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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 D. B. Kibler

Pill Florida hard-rock field extends from Suwanee and Columbia Counties in northwest Florida to south of Croom, Florida, in Hernando County this area is approximately 100 miles long and varies from 2 to 30 miles 1n width Florida hard-rock phosphate was discovered at Hale Springs, about one mile northwest of the town of Dunnellon Marion County, in the year 1888, by Albertus Voight who lived within a few hundred yards of the spring Soon after this discovery there was a great influx of land speculators and wildcat operators into the vicinity of Dunnellon A few years later phosphate was found in Alachua, Levy, Citrus and Hernando Counties, and a great number of small crude plants were built from Newberry, Alachua County, all the way to Croom, Hernando County Phosphate was found in many places as "outcrops " Looking for outcrops was the first method used by the early prospectors in searching for deposits Several years passed before any systematic method of prospecting was used EARLY MINING The early method of mining hard-rock phosphate was with picks and shovels, wheelbarrows, mules and wagons The pick-and-shovel method was used altogether until about 1900, when some of the larger operators began to use railroad-type steam shovels of from 1/2 to 1-yd capacity Picks and shovels, with negro labor loading the phosphate ore (called "matrix") into wooden side-dump skip-cars, was continued until about 1907 From the discovery of hard-rock phosphate until approximately 1905, overburden was removed with mules and scrapers At some places, the overburden was loaded into side-du nip skip-cars by negro laborers and the cars were then pulled up an incline with a steam hoisting engine The maximum depth of overburden that could be economically removed by hand labor mules and scrapers was approximately 15 feet About 1905 one of the companies erected a producer-gas powerhouse near Dunnellon and generated its own electricity and about the same time the larger companies began using hydraulic methods for the removal of overburden From the year 1888 through the year 1939, approximately 75 companies were operating at one time or another in the hard-rock territory, on approximately 500 locations The hard-rock deposits are more irregular and have higher mining costs than the pebble-rock deposits, therefore they have not been competitive in the domestic market, but because of the higher grade of the hard rock it is in demand for the export trade Discovery of phosphate outside of the United States has made it increasingly difficult in recent years for the hard-rock companies to survive, so today only three companies are operating These

Jan 1, 1941

By S. Harries Daddow

IN order to get an idea as to the strength of steel rails, it will be well to review the tests to which iron rails have been subjected. In England, Mr. Ashcroft found that the best 80 pound rails broke under a 300 pound weight, falling 15 feet. In Germany the Society of Railway tyfanage1-s determined 011 and have long applied a test of 1000 pounds falling 101/2 feet, as the standard which all first-class iron rails must reach. In this country no inspection nor test is applied, but tests made show that iron rails fro; our most reliable makers, break under a G foot fall of a 1500 pound drop as an extreme test, most of those tested breaking under a far less test; some breaking with less than a 3 foot fall of the same weight. Everywhere where steel has been used, engineers have come to the conclusion that some test is required to show the regularity and strength of the product. As compared with iron, the tests which steel will stand are wonderful. After numerous experiments partially based on the experience of the rail-mill at Graz, belonging to the Southern Railway of Austria, the Society of German Railway Managers fixed upon a test of 2000 pounds falling 138 feet. They found that this test represented the steel which suited their necessities, and also found that with steel of otherwise average purity, this test represented about one-half per cent. of carbon, and made it a rule to take no steel containing under three-tenths of a per cent. of carbon, because it was too soft. They expressed a hope that a harder steel could soon be made tough enough to stand the same test. I n England, a test was adopted of 2240 pounds, falling 15 to 17 feet on the rail on heavy bearings. This test has been found satisfactory under heavy traffic on average road-beds, and has been invariablyPILLAR of coal, which are designed and left in our mines as the means of supporting the overlying strata of our coal-beds, and securing protection to the miner, are not only insufficient for these purposes, but the most objectionable means of providing the desired security to life and property. Though such pillars are left at a great sacrifice to the owners of collieries and mineral lands, loss to the resources of the commonwealth, and ultimate privation to the public, they defeat the very ends for which they are designed, and not only do not secure life and property, but are as fatal to the one as ruinous to the other. Propositions.-It is eminently desirable that the resources of the Common wealth-particularly our mineral wealth in anthracite coal, which is limited-should be carefully utilized and made available, not only to ourselves but our posterity. Yet, speaking as an anthracite miner, we are wasting our resources of coal with a recklessness which will bring ruin in the end, unless checked, not only to the iron manufacturing interests of the East, whose chief protection, in competition with the iron-masters of the interior, lies in a cheap and abundant supply of anthracite furnace fuel, but to the best interests of the State. It is, consequently, not only desirable, but necessary, that we should realize every ton of coal from each colliery, and every acre of coal area, in order that our resources may not be wasted at present, to breed want in the future, and to realize the greatest present benefit to the mine, the miner, and the public. It is not possible, however, to secure these ends, if we continue to leave, as we do at present, from one-third to one-half our resources in anthracite as pillars in our mines. But our sad bills of mortality, our abandoned collieries, and our yawning mountain-sides, present ample evidence that even this enormous waste of coal, though left for the purpose of protecting life and property, is as totally inade-

By C. P. Lawhon, J. P. Simpson, W. M. Evans

Recent efforts to design drilling fluids for increased drifting rates have confirmed some laboratory results of other investigators, but have also produced additional data that should be considered. These data were obtained under controlled test conditions using a microbit drilling machine. Clays and some polymers have previously been reported to cause reduction in drilling rate. Recent data have shown that under laboratory conditions, suspensions of a single day or polymer have sometimes given faster drilling rates than when water was used. Measurements have been made of clay suspensions and polymer suspensions comparing filtration (I) under API conditions, (2) while drilling with temperature of 150F and differential pressure of 1,000 psi and (3) under dynamic conditions after drilling. Some correlation between instanraneous filtration (white drilling) and drilling rate has been observed. INTRODUCTION Several papers have been presented that related drilling fluids to penetration rate. Generally, it was found that a decrease in the solids concentration resulted in significant increases in the drilling rate. Of course, this change also resulted in a decrease in the viscosity of the drilling fluid.' Conclusions from investigations by this laboratory are in agreement. Data have shown that of the simple mud measurements commonly made at the drilling rig (density, plastic viscosity. yield point, API filtrate and total solids), only the density and total solids have a significant relationship to the drilling rate in Berea sandstone when attempting to correlate a single mud property individually.' More recent drilling rate experiments have been designed to study (1) effects of individual clays and polymers on drilling rates in Berea sandstone and Lueders limestone, (2) the relationship between drilling rate and dynamic filtration as measured after drilling and (3) the relationship between drilling rate and dynamic filtration as measured during drilling. Data show that drilling rates are dependent upon type and concentration of particles, type of formation and filtration of the individual fluids while drilling. Mud pressure: pressure of drilling fluid as measured after leaving the drilling chamber (Fig. 1). This is taken to be approximately the mud pressure just past the bit and at the face of the formation. Terrastatic pressure: pressure representing weight of overburden. Formation pressure: pressure of formation fluid as measured at outlet of drilling chamber (Fig. 1). This is taken to be approximately the pressure of fluid in the interstices of the formation. Differential pressure: difference between the mud pressure and formation pressure. LABORATORY EQUIPMENT AND TESTING PROCEDURE The drilling equipment was described in two previous publications."' Main components are a drilling chamber, filter-heater, rotary drive and variable-speed circulating pump. Auxiliary pumps supply pressure boosts for the mud, terrastatic and formation pressures. All equipment is designed for 15,000 psi and 500F. Capacity of the circulating system is approximately 7 gal. The mechanical design was facilitated by moving the rock down onto the bit. Data collected with this design should not differ from that obtained by a normal design where the bit moves into the rock. Drilling fluid is pumped through 50 ft of ID pipe coiled in an oil bath, enters the rotary shaft at a right angle and is pumped through the jets on the bit (Fig. 1). Most of the drilled solids are extracted by a screen mounted in the circulating system on the suction side of the pump. Data reported in this paper were obtained by controlling these parameters: mud pressure, 5,000 psi; formation pressure, 4,000 psi; terrastatic pressure, 5,000 psi; force on bit, 1,000 Ib; formation, Berea sandstone and Lueders limestone; flow rate, 7 gal/rnin; bit, 11/4-in. diameter with two 0.078-in jets; mud temperature. 150F; and rotary speed, 60 rpm. Mud pressure was controlled at 5,000 psi, thus giving a differential pressure of 1,000 psi even though the fluid densities varied. Cores of 3%;-in. diameter and 8 in. long were selected from quarry blocks to provide some control of grain size distribution, permeability and porosity. A 2-in. section was cut off each core and a I -in. diameter plug was taken from this section. Permeability to 5 percent by weight sodium chloride solution was determined and the large cores were

By Robert L. Akre

When Marco Polo visited China in the 13th century, no one knew what black powder was except the Chinese; they knew enough to make dazzling fireworks with it. But the realization that black powder could also do useful work came much later and, like all important discoveries, it altered the course of history. It was in the 14th century that black powder was first used to break rock in a very crude way; there were no drills and the powder was simply poured into cracks and exploded by setting it afire. Because its energy value was pretty low, the need for something more powerful was felt when the industrial revolution began. In the 1850s, miners began experimenting with liquid nitroglycerine on a limited scale. This was a very sensitive and dangerous explosive. Fortunately in the 1860s, Alfred Nobel succeeded in stabilizing nitroglycerine by absorbing it in kieselguhr-and a new product, dynamite, was born. With it, miners were able to unleash the great energy of nitroglycerine for blasting purposes. But dynamite was still a very sensitive explosive. In subsequent years, other explosives of various strengths and characteristics were developed, such as blasting gelatin, gelatin dynamite, ammonia dynamites, (all containing some nitroglycerine or nitrostarch), and liquid oxygen explosives. These products and their variations supplied the blasting trade for many years. A grained ammonium nitrate product containing some carbonaceous material entered the market in the 1930s. This explosive had below-zero sensitivity-meaning: a No. 6 blasting cap imbedded in it would not detonate it. A more sensitive initiator, called a primer, was needed to detonate this mixture. From Rags to Primacord to Solid-State The first initiator for an explosive charge was probably a rag slowly burning its way to the charge; this method was quite unreliable. Then came the burning fuse, which was an improvement. Next was the nonelectric blasting cap initiated by a fuse. With these initiators, a miner needed quick reflexes and good legs; upon lighting the fuse, he had to run immediately for cover. Development of the electric blasting cap that allowed for accurate timing eliminated this hazard; the electric cap, however, introduced other safety problems because of its susceptibility to extraneous electricity, e.g., ground currents, lightning, and static electricity. These caps also became available in millisecond delays. Development in the mid-1930s of Primacord, a detonating fuse insensitive to electrical currents or impact, further reduced blasting hazards, and is generally acknowledged as the safest known means of initiation. Eventually, Primacord millisecond connectors also became available for delay patterns in blasting. In the mid-1960s, the Primadet delay was introduced; it is a practical nonelectric detonator system that offers the precise timing of electric blasting caps-and is immune to the hazards or effects of extraneous electricity. Recently, Research Energy of Ohio, Inc. introduced a new type of solid-state blasting machine that combines a sequential timer and delay caps. It enables the efficient breakage of rock with a minimum amount of shock, ground vibration, and noise. Improvements in Blast-Hole Drilling World War II created an enormous demand for coal and other minerals in the U.S. and elsewhere. Great efforts and large amounts of capital were spent to find new mineral deposits and develop better mining methods. But while mechanization in mining proceeded at a rapid pace particularly in open-cut work, there was a definite lag in developing new or improved machines for drilling blast holes. The industry continued to depend largely on horizontal, churn, and pneumatic drills. No better machine was available for large scale production. The need for improvement in this phase of mining became more acute in the post-war years. Despite efforts toward further mechanization, mining costs rose rapidly because of mounting inflation and increasingly high wages. In most operations, drilling and blasting the overburden became the principal item of cost. Therefore, whatever size holes were being drilled, the holes had to be spaced so that any foot of the bore hole could be loaded with the maximum load required for the number of cubic yards of material that each foot of the hole was carrying. With the smaller holes that were being drilled, the proportion of drilling cost to the total drilling and shooting cost was much higher than it would have been with larger holes (because of the closer spacing required by smal-

Jan 1, 1977

By Arthur Phillips

THE normal method of preparing metallic alloys for commercial use involves the preparation of a melt containing the given components in the chosen proportions and allowing the homogeneous liquid mass to solidify in a mold of the desired form. The solidification is frequently accompanied by a segregation of the alloying elements in different parts of the casting. When the segregation is occasioned primarily by marked differences in density of the solid and liquid phases, it is termed "gravity" segregation. When the segregation conforms to a. selective freezing in harmony with the teachings of the equilibrium diagram of the alloy system-i.e., the lower melting phases are concentrated in the regions of the casting last to freeze-it is often referred to as " normal" segrega-tion. However, in many cases the lower-melting part of the system is concentrated in the parts of the casting first to freeze and the result in this case is termed "inverse" segregation. To complete the. terminology of the subject, normal segregation in a single phase is usually called "coring" and the word will be used in that sense in this paper. Inverse segregation, particularly when the liquid phase is exuded or sweated out on the surface of the casting, is sometimes called "location." Unfortunately, some ambiguity has arisen from the use of this term and it is perhaps advisable to confine its use to the dictionary definition; namely, "The separation of two phases by heat sufficient to melt one but not the other." The gravity and normal types of segregation are both well understood and to some extent are controllable by taking advantage of the most favorable cooling rate for a given casting condition. Inverse segregation has received considerable attention from several investigators- but none of the theories offered seem to account in a convincing way for the many examples of this type. The observations made in the present work on segregation in single crystals, and in some other castings, tend to support one theory of the mechanism of inverse segregation and definitely to

Jan 1, 1937

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By D. E. Swets, R. C. Frank

It is well known that hydrogen is introduced into iron or steel as a result of many chemical processes (acid pickling, electrolytic cleaning, plating, etc.). One of the reactions that has been of recent interest1 is the reaction between an iron surface and water vapor. It was shown a few years ago2-4 that hydrogen can be introduced into steel at an accelerated rate during abrasion as a result of this reaction. Grun-berg and Scott have also observed that water in mineral oil lubricants increases pitting failure in ball bearings5 and they have suggested that hydrogen from the water is the primary cause of this effect.' In this laboratory, the question was raised as to whether or not hydrogen is also introduced into the metal surface of a bearing as a result of the decomposition of the hydrocarbon lubricant itself, and an experiment was performed to try to find a satisfactory answer. All steel parts contain some residual hydrogen. Therefore, it appeared that the best way to carry out this experiment without the need for highly accurate quantitative analyses was to use deuterium as a tracer. The natural abundance of deuterium in H2 is only 0.015 pct. The tracer was obtained in the form of deuteroparaffin (CD,(CDJ, CD,) and 0.25 g were dissolved in 20 cc of mineral oil to form the lubricant to be used in the tests. The bearings used were New Departure Type QOLOO ball bearings with a ball diam of 0.187 in. Prior to adding the mineral oil-deuteroparaffin lubricant, the bearings were cleaned in warm trichloroethylene to remove the packing grease. After packing with the new deuterated lubricant, the bearings were operated in a bearing fatigue test machine under a radial load of 190 lb and a thrust load of 190 lb at a speed of 3800 rpm. The expected life under these conditions is about 500 hr. Two tests were made; one for a period of 27 hr and the other for a period of 102 hr. The bearings achieved a temperature of 120o F during the tests. When the tests were stopped the balls were mechanically removed from the bearings and were immediately placed in liquid nitrogen to reduce degassing until the analysis for deuterium could be made. Before analyzing, the balls were warmed to room temperature and scrubbed with several degreasing agents to remove all traces of the deuteroparaffin mixture. This cleaning procedure was shown to be satisfactory by running a control test in which one ball bearing was subjected to all parts of the test except running in the fatigue machine. The hydrogen and deuterium were removed from the balls using a hot extraction apparatus attached to a mass spectrometer. Four balls from each bearing were analyzed. Each one was analyzed separately by removing it from a cold storage volume of the hot extraction apparatus and transferring it to the oven tube with a magnet. As the gases were evolved they were analyzed with the mass spectrometer. Since the hydrogen and deuterium pass through steel in the atomic form and since there are many more hydrogen atoms than deuterium atoms in the sample, the probability of forming an HD molecule is greater than forming a D2 molecule. For this reason the evolution of HD and H was followed as each ball was placed in the oven. The results showed that as each ball from the test bearing was dropped into the oven, the mass spectrometer recording of the HD evolution increased by about ten divisions. When balls from the control test bearing were dropped into the oven, the increase was about one division or less. The hydrocarbon background in the mass spectrometer was also monitored to see if hydrocarbons or deuterocarbons were given off when the balls were dropped into the oven, but no change in the hydrocarbon peaks was observed. Since the balls contained a fair amount of residual hydrogen, isotope ratio measurements were made on the gas obtained from each ball. The D/H value found for those balls which had been operated in the fatigue testing machine was consistently about 0.3

Jan 1, 1962

By D. K. Deardorff, Earl T. Hayes

An improved technique is described for the accurate determination of melting points of metals in the temperature range 1500' to 2500°C. The improvements consist of gradient heating and refinements in cavity preparation to obtain true black-body conditions. The melting point of hafnium, as determined by this method, is set at 2222°±30°C. This is over 200°C higher than one of the values reported earlier. Discrepancies in the previously reported values for the melting point of hafnium are explained. The melting points of zirconium and titanium are found to be 1855O±15OC and 1668°±10°C, respectively. Reproducibility of results was ±3OC. PRIMARILY, this report is being made to correct a 1975o±25oC1 value for the melting point of hafnium, and to present an improved method for melting point determination. As a matter of interest, the technique was also applied to determining the melting point of zirconium and titanium. There is a wide difference in the melting point of hafnium as reported by competent investigators. DeBoer and Fast' reported a value of 2230°±500C, and later work of McPherson, as reported by Aden-stedt, placed the melting point at 1975o±25oC. Zwikker" calculated that the melting point was 2430°C. In resolving this discrepancy, improvements were made in the procedure for determining the melting points of refractory metals in the range 1500" to 2500°C. Special techniques are necessary to determine the melting point of these metals accurately. Since the metals oxidize in air above 900oC, the determinations must be carried out in an inert gas or vacuum. Also, every known refractory contaminates them to some extent. In addition, the attainment of true black-body conditions is always difficult. DeBoer and Fast actually determined the melting point of Hf-Zr as-deposited iodide process alloys and extrapolated to 100 pet Hf. McPherson employed a tungsten wire suspension similar to that described by Schramm, Gordon, and Kaufmann,1 and used hafnium metal produced by the iodide process. There was no apparent reason for the wide spread in melting points, since the quality of the metal was very good and the work was under the direction of highly competent investigators. Retracing some of this work revealed one understandable error in the case of hafnium, and led to development of an improved technique for determining melting points of reactive metals in the range 1500" to 2500°C. Material Crystal bar hafnium, zirconium, and titanium were used for this work, with analyses as shown in Table I. The hafnium was of the highest purity that has been prepared, though not as pure as the zirconium and titanium. At the instigation of the Pittsburgh Area Office of the AEC, a special lot of Hfo2 was purified, converted to the tetraflouride, and bomb-reduced with calcium, all at the Iowa State College Laboratories. This crude hafnium metal was then refined by the iodide process at the Foote Mineral Co. All specimens were cut with a Sic wheel, ground, pickled, and dried carefully before use. Procedure General Tungsten Suspension Method—In this method, a small specimen is suspended by a fine tungsten wire in a slender, induction-heated tungsten or tantalum cylinder, all under vacuum. The melting point is determined by heating the specimen slowly while observing it with an optical pyrometer focused upon a portion of the specimen that radiates as a black body. This means that there should be no reflected radiation, either from colder objects near the pyrometer or from hotter surfaces. The induction heater would be the only hotter object and, if it is slender enough, the specimen will attain the same temperature. Often a slender hole is drilled into the specimen as a source of black-body radiation. This was the general method used by McPherson in obtaining his value of 1975°C for the melting point of hafnium. In trying to repeat this work, it was found that the points of contact between the

Jan 1, 1957

By J. A. Bailey, J. H. Tundermann

The dihedral angles of the solid-liquid interfaces were measured at various temperatures above the solidus and the interfacial energies calculated when small additions of copper, indium, lithium, magnesium, antimony, and silicon were made to an aluminum alloy containing 3 pct Sn. When the results were compared with those of the Al-Sn alloy some differences were found which could be interpreted in terms of the ability of the added element to enter into solution or form intermetallic compounds with the aluminum and tin. It was shown that in some cases considerable changes in the shape of intergvanular liquid films can be brought about by comparatively small compositional changes in the alloy. DURING the melting or solidification of an alloy a temperature range is usually found where the presence of a liquid phase may be detected at the grain boundaries of a solid. It is believed that the presence of this liquid phase is responsible for hot tearing in castings and welds and hot shortness in the working of some alloys at elevated temperatures. Rosenberg, Flemings, and Taylor1 in a study of the solidification of aluminum castings have indicated the importance of intergranular liquid films and shown that their shape and distribution at the end of solidification effect the hot tearing characteristics of the material. The shape of such intergranular liquid films are determined largely by the ratio between the solid-liquid interfacial energy (yLS) and the grain boundary energy (ySS). A measure of this ratio (yLS/ySS , relative interfacial energy) is the dihedral angle 8. The dihedral angle 0 is related to the relative interfacial energy by the following expression: Rogerson and Borland 2 have also suggested that the shape of the intergranular liquid is an important factor in determining the susceptibility of a material to hot shortness. They showed that on a comparative basis materials having the lowest dihedral angles at a given temperature gave the greatest severity of cracking. They stated that liquid in the form of globules should be less harmful than liquid in the form of extensive films as more intergranular cohesion should be possible. Rogerson and Borlland 2 also showed that the susceptibility of an A1-Sn alloy to hot cracking can be reduced by small additions of cad- mium. It was found that the cadmium gave an increase in the dihedral angle at all temperatures. Ikeuye and smith3 investigated changes in the dihedral angle and relative interfacial energy with temperature for a number of ternary alloys formed when small additions of bismuth, cadmium, copper, lead, and zinc were made to an A1-Sn alloy. They found that in most instances changes in the dihedral angle were caused by compositional changes in the liquid phase; as the composition of the liquid approached that of the solid the dihedral angle decreased. They noted that the addition of a third element which was soluble in both the liquid and solid phases at a given temperature may decrease the dihedral angle (e.g., the addition of copper or zinc) but otherwise the ternary alloys formed exhibited dihedral angles between those of the A1-Sn binary alloy and those of the binary alloy of aluminum with the added element. Dwarakadasa and Krishnan4 investigated the changes in dihedral angle and relative interfacial energy with temperature when small additions of magnesium, iron, silicon, manganese, sulfur, cobalt, and silver were made to a copper alloy containing 3 pct Bi. They found that in all cases the added elements gave an increase in the dihedral angle and relative interfacial energy when compared with the values obtained for the simple binary alloy at the same temperature. It was noted that an increase in temperature gave a decrease in dihedral angle and relative interfacial energy in each of the ternary alloys studied. Similar results have been obtained by Ramachandran and Krishnan5 for the addition of small quantities of lead. This paper describes the application of dihedral angle measurement to the determination of the shapes of liquid phases at various temperatures above the solidus when small additions of copper, indium, magnesium, lithium, antimony, and silicon are made to an aluminum alloy containing nominally 3 pct Sn. An attempt is made to correlate the measurements with the relative solubility of the added elements in tin and aluminum. The work was undertaken to provide more data concerning the effects of temperature and composition on the shape of liquid films above the solidus. EXPERIMENTAL PROCEDURE In the present work ternary aluminum alloys containing nominally 3 pct Sn and small additions of high-purity copper, indium, lithium, magnesium, antimony, and silicon were made. The alloys were melted in a graphite crucible under an inert atmosphere of argon and cast into ingots 6 in. long by 0.5 in. diam. The ingots were then cut into rods 1.5 in. long, given a 50 pct cold reduction, and machined into test pieces 0.5 in. long by 0.5 in, diam for heat treatment. The alloy samples were annealed at the various test temperatures between the liquidus and solidus for approxi-

Jan 1, 1967

By A. E. Jenkins, L. A. Baker, N. A. Warner

Rates oj decarburization of levilated Fe-C droplets conlaining 5.5 to 0 pct C have been measured at 1660°C. Gas mixtures of 1, 10, and 100 pct 0, with helium diluenl were used at velocities of 12.5 and 62.5 cm per sec. Rates were independent of carbon concentration in the mell and in good agreement with the calculated rule of oxygen diffusion through the gas boundary layer. The effects of flow rale and total pressure are as predicled and the rates are approxitnalely 2.5 times those with CO2 as oxidant. The mass-transfer correlation used incorporaled the efject of natural convection as well as forced conrection. Graphile spheres are shown to oxidize at the same rate as Fe-C droplets under the same experimental codlions. It is concluded that, for high carbon concentrations in the melt, the rate of- decarburizalion is controlled wholly by the rate of gaseous diffusion. Rate measurements with pure CO, are reported for low carbon concentrations where CO bubbles nucleate within the droplet. Under these circumstances the decarburi-zation decreased with carbon concentration and it is proposed that carbon diffusion is significant in conlrolling the decnvburization rate. In an earlier paper1 decarburization rate measurements were reported for levitated Fe-C alloys at 1660°C but with CO2 as the oxidant. The decarburization rate was found to be independent of carbon concentration in the melt but slightly affected by total pressure. The authors were unable to explain the slight pressure effect but in all other respects the results were consistent with control by diffusion in the gas boundary layer. Subsequent work has been directed at finding the reason for the slight pressure effect and whether the kinetics with oxygen as oxidant parallel those with CO2. Recently Ito and Sano2 have shown that with water vapor-argon atmospheres the decarburization rate is gaseous diffusion controlled until an oxide film appears on the surface. In this work the melts were contained in crucibles. MASS TRANSFER IN THE GAS PHASE In the earlier analysis1 only forced-convection mass transfer was considered. Subsequent recognition of the existence of some free-convection mass transfer explained the observed small effect of total pressure on the decarburization rate. Steinberger and Treybal3 and Kinard, Manning, and Manning4 have developed correlations involving the linear addition of the contribution of radial diffusion, free and forced convection. Steinberger and Treybal&apos;s correlation was chosen as the most applicable to the present work since it correlated most of the data available in the literature and handled the low Reynolds number region exceptionally well. The correlation for (Gr&apos;Sc) < 108 is where Nu&apos; is the Nusselt number for mass transfer based upon the total surface of a sphere in an infinite medium, G&apos; is the mean Grashof number for mass transfer defined by Eq. [2], Sc is the Schmidt number (µ/pDAB)f, Re is the sphere Reynolds number (dpu,pf/µf), p is the viscosity of the gas (poise), p is the density of the gas (g cm-3), Dab is the binary diffusivity for the system A-B (sq cm sec-&apos;), dp is the sphere diameter (cm), u is the approach velocity of the gas (cm sec-I), and subscript f denotes the property value is computed at the film temperature Tf defined by Tf = +1/2(To + Tr) where To is the specimen temperature and T, is the approach gas temperature (oK). Natural convection occurs when inhomogeneities exist in gas density. These may be caused by concentration gradients, temperature gradients, or both. In the present work the temperature gradient between the sphere and the bulk gas was very large and in some cases, for example the runs with pure oxygen, the concentration gradient was also appreciable. The Grashof number defined by Mathers, Madden, and piret5 was used since it took account of both temperature and concentration gradients: where Gr&apos; is the Grashof number for mass transfer (p2fgd3|-yA-yA|/µ2f), Gr is the Grashof number for heat transfer (p2f gd3p|To - T,]/µ2fTf), Pr is the Prandtl number (cpµ/k)f, g is the acceleration due to gravity (cm sec-&apos;f, a is the concentration densification coefficient (1/p)(ap/ayA)T, yA is the mole fraction of component A at the gas-metal interface, yA is the mole fraction of component A in the bulk gas stream, cp is the heat capacity of the gas per unit mass at constant pressure (cal g-I OK-&apos;), and k is the thermal conductivity of the gas (cal cm-&apos; sec-1 OK-1). Mathers et al. tested this combined Grashof number

Jan 1, 1968

By B. E. Terkelsen, B. J. Piearcey

A study has been made of the effect of unidirectional solidification on the creep behavior, stress-rupture properties, and thermal shock resistance of four nickel-base superalloys. The alloys Mar-MZOO, B-1900, IN 100, and TRW 1900 show improved rupture ductility and thermal shock resistance when tested with the columnar grains parallel to the major stress axis during test. The relative improvement in creep-rupture properties depends on the intrinsic strength of the alloy, a property which depends on composition, heat-treatnient, and crystallographic orientation. The data clarifies some of the factors affecting the properlies of the cast nickel-base superalloy. COMPONENTS designed for high-temperature use have, in recent years, been fabricated by precision casting techniques using nickel-base alloys developed specifically for use in the conventionally cast condition. This development was a result of both the increasing complexity of the component and the recognition that high-temperature strength was incompatible with workability. The use of castings can be economically favorable, but, more important, the recent complex designs of air-cooled gas turbine blades and vanes in alloys which possess the necessary high-temperature strength cannot be forged. Common modes of failure of high-temperature components are excessive creep, creep rupture, and thermal fatigue. If rupture occurs then the mechanism is usually by inter crystalline cracking along those grain boundaries oriented transverse to the major stress axis. In the stronger alloys, rapid propagation of intercrystalline cracks result in apparent premature failure demonstrated by the absence of third stage creep in a creep-rupture test and low rupture ductility. Tensile ductility shows a similar trend, that is, decreasing ductility with increase in strength. It is not surprising, therefore, that increases in creep strength have only been obtained with a loss in resistance to thermal shock, a property which shows a dependence on tensile ductility. VerSnyder and ~uard&apos; showed that the application of unidirectional solidification to a brittle Ni-Cr-A1 alloy both improved the rupture life of the alloy and increased rupture ductility. Since this casting method results in columnar grains, it appeared that the solution to the lack of ductility in nickel-base alloy components was the elimination of the source of failure, namely the transverse grain boundaries. This concept was recently developed2 to produce cast-to-size gas-turbine blades and vanes consisting entirely of columnar grains oriented parallel to the major stress axis of the component. Not only did the process impart increased rupture life and ductility to the components, but it also increased their resistance to thermal shock. During this development, the effect of unidirectional solidification on the properties of several alloys was investigated. The resulting data allows certain conclusions to be drawn regarding the factors affecting the creep and stress-rupture properties of the cast nickel-base superalloy and also its resistance to thermal shock. Detailed information was obtained on the alloys Mar-MZOO, B-1900, In 100, and TRW 1900. The composition of the alloys studied are shown in Table I. MATERIAL PREPARATION AND TESTING The conventionally cast alloys are cast as +-in.-diam bars in innoculated shell molds under conditions designed to maintain control of grain size. Unidirec-tionally solidified casting were produced in the form of 3-in.-diam ingots. Specimens from the latter were machined such that the axes of the columnar grains were parallel with the axis of the test bar, except in certain cases where the transverse properties of the material were being evaluated. The specimens were tested in an axial loading creep machine.&apos; Temperatures were measured with thermocouples, attached just outside each end of the gage length, to assure uniform temperature along the entire specimen. Chromel/alumel thermocouples were used up to 1800"F and Pt/Pt-10 pct Rh thermocouples above 1800"F. The specimen temperature was recorded and maintained within i2"F throughout the test. Creep extensions were measured automatically with extenso-meters attached to ridges on the specimen and recorded continuously using linear variable differential transformers and multipoint recording equipment. MICROSTRUCTURE The microstructures of transverse sections of the four alloys studied are shown in Figs. 1 and 2. Fig. 1 shows optical micrographs of the alloys, both in the conventionally cast and unidirectionally solidified conditions. Each alloy displays a cored dendritic structure, a distribution of MC carbide, and the presence of the y — y&apos; eutectic constituent.~ In the case of IN 100 and B-1900, Fig. 1 indicates that in these specimens the eutectic is degenerate. That is, it consists only of y&apos; pools indicating that the y constituent has been solutioned during the cooling period after solidification. The major effect of unidirectional solidification on the microstructures of the alloys is a tendency to promote a more dendritic form of MC carbide and an increase in dendrite arm spacing, both effects being a result of the slower solidification rate in the unidirectional solidification technique. V, lec tron micrographs of transverse sections of the four alloys in the two cast conditions are shown in

Jan 1, 1968

By J. C. Bierlein, R. A. Dodd

Endurance strengths at 10&apos; cycles, fatigue-hardening rates, and endurance strength/0.2 pct proof stress ratios have been determined jbr a range of Cu(Ni), Cu(Si), and S.R.0. Cu(Au) solid solutions. Some douht is cast on simple cross slip models of fatigue hardening in view of opposite composition dependencies of hardening displayed by Cu(Si) and Cu(Au). The temperature dependencies of hardening also are the opposite of predictions made on the basis of a cross slip model. A correlation apparently exists between the fatigue strength/0.2 Pc~ proof s1.re.s~ ratios and rates of fatigue hardening. An increase in PS/PS due to alloying or temperature change is accompanied by a decrease in hardening rate, and vice versa. In recent years there has been much interest in the determination of the dislocation structure of fatigued metals and alloys. The accumulated evidence, e.g., Refs. 1 to 5, suggests that the structure may be dependent on the stacking fault energy, 7, of the fatigued metal in the same way that fatigue hardening rates have also been shown to apparently depend on u .6&apos; 7 The above research followed the various earlier theories relating crack nucleation to ease of cross slip, e.g., Refs. 8 to 131 so "ggesting that y may indeed be the parameter of principal significance in all facets of the fatigue process. However, comparatively little attention has been paid to correlating engineering fatigue data with observations of the above type. Certainly, it would be useful if potential engineering fatigue performance could be assessed from a knowledge of easily determined alloy properties, and the present research originated from this standpoint. TO investigate the widest Possible range of 7 would require the use of two solvent bases, e.g., aluminum and copper, but a reasonable coverage can be provided by copper-based solutions alone. Therefore, it was decided to work with Cu(Ni) and Cu(Si) solid solutions, the approximate stackillg fault energies of which are given in Table I. The y range extends from low, Cu(7.5 at- Pet Si), to moderately high in Cu(2-5 at. ~ct ~i) and two of the Cu(Ni) alloys. The values listed in Table I should be regarded as qualitative only, being derived as follows. Dillamore and smallman14 quote a value of 85 i 30 erg.cm-2 for the stacking fault energy of pure copper, based on an earlier value due to Howie and swannl5 corrected by Brown&apos;s formula.&apos;&apos; Since the ratios (alloy)h(pure copper) have been reported17,18 for Cu(Ni) alloys containing up to 30 pct Ni, approximate ) values for these alloys can be computed, and a rough estimate of 7 for Cu(50 at. pct Ni) obtained by extrapolation. The relatively low y value obtained in this way for Cu(50 at. pct Ni) coincides with the observation of Nakajima19 that the stacking fault probability is a maximum at this composition. Likewise, the y values for the three ~u(~i) alloys are estimates based on values given by Swann and Nuttingo corrected on the basis Of Brown&apos;s estimate that the true 7 values are probably 2.3 times greater than those originally computed. In addition to the above alloys it was decided to investigate short-range ordered (s.R.O.) CU(AU) alloys containing up to 25 at. pct Au. This last alloy has been shown to have a well-defined planar arrangement of dislocations when deformed,21,22 probably due to cross slip being restricted by the S.R.O. Engineering fatigue data was to be represented by the determination of endurance strengths, and these were to be correlated with fatigue hardening and mechanical property data. EXPERIMENTAL I, order to study the desired properties and property changes, the following alloys were prepared: Cu(2.5 at. pct Si), Cu(5.0 at. pct Si), Cu(7.5 at. pct Si), Cu(5.0 at. pct Ni), Cu(25.0 at. pct Nil, Cu(50.0 at. pct Ni), Cu(5.0 at. pct AU), Cu(15.0 at. pct AU), Cu(25.0 at. pct AU). The copper and gold were zone-refined, while the silicon was semiconductor grade. The nickel was of 99.95 p,t. purity.* All alloys were induction-melted in a *Kindly supplied by the International Nickel co. helium atmosphere, appropriate precautions being taken to avoid segregation in the Cu-Au series. Rod stock was obtained by rolling and swag,ng. A few Bridgman single crystals were grown for fatigue-hardening studies, but most material was machined into polycrystalline fatigue speciments of the design shown in Fig. 1, and into polycrystalline tensile and fatigue-hardening specimens of simple cylindrical design. All specimens except Cu(Au) were annealed; the latter were quenched from above T, to produce short-range order. A few of the quenched alloys were examined for long-range order by step-scanning over

Jan 1, 1969

By H. C. Johnson, J. K. Elliott

One of the primary requirements for successful operation of an enriched gas-drive project is to control the composition of injection gas. This can become a serious and difficult problem, particularly in cases where the enrichment material is being furnished from a number of field -produced gas streams. It is possible to effect control of the injection gas composition through frequent or continuous sampling; however, this can be extremely costly and, in many cases, impractical due to laboratory requirements of time. Another alternative would be to provide a calculation technique which would be flexible and sufficiently accurate to predict composition of the liquid and gas streams of interest at any point in the system. The purpose of this paper is to discuss a technique that was used successfully on an operating enriched gas-drive project for developing information which could be used for controlling composition of the injected gas. FIELD OPERATIONS The particular field (hereafter called Example field) in the example operation being discussed is composed of four oil reservoirs (A. B, C and E) and one gas condensate reservoir (D). Casinghead gas from the oil reservoirs and gas from the gas condensate reservoir are gathered through a field gathering system as shown in Fig. I for injection into Reservoir C. The gas mixture which is recovered from the five reservoirs for injection purposes is composed of gases liberated in 19 individual separators, each operating at a separate temperature and pressure. PROPOSED CALCULATION TECHNIQUE It is well known that vapor-liquid equilibrium calculations in general use throughout the petroleum industry can be used to predict reliably the phase behavior of hydrocarbon mixtures, particularly at pressures less than 1,000 psig. It is then a simple matter to account for the material on a ComPonent basis by m&apos;&apos;ing flash and material balance calculations at each separation point in a hydrocarbon system. Accordingly, it was proposed to use vapor-liquid equilibrium and material balance cal- culations with a medium-sized electronic digital computer as a basis for developing a control procedure for use in controlling injection gas composition in the enriched gas-drive project. Although the approach is a simple one, the numerous vapor-liquid equilibrium calculations involved make the problem laborious; in this particular case, it would have been impractical to make sutficiently complete analysis without the aid of digital computing equipment. SAMPLING AND VERIFICATION OF CALCULATION PROCEDURE To obtain representative gas and liquid stream samples and to provide a quantitative measure of overall system Performance for comDarative purpLses, a thorough test of the field and plant system was conducted in the summer of 1957. Oil production at each battery was sta-

By A. S. Nowick, E. S. Machlin

ONE of the main criteria used to rate the heat-resisting properties of alloys is stress rupture.1 During a stress-rupture test a tensile specimen is held under a constant load at a constant temperature until it fractures. The chief measurement made during this test is the time required for rupture at the specific test stress and temperature. It was found empirically from a series of stress-rupture tests at a constant temperature that when the logarithm of the time for rupture is plotted against the logarithm of stress a straight line is obtained within experimental error.2~3 This method of showing stress-rupture data has been adopted by many investigators and the KACA.4 By interpolation and extrapolation from these plots, values of the stresses required to rupture the specimens (the rupture strengths) in 10, 100, and 1000 hr are obtained for specific temperatures. Alloys are then rated for a particular application on the basis of their rupture strengths at the rupture life that most nearly represents the application. Inasmuch as stress rupture is an important criterion in rating heat-resisting alloys, it would be advantageous to know the quantitative dependence of the time for rupture on stress, temperature, com- position, and structure. In order to obtain this information, an investigation was made at the KACA Cleveland laboratory during the spring of 1945. The theory of rate processes was used because it has been found to apply to certain processes such as chemical reactions, viscous flow, and creep that occur at a definite rate for given conditions. It was thought that stress rupture was such a process. An equation was derived that gives, for a given com- position and structure, the dependence of the time for rupture on stress and temperature. The investigation is part of a general program to provide information that will lead ultimately to the development of better alloys in order that the efficiency and power output of gas turbines used in aircraft propulsion can be increased. THEORY The theory of rate processes will first be discussed as a general theory. It will then be shown that if stress rupture of heat-resisting alloys can be treated as a rate process, certain equations must be satisfied. Later sections will then show that these equations are satisfied. General Theory of Rate Processes The theory of rate processes5 eveloped by Eyring and others has been applied to chemical reactions as well as to other processes such as viscosity of liquids and diffusion. In every case in which rate- process theory can be applied, there is a small subdivision, so that the macroscopic process is the net effect of all the small processes. This smallest subdivision is called the "unit process.&apos;&apos; For example, in a chemical reaction the unit process is

Jan 1, 1947

ON Oct. 5, 1926, the day before the general ses-sions of the fall meeting of the American Insti-tute of Mining and Metallurgical Engineers at Pittsburgh, a round table conference on the combus-tibility and testing of coke was held at the Bureau of Mines Experiment Station. There were about fifty present, with A. C. Fieldner, chief chemist of the Bureau of Mines, as chairman. The following organi-zations were represented: American Institute of Min-ing and Metallurgical Engineers, American Society for Testing Materials, American Gas Association, Eastern States Blast Furnace and Coke Oven Association, Gas and Fuel Division of, American Chemical Society, and Southern Ohio Pig Iron and Coke Association. In opening the proceedings, Mr. Fieldner explained that the meeting had been called at the suggestion of several members of the Institute and members of other organizations. The subject is of interest to the pro-ducer and the user of coke whether it be in a blast furnace, cupola furnace, house-heating furnace, open grate, gas producer, or in a water-gas generator. There has been much confusion on this subject largely because there is no common definition of combustibility. Does the blast-furnace superintendent, the coke-oven operator, and the fuel engineer have the same under-standing of the term "combustibility"? If a common understanding can be reached, many differences of opinion will disappear. COMBUSTIBILITY OF COKE R. H. Sweetser of Columbus, Ohio, disagreed with the statement of P. H. Royster, T. L. Joseph, and S. P. Kinney in Reports of Investigations, Serial No. 2524, of the Bureau of Mines, in which it was stated that the coke-oven op-erator cannot change coke combustibility by modifying oven practice. Mr. Sweetser held that the coke-oven man can change the combustibility of coke. Blast-furnace men know that coke that will burn easily with low pressure and will. come down in the regular way in the furnace can be pro-duced from a given mixture of coal. His idea of the combustibility of coke is the rate of flow through the com-bustion zone of the blast furnace. If the coke does not pass through in normal manner it is highly incombustible. H. J. Rose of the Koppers Co., Pittsburgh, objected to being pinned down so closely on this phase of the com-bustibility and incombustibility of coke. Coke-oven men are frequently obliged to change oven conditions to make a coke which gives blast-furnace men what they want. The size of the coke and the screening have an important bear-ing on combustibility, and there are many cases on record where by simply changing the different sizes of the coke, everything worked smoothly, and that is a much more combustible coke.

Jan 1, 1927

By S. H. Williston

IT is not often that bore hole surveys can be checked by actual civil engineering methods. A recent Arizona survey was checked by normal surveying methods and the comparison of the results should be of value to both oil and mining men. During the summer of 1948 the Phelps-Dodge Corporation, at its Copper Queen property near Bisbee, Ariz., drilled a 1245 ft, 8 in. diam, churn drill- hole in a mineralized area and cased part of it, intending to use it to transfer mill tailings for stope fill. The hole, as frequently occurs, was not straight, and, in endeavoring to locate the bottom in- the underground workings, they found no evidence of the hole at the underground coordinates directly below the surface location. The noise of the drilling tools was reasonably clear, but the direction of sound was uncertain. Preliminary tests with available equipment were not successful in locating the bottom of the hole. Be- cause of the mineralized character of the area and the fact there was some casing in the hole, any magnetic method of well surveying would give results &apos; of doubtful value.

Jan 1, 1950

J. T. LITTLETON, JR., ? Corning, N. Y. (written discussion?).-This. discussion will add little that has not been brought out but will show how the problems encountered in the Corning Glass Works were overcome. The chief points of consideration in any equipment are, first, the work the equipment is called upon to do; second, the installation; and, third, the man who will use it. These three points should determine the type of apparatus adopted. If only rough measurements, merely a little better than the eye, are desired, the cost of the instruments should be considered; but if accurate temperature control is necessary, the cost of the equipment deserves only small consideration. There is no question that the real problem for any factory is the installation, making sure that the elements really give the temperatures desired; also, the instruments must be so designed that any man can use them.

Jan 12, 1919

By H. W. Hardinge

DISREGARDING for the present the economic side of a new device, let us turn to that feature of the conical pebble-mill which is of interest from a scientific point of view, and consider the device as a puzzle in which the theories of the cylindrical type of mill have been increased. Many articles have been written on the theory of the tube-mill, and explanations have been made which do not explain.; but these have evolved suggestions of practice which have resulted in changes in the tube as to length, diameter, feed, discharge, speed of rotation, rotation on hollow trunnions, rotation on rings, and changes in the operation as to quantity and size of pebbles, charge of load above or below the axis, crushing by causing the larger pieces of the material of the charge to act as grinders, etc. The practical worker in crushing is first interested in the endeavor to reach an economic means of accomplishing a desired end; but the improvements in crushing-practice have been largely left to the manufacturer of machinery, who, as a rule, has little, if any, knowledge of the specific requirements-such as sizing for concentration without pulverizing the metals, instead of pulverizing the rock or gangue; the metals being the more friable, while the rock is tough and not so easily disintegrated. A reversal of this practice is the aim of sliming direct for cyanidation. In the ordinary cylindrical mill, having a diameter of 4 or 5 ft. and a length of from 15 to 27 ft., it has been found that the maximum size of the particles of the charge must not exceed 1 mm. (about 25 mesh), some of which, upon entering the mill, is immediately reduced to a slime. The work upon the individual particle having been finished, it should be passed out of the mill; but, instead of this, the finely comminuted material

Jan 7, 1908

By S. R. Seagle, R. Schuhmann, N. A. Parlee

Rates of CO evolution and CO absorption were measured for liquid-iron alloys containing from 0.15 to 4.4 pet C, using a modified Sieverts apparatus. The alloys were held in alumina crucibles, so that both crucible-metal and gas-metal reactions occurred simultaneously. The data are interpreted on the hypothesis that the C-O reaction rate is controlled by oxygen diffusion across the boundary layers at the gas-metal and crucible-metal surfaces. CARBON-monoxide evolution from liquid Fe-C-0 alloys is a key reaction in steelmaking processes, both in the steelmaking furnace and in the ingot mold. Also, this reaction probably is an essential step in the desulfurization of iron under blast-furnace conditions, for which carbon is the principal reducing agent or deoxidizer present in the iron. The thermodynamic properties of the solutions of C and 0 in Fe and the equilibria of these solutions with gaseous CO and CO, have been investigated in some detail and are reasonably well understood. However, while these equilibrium data have accumulated in the laboratory, other data have accumulated to show that equilibrium conditions are often not achieved under plant operating conditions. Thus, an understanding of the rate and mechanism of the carbon-oxygen reaction not only has theoretical interest, but ultimately may assume considerable practical importance. Reaction Mechanisms and Rate Equations The over-all reaction under consideration is C (in liquid Fe) + 0 (in liquid Fe) + CO (gas) [I] Although this appears to be a straightforward heterogeneous reaction, involving just two phases (liquid metal and gas), a wide variety of reaction mechanisms has been proposed. Different authors have expressed divergent views as to the nature of the rate-controlling steps. Accordingly, a brief discussion of the possible reaction steps will be given. 1) Homogeneous Reaction Within Liquid Iron— Feild&apos; and Jette2 have applied chemical reaction-rate theory as if the C-0 reaction were a homogeneous, second-order reaction occurring within the liquid-metal phase. This mechanism necessarily produces CO "molecules" dissolved in liquid iron. In order to yield CO gas, the dissolved CO must nucleate CO gas bubbles, and the dissolved CO also must be transported to the bubble surface where it enters the gas phase. However, this mechanism is inconsistent with present concepts of the structure of liquid-metal solutions. 2) Reaction at Gas-Metal Interface—At the surface of contact between gas and metal, a second-order reaction between dissolved C and 0 may occur to produce a CO molecule which enters the gas phase. This reaction presumably involves an "activated complex" structure in the interface. Some such surface mechanism appears essential because the carbon and oxygen do not occur in the same species in the two phases and therefore must react in some way at the surface. At liquid-iron temperatures, calculations based on reaction-rate theory indicate that the surface reaction must proceed extremely rapidly and thus cannot be a rate-determining step in the C-O reaction under ordinary conditions.3 ccordingly when the over-all reaction is measurably slow, the surface reaction may be considered at equilibrium; that is Cc* Co* = m&apos;Pco [2] in which Co* and Co* are the concentrations of carbon and oxygen (weight per unit volume of metal), respectively, in the liquid-metal phase at the interface, Poo* is partial pressure of CO in the gas phase at the surface (atmospheres), and m&apos; is the mass-action constant for Reaction [I]. Since activities of C and 0 are not strictly proportional to concentrations, m&apos; is not a true thermodynamic equilibrium constant but varies with carbon content.&apos; 3) Mass Transport—If the reaction is to proceed at the gas-metal surface, as described above, dissolved carbon and oxygen in the liquid iron must come to the surface and gaseous carbon monoxide must move away from the surface. Details of the mass-transport mechanisms depend on the kind of system under consideration. For a stirred metal bath in contact with a CO gas phase, the transport of C and 0 to the surface can be described by 1 Do Mols CO evolved per sec = — 1/16— Do/do Agm (CO-Co*) = 1/12 Do/do Agm *(Co-Co*) [3] In this equation, Do and D, are the diffusion constants for oxygen and carbon in liquid iron, 6, and 6,. are the boundary-layer thicknesses, A,,,, is the

Jan 1, 1959