional drilling of water-intake and producing wells would increase the total production of the field. It is apparent that increased drilling of oil and water-intake wells does not take place except under stimulps of a favorable price; and while oil prices during 1941 were moderately favorable, they were not sufficient to prevent a mild decline. Too many wells were drilled in the Bradford field in 1937, but this was compensated by subnormal drilling activities in 1938 and 1939 and a large increase in 1940, The increase in 1941 over 1940 was about 7 per cent. The effect of new drilling is becoming less pronounced on a per well basis because more properties yielding less per acre are being drilled than were drilled in former years. Central and Southern Pennsylvania The production in central and southern Pennsylvania amounted to a total of

Jan 1, 1942

By Arthur C. Simmons

The State of Pennsylvania produces approximately 60 per cent of the total production of Pennsylvania Grade oil, and naturally represents the dominant factor in the area producing that grade. The producing area comprises the states of New York, Pennsylvania, West Virginia, and a small part of Ohio. The importance of this area is too commonly neglected because it produces only 2 per cent of the total amount of crude produced in the United States. It is, of course, unimportant in its percentage of total crude production, but extremely important for its production of lubricating oil. The lubricating fraction from a barrel of Penllsylvania Grade crude oil represents about 22 per cent of the total, whereas the lubricating fraction from the total United States production represents only about 2.5 per cent of the crude oil. The Pennsylvania Grade area produces about 6,000,000 bbl. of lubricants, which is 15 to 20 per cent of the total produced in the United States. All Pennsylvania Grade lubricants are classified as "high-grade," and with a production of 15 to 20 per cent of the total lubricants, it appears probable that the Pennsylvania Grade area accounts for 25 to 50 per cent of the high-grade lubricants produccd in the United States. Production Bradford Field The production figures quoted in Table I apply only to the part of the Bradford held that lies wholly within the state of Pennsylvania; approximately 15 per cent of the Bradford field is in Cattaraugus County, New York, and 10 per cent of the production is obtained from that sector. The Bradford-field production in 1941 was 12,729,900 bbl. as compared with a production in the year 1940 of 12,748,279 bbl., or a reduction of 18,379 bbl. The year 1941 represents the fourth successive year in which production in the Bradford field has declined. All of the production from the Bradford field is obtained by water-flooding methods and increases or decreases in production are due more to economic factors than to any physical limitations of the pool, inasmuch as additional drilling of water-intake and producing wells would increase the total production of the field. It is apparent that increased drilling of oil and water-intake wells does not take place except under stimulps of a favorable price; and while oil prices during 1941 were moderately favorable, they were not sufficient to prevent a mild decline. Too many wells were drilled in the Bradford field in 1937, but this was compensated by subnormal drilling activities in 1938 and 1939 and a large increase in 1940, The increase in 1941 over 1940 was about 7 per cent. The effect of new drilling is becoming less pronounced on a per well basis because more properties yielding less per acre are being drilled than were drilled in former years. Central and Southern Pennsylvania The production in central and southern Pennsylvania amounted to a total of

Jan 1, 1942

By W. O. Hotchkiss

DURING the summer of 1927, the Department of Terrestrial Magnetism of the Carnegie Institution of Washington joined with the Michigan College of Mining and Technology in conducting a series of earth-resistivity measurements in the Michigan copper country. The geological structure in this section is quite varied and fairly well known. The purpose of the investigation was to discover the correlation between the variations in electrical resistivity of large masses of soil and rock in place and the geological structure below the surface. The work done may be roughly divided into two parts: (1) Measurement and study of the variations in resistivity with depth, or with volume, to establish such general relations as exist between the two: and (2) the determination of the specific resistivity of various formations in order to make available more fundamental data which may aid in the interpretation of the results of the former type of measurement. A report by Mr. Rooney, which gives in detail the measurements made and the results obtained, forms the basis for this article.

Jan 1, 1928

By R. P. Agarwala, M. S. Anand, S. P. Murarka

Using the residual radioactivity technique, grain boundary diffusion of chromium in the a phase and lattice diffusion in the a and the ß phases of zirconiuttz have heen studied. The diffusivities (in units of square centiwzeters per second) have heen expressed as THE rate of diffusion of atoms along surfaces and grain boundaries is much greater than that through the bulk of metals. These processes dominate over volume diffusion at lower temperatures and can be isolated from it by virtue of the fact they yield high diffusion coefficients and low activation energies. In zirconium, however, it has been difficult to identify the volume-diffusion parameters separately. The values of diffusivities in a and ß phases yield activation energies which are much lower than those for volume diffusion calculated from semiempirical or empirical relations.1-3 Diffusion frequencies (Do) are also low, especially in the a phase, and they yield negative entropies of activation.4 Similar results have been obtained for the diffusion studies in titanium.5 It is yet to be investigated whether in these cases diffusion is controlled by some extraneous factor like high reactivity of these metals, or some different mechanism is operative as suggested by Pound et a1.6 However, Federer and Lundy,7 in a recent study of the diffusion of zir-conium-95 and columbium-95 in zirconium, and Gibbs et al.,8 in the study of impurity diffusion in titanium, found a temperature dependence of D, Do, and Q. Their study yielded low values of Do and Q at low temperatures, as has been found by other workers, and fairly high values at high tempera-

Jan 1, 1965

By M. J. Pool, P. J. Spencer, J. R. Guadagno

THE present work was carried out as part of a general program to study the magnitude and concentration dependence of exothermic heats of solution of various metals in liquid tin. Thermodynamic data for the Te-Sn system are very limited, particularly for dilute alloys. Indeed, apart from the prior heat of solution determinations of Pool,1 the only other published values are those of McAteer and seltz2 who carried out electromotive force measurements on solid alloys of compositions from 75 to 95 at. pct Te at temperatures between 543° and 668° K, of Colin and Dro-wart3 who made mass-spectrometric studies of the vapor in equilibrium with solid SnTe, and of Robinson and Bever4 who determined the heat of formation of SnTe by solution calorimetry. The present work thus provides further thermodynamic information for this system, specifically in a temperature range where the solubility of tellurium is very limited. The liquid metal solution calorimeter used in this investigation has been described previously.' No further discussion of its design or operation will therefore be given here. For each series of measurements a tin bath consisting of approximately 70 g of 99.99 pct pure Sn was carefully weighed out and inserted in the calorimeter which was maintained at the desired temperature to within ± 1/4°c. Tellurium, of 99.999 pct purity, was supplied by Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp. Approximately 0.0006 to 0.001 g-atom specimens of tellurium were used for each experimental run and these were added to the calorimeter from a temperature of 273" K. Heat of solution values were calculated by analysis of a strip-chart recorder plot of the heat effect accompanying the solution of each sample in the tin bath. The heat capacity of the latter was determined at regular intervals during a series of tellurium drops by using pure tin or tungsten calibration samples, the heat contents of which were obtained from the standard compilation of Hultgren et al5 The composition of the bath was calculated after each drop from a knowledge of the weights of tin and tellurium added. Values of the heat of solution of tellurium at 725" and 775° K are listed in Table I together with the corresponding tellurium contents of the alloys. The data are also plotted as a function of tellurium concentration in Fig. 1, which includes the equivalent data obtained by pool' at 750° K. It can be seen that the heat of solution remains

Jan 1, 1969

By J. Wade Watkins, E. S. Mardock

The accurate evaluation of reservoir-performance characteristics in the secondary recovery of petroleum by water flooding requires use of a water tracer that may be injected into water-input wells and detected at oil-production wells to supplement data obtained from core analyses, wellhead tests, and subsurface measurements. Radioactive iodine has been used successfully as a water tracer in field tests to determine: (I) relative rates and patterns of flow of injected water between water-input and oil-production wells and (2) zones of excessive water entry into oil-production wells. Laboratory evaluations of potential water tracers, previous tracer studies, the value of using a radioactive tracer, general field procedures, and the use of surface and subsurface instruments for the detection of the emitted gamma radiation, are summarized. Data from the field tests are presented graphically and discussed in detail. It is concluded that the radioactive-tracer method, using radioactive iodine, may be used successfully to measure either the relative rates and patterns of flow or zones of excessive water entry into wells under conditions of comparatively rapid transit time between wells. INTRODUCTION Extensive use is made of data obtained from core analyses, wellhead tests, fluid characteristics, and subsurface measurements in evaluating the sweep efficiency of water injected into oil sands for the recovery of oil. Theoretical flow rates and patterns may be calculated from those data using radial-flow formulas, if it is assumed that the physical conditions in the productive formation are homogeneous. Unfortunately, homogeneous conditions rarely, if ever, exist in oil-productive formations. The use of a tracer that may be injected into an oil sand and detected quantitatively, or even qualitatively, at offsetting oil-production wells provides basic data that may be used in determining more accurately the subsurface rates and patterns of flow of injected water between wells than is possible by theoretical calculations based on assumed conditions. Consideration of the data obtained by using a water tracer assists in the application of remedial measures to water-input wells, such as plugging of channels, or selective plugging of highly permeable zones, thereby effecting a more uniform flood and a greater ultimate oil recovery. A water tracer should have the following characteristics: (1) low adsorption on solid reservoir material; (2) high solubility in water; (3) low or negligible solubility in crude petroleum; (4) a wide range of solubility of compounds that may be formed by chemical reactions with ions present in reservoir rocks or waters; (5) high detectability in low concentrations by portable apparatus; and (6) general availability at low cost. Additional desirable characteristics are that the tracer should be nonhazardous in nature under normal working conditions and quantitatively detectable in the well bore, as well as at the surface. Review of Previous Tracer Studies The need for a water tracer has been recognized for many years. As far back as 1906, Dole1 described the use of fluorescein in flow-rate studies made in France in 1901. In 1921, Ambrose" discussed in detail the use of organic and inorganic dyes, chlorides, nitrates, and other anions, lithium salts, and the Slichter electrical

Jan 1, 1955

By Luke L. Y. Chang, Bert Phillips

A number of molybdenum oxides have been synthesized and their crystal structures have been described.' No data have been published on the stabilities of these oxides nor on the phase relations in the system Mo-0. It is probable that the tendency toward oxidation of both the metal and the oxides with low oxygen content in addition to the high volatilization rate of the oxides with high oxygen content have precluded accumulation of reliable data for establishing phase relations. These problems make experimentation difficult, but a modifi-

Jan 1, 1965

By H. K. Work

THE instrument for the rapid determination of carbon in steel, described in this paper, was developed originally to facilitate the opera-tion of the pilot-sized open-hearth furnace in the Jones & Laughlin Research and Development Laboratory. In this small furnace, with its shallow bath, the drop in carbon is accelerated, and a rapid, reliable test for carbon content is indispensable. This problem becomes rather acute when it is desired to finish heats at a carbon content higher than can be estimated with any degree of accuracy by the fracture test. Several independent methods for determining carbon were investigated, therefore, and it was found that a relatively simple magnetic device could be made to give reproducible results. A laboratory instrument was designed and set up for the use of the furnace operators. It was tested exhaustively in the laboratory and was used with considerable success for following the carbon content in the furnace bath. As soon as suffi-cient data had been compiled to indicate that the instrument might have a wider application, a more rugged model was constructed and placed in the mill to be tested on commercial heats. Finally, about a year ago, instruments were furnished to the plant open-hearth shops, and these have been in use since that time. As a matter of convenience, the instrument has been named the "Carbanalyzer," and will be referred to by this designation in the following pages. ?

Jan 1, 1939

By J. E. Pogue

It is the purpose of this paper to attempt to establish three theses which may be stated in advance as follows: 1. The crude oil potential is the accumulation of surplus initial production. 2. The crude oil potential is a semi-inventory and therefore is a causal factor in the price of crude petroleum. 3. The price of crude petroleum no longer correlates with above-ground inventories but does correlate with corrected inventories (i. e., above-ground storage plus the inventory equivalent of the crude oil potential). The factors and principles set forth in this study are thought to yield an approximate answer to a number of questions of active interest in the petroleum industry today, to wit: (a) How long would be required to eliminate the potential if all drilling ceased? (b) What would be the indicated crude oil production of the United States in 1931 if proration were abandoned? (c) What economic change would be necessary to warrant a higher price for crude oil? Definitions For the purposes of this study the following definitions may be stated: The crude oil potential in the United States is the quantity of oil that all the oil wells would make the first 24 hr. if permitted to flow unrestricted. The surplus potential is the above-mentioned quantity minus the volume currently produced. Initial production is the first day's unrestricted flow of an oil well. Aggregate initial production is the sum of the initials of all wells completed during a year. Surplus initial is the initial not needed to bring production into balance with demand. The surplus initial is equal to the crude oil potential minus the current rate of production. The annual production-equivalent of the crude oil potential is the volume of oil that would be produced in one year if all wells were permitted

Jan 1, 1931

By J. J. B. Rutherford

IT is now well known that troublesome intercrystalline corrosion may occur in austenitic stainless steels following exposure of the metal to a temperature within the range 1000° to 1500° F. (540° to 815° C.). The present paper describes a satisfactory method of estimating the extent of such corrosion, based on the measurement of the electrical resistance of a specimen before and after attack. This new method enabled us to study quantitatively the effect of several factors upon intergranular corrosion in the 18 Cr, 8 Ni type of alloy. The results show that susceptibility to this attack increases with increasing carbon content and grain size and appears to pass through a maximum for certain combinations of temperature of sensitization and period during which the alloy was maintained at that temperature; and are in complete accord with our interpretation of the mechanism of this phenomenon. The method is probably applicable to other metals or alloys subject to intercrystalline attack, such as the aluminum alloys of the duralumin type. The methods hitherto in use for estimating the degree of intergranular attack fall into three types: (1) microscopic examination,1 (2) macroscopic examination of fractures, and (3) determination of the time required for complete failure or disintegration .2 None of these lends itself very well to a measurement of the extent of corrosion. The first two are qualitative in nature and the third provides an arbitrary value largely dependent on individual judgment, since failure is a progressive phenomenon and not a sudden event. Our experience is that weight-loss determinations, although valuable in some types of corrosion investigations, bear no simple relation to intercrystalline corrosion in this type of alloy, as is to be expected since the phenomenon probably involves only the thinnest films between adjacent metallic grains.

Jan 1, 1932

By E. A. Beck

For a number of years many attempts have been made to use thermit in order to do away with piping in ingots. Some of these attempts were successful, while others did not give the expected results. Nearly every plant had its own method of using the thermit, and no special care was taken to study the results or to find the causes for lack of success. Formerly the principle of the process was to decrease the piping by introducing a can filled with thermit, attached to an iron rod, into the head of the ingot directly after it had been poured. In this case the thermit reaction took place in the upper part of the ingot, and it was thought that through the heat produced the head would keep liquid longer and piping thus be reduced. In other words, the aim was to keep the head of the ingot open by making use of the heat of the thermit reaction, which would thereby give the gases in the steel sufficient time to escape. This result can be attained by the application of a large enough quantity of thermit, but it would not be economical in general practice, and could only he used for high-grade material. Many steel-makers abroad and in this country have had this experience. The Th. Goldschmidt A. G., Germany, has, therefore, made a special study of this question with the cooperation of a well-known steel company, and has worked out a new method for the application of thermit for this purpose. The results obtained have been most satisfactory and reliable, and this process is now used in Germany on a large scale in many prominent steel-works. The thermit is applied in cans, as in former years, but the principle of the process is entirely different. The object of using the thermit is not to heat the steel and keep it liquid,

Jan 1, 1914

By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-'; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann's and Planck's constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962

By C. W. Sherman, J. Chipman, H. I. Elvander

THE pronounced and usually deleterious effects of sulphur on all ferrous metals and the resultant necessity for its control in metallurgical processes have stimulated many investigations of the system iron-sulphur. The data required for thermodynamic study of the behavior of sulphur in molten iron and steel include the activity and free energy of the dissolved sulphur and its heat of solution. Such data are also of theoretical interest since there is all too little information available concerning solutions of nonmetallic solutes in metallic solvents. It was the purpose of this investigation to attack the problem very directly by a study of equilibrium at several temperatures in the reaction H2 (gas) + S = H2S (gas) [1] K1 = PH2S /PH2 as where the sulphur is present in the liquid iron in amounts up to several percent by weight. Such a method of attack is not new since several careful studies have already been reported. It is planned, however, to extend the study to other metallic solvents and particularly to determine the effects of the various alloying elements on the activity of sulphur in liquid iron. This paper presents the results on molten iron-sulphur alloys containing up to 4 pct sulphur in the temperature range 1530°-1730°C. Literature Review The significant researches on dilute molten solutions of sulphur in iron include those of Chipman

Jan 1, 1951

By B. D. Cullity, O. P. Puri

The magnetostrictia of nickel after increasing amounts of plastic elongation was measured at field strengths up to 1500 oe. In addition, the residual stress was measured by means of X-ray line shifts. The observed decrease in magnetostriction following plastic strain is shown to be associated with residual compressive stress. If a metal bar, whose longitudinal axis is taken as the x direction, is plastically elongated in the x direction and then unloaded, X-ray diffraction measurements will indicate the presence of a residual compressive macrostress 0%. However, stress measurement by means of mechanical relaxation does not reveal any macrostress. In a previous paper1 the fictitious macrostress indicated by X-rays was ascribed to a particular distribution of micro-stress, namely, one in which the bulk of the material was stressed more or less uniformly in compression and a very small portion in tension. It was shown that this distribution would account for Neurath's measurements2 of magnetic losses in silicon steel, because of the effect of residual stress on magnetostriction. The present paper is concerned directly with magnetostriction, in nickel, and with the effect on magnetostriction of the residual stress created by plastic elongation. The residual stress was determined by measurements of X-ray line shifts. MATERIAL AND METHODS Commercially pure "A" nickel was investigated. Its nominal composition, in weight percent, is 99.4 Ni + Co, 0.2 Mn, 0.15 Fe, 0.1 Cu, 0.1 C, 0.05 Si, and 0.005 S. Magnetostriction was measured by means of SR-4 electrical-resistance strain gages mounted on specimens 1/4 in. sq and 8 in. long. Magnetic fields up to about 1500 ce were provided by a multilayer, non-cooled solenoid. A considerable amount of heat was developed at the higher field strengths, and, to avoid errors due to changes in the specimen temperature, the following procedure was adopted. Each measurement of the magnetostriction X at a particular field strength H was preceded by demagnetization and an adjustment of the strain indicator to zero; the field H was then quickly switched on and the strain read immediately. Curves of ? vs H were flat for field strengths above about 750 oe for all specimens, and this constant value of X was accordingly taken as the saturation magnetostriction ?s The X-ray measurements of residual stress were made with a Norelco diffractometer on specimens cut from flat bars 1 1/4 in. wide, 1/8 in. thick, and 12 in. long. These measurements were confined to lattice planes parallel to the surface of the specimen. Two reflections were studied: the 311 CrKß line at 28 = 157 deg, and the 420 CuKal line at 28 = 155 deg. The line centers were determined by fitting a parabola to the peak of the line, as suggested by Ogilvie3 and as modified by Koistinen and Marburger.4 The CuKa doublet from the plastically elongated specimens was first resolved by the Rachinger method5. All X-ray measurements were made by counting at fixed angular positions. RESULTS The results of the magnetostriction measurements are shown in Fig. 1 and Table 1. The magnitude of

Jan 1, 1963

By J. H. Brophy, J. Wulff, H. W. Hayden

The mickel-activated sintering of tungsten occurs in two stages of densification. A kinetic analysis of the second stage has been based on an appropriate model of the process. As in the first stage, the rate-controlling mechanism for the second stage is also the solution of tungsten in the nickel carrier phase. The transition from the relatively rapid first-stage results from the spherozdization of pores and the initiation of grain growth. Finer grain size due to higher-nickel content leads to more rapid and higher degrees of densification 1 HE sintering of tungsten is accelerated by small additions of nickel, cobalt, and iron.' Experimental evidence in detail has shown that nickel-coated, hydrogen-reduced tungsten powder may be sintered to more than 90 pet of theoretical density at l100o C.2, 3 Simultaneously, a kinetic analysis of the process showed that it took place in two distinct stages. In the first stage, nickel evidently served as a carrier phase through which tungsten atoms could move. This stage was kinetically similar to the "solution-precipitation" step postulated when the carrier phase is a liquid,4 although in the Ni-W case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in microstruc-tures at the temperatures under consideration. It has been shown that this stage corresponds to a process which is rate controlled by a phase boundary reaction.3 More recent evidence has been presented5 showing that after the initial rapid stage of sintering, densification continues in the final stage but at a slower rate, although no mechanism for this stage of densification was defined. An analysis of later stages of densification in solid state sintering has been presented,6 but it is not directly applicable in the present case of activated or carrier phase sintering. It is the purpose of this investigation to study the final stage of nickel activated tungsten sintering in greater detail The effect of varying nickel content has been examined, and a possible kinetic mechanism defined. EXPERIMENTAL PROCEDURE AND RESULTS Commercial hydrogen-reduced tungsten powder from Wah-Chmg Corp., having a nominal particle size of1 µ and a B.E.T. specific surface area of 5500 sq. cm per g was mixed with aqueous solutions of hydrated nickel nitrate in proportions sufficient to produce nominal compositions of 0.25, 1, 3, and 5 wt pet Ni. This solution was then evaporated to dry-ness at approximately 150" C for 15 hr. Following evaporation, the resulting powder cake was broken with a mortar and pestle and reduced in hydrogen at 800oC for 1 hr. Following reduction, the powder

Jan 1, 1962

By G. L. Corrigan, J. R. Coleman

Four factors that largely determine the end product obtained when cement and water are mixed are the chemical compo ition of the cement, the fineness to which the cement is ground, the amount of mixing water used, and the procedure used in mixing the slurry. In order to study the effect of two of these factors, the other two, the chemical composition and method of mixing, are kept constant, leaving as variables fineness and water-cement ratio. Through years of experimentation and usage it has been well established that the reduction of cement clinker to a very fine state by grinding improves its cementing value, principally because the reaction between cement and water takes place only at the surface of the cement particle, further action being hindered by the accumulation of reaction products that tend to coat the unreacted material. Therefore, the more finely ground a cement, and the greater the surface exposed in proportion to its mass, the more rapid is the hydration rate. Similarly, the greater the surface exposed, the greater the proportion of the cement that reacts, and the lower the amount of residue that is unreacted and so remains inert and unable to make any contribution to cementing properties.1 Although it is more expensive to manufacture a finely ground cement than a coarser cement, the advantages of fine grinding of construction cements were so marked that the fineness of cement has increased considerably in past years. When the manufacture of special oil-well cements was begun, it was necessary to consider properties of cement that previously were considered of minor importance, foremost of these being pumpability. Since, with the water-cement ratio constant, a finely ground cement will produce a neat slurry of higher consistency and shorter time of pumpability than will a coarser cement, there is a tendency to grind oil-well cements to a lower degree of fineness. Therefore, in order to produce oil-well cements that will make a slurry having a long time of pumpability, cements are manufactured that because of their coarseness generally are poorer cementing materials than some of the more finely ground construction cements. On the other hand, often it is necessary to pump oil-well cements for long periods of time to place them properly behind a string of casing in a deep well, and since high strength is not of foremost importance for such cement, there is room for considerable controversy concerning the proper fineness range.

Jan 1, 1941