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By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By E. J. Quinn, M. F. Fogler

In a recent paper, Rawdon and Mutchlerl gave some exceptionally interesting results on the Brinell and scratch hardness of severely cold-worked metals. In their work, they found that, on continued cold rolling, the metal hardened up to a particular point and then reversed and became softer; this was true for both Brinell and scratch hardness values. The generally reported behavior2 of metals, with respect to Brinell tests on cold-worked material, is that the metals harden up to a certain point and then, on further cold rolling, no change in Brinell hardness occurs. Jeffries and Archer3 state that there is little difference between the scratch hardness of annealed and cold-worked metals; the work of Faust and Tammann4 also indicated no difference between the hardness of annealed and cold-worked copper. Rawdon and Mutchler found, when they plotted the reduction ratio (initial thickness divided by thickness after rolling) against the hardness value for the cold-rolled material, that the hardness number increased up to a reduction ratio of about 3 and then decreased and became even smaller than that for the annealed metal. This behavior was reported for both scratch and Brinell hardness; Figs. 1 and 2 show their results for Brinell hardness on the metals for which they published data. This is an exceptionally interesting phenomenon, if it occurs under all conditions of rolling, and would have an important bearing on the practice of cold

Jan 1, 1925

By Joseph W. Leonard

The purpose of this paper is to review and discuss some of the less evident and sometimes neglected opportunities for progressive developments in coal research. While a great deal of both promotional and technical information flows from some areas of coal research, output deficiencies in other areas of activity have reached a magnitude where important developments have been, and will increasingly be, unfavorably affected. These areas mainly involve coal mining and preparation. Some recommendations for the intensification of effort in these areas follow: Coal Mining While a huge tonnage of in-the-ground coal is assured, the location and distribution of these tonnages are becoming less favorable. The easy-to-mine coal which is located in or near population centers has been, or is being, mined. The vigor with which the less accessible reserves are recovered by the mining industry depends largely on the condition of the coal market at the time of mining. Hence, during a buyer's market, the commercially oriented mining industry is compelled to mine the easier and less costly reserves. Conversely, during a seller's market, the need to rapidly expand production results in more difficult mining and higher cost coal as few obstacles are encountered in finding markets. Hence, a seller's market tends to enhance the recovery of reserves while a buyer's market does not. One reason for today's fuel supply problems is that the Nation has recently emerged from a long-term coal buyer's market which lasted from about 1950 to 1968. During that period, national policy caused severe production cutbacks which regretably drove the industry to mining only the more accessible and better quality reserves. Often in order to remain in business, many hundreds of millions of tons of more difficult to mine reserves were abandoned and lost behind caved areas. Many of these reserves are close to population areas and would not have been lost in a more stable economic climate. It is difficult to fully account for all the impacts that were caused by the great buyer's market of the 1950s and 1960s. Besides the obvious loss of reserves that were once considered national wealth, the mining of better reserves tended to produce a generation of technically optimistic mining people. Mining people frequently became accustomed to looking at nothing less than outstanding mining conditions as a result of the declining market. Many are now and have long since received a re-education in the other half of mining. Going from many years of mining accessible, select and easy-to-win reserves, to the crash-driving of development entries in reserves that were considered unworthy of mining during 50s and 60s, frequently results in a much higher rate of encounter with in-seam and out-of-seam rock as well as with coal-deficient areas or "washouts." Intensive entry driving activity and compulsory non-selective mining in sometimes lean reserves were brought on by the need to rapidly open up new supplies of coal. Working under these requirements presents a continuing reminder that much more needs to be known about the relatively esoteric art of planning the best direction for driving entries in order to insure that a more consistent and greater supply of coal is available during early mine development. All of the preceding discussion tends to point to a need for a better estimate of those reserves of coal that are likely to be mined in the future. Such estimates should not be limited to the compilation of the amount of coal in the ground; but, where possible, should also include information concerning the capability for producing this coal. After all, a coal seam of ample thickness may have a degree of thickness variability, undulation, bad roof or floor, so as to make what would otherwise appear to be an attractive mining condition untenable. Underlying the problem involving the feasibility of producing known reserves is the need to develop better methods for the characterization of coal seams and associated lithotypes, based on drill core data, once at area is selected for mining. Reserves and their characterization involve aspects of exploration technology that are frequently considered mature. The resulting technological deficiencies may be the main reason why coal exploration frequently does not end with core drilling of a property, as it should, but extends into the mining operation during the driving of development entries. When exploration is extended to the driving of development entries, the near absence of integrated decision-making theory involving mining, geology, mathematics, and economics becomes, once again, all too painfully apparent and frequently results in very costly rationalizations. Hence, by the formal initiation of a concentrated program to combine the cyclical effects of economics with geology and mining, more relevant estimates of reserve distribution, tonnages, and production capability should be forthcoming. Moreover, a similar formal effort is needed to develop a combination of the most advanced concepts of mathematics, geology, and mining to better "see" coal seams as a means to favorably implement many long-range decisions involving mine safety and productivity. Much more applied research needs to be done on coal mining systems for mining in thin seams and/or under bad roof. Current difficulties in both of these areas at recently opened coal mines should provide a sobering glimpse into the future. Full-scale applied research, sponsored by appropriate federal agencies, is urgently needed on a scheme involving a new combination of established mining and preparation elements. The scheme may include: (1) a continuous mining machine remotely operated by a miner stationed at some distance behind the machine using a cord attached control box; (2) hydraulic transport of coal through pipes from the mining machine to a coarse refuse removal grid, crusher, and then on to portable concentrating equipment; (3) the hydraulic transport of clean coal out of the mine in pipes to the surface for thermal dewatering, if neces-

Jan 1, 1974

By W. Irwin Moyer

Two methods for the rapid valuation of oil properties are in common use. The one best known and most widely used is the "per barrel" value, based on the present daily production of the well, without regard to its past performance or the history of the sand or pool from which it produces. The second method is the "time to pay out," or the lengt of time required for a well to place itself upon the credit side of the ledger, from which time the returns from its production (less the operating expenses) will be clear profit. The time basis for valuation is also commonly used in the appraisal of an undeveloped lease. In most oil fields, it is not thought good business to invest in production that will not pay out in at least 4 to 5 years. Nearly all buyers (except in certain regions of very persistent production like the deep-sand territory of the Appalachian field) expect wells to pay out in considerably less time than this. Like the barrel-per-day price, the time necessary for a well to pay out has been determined for each field, so that one frequently hears a field or district referred to as having a certain time to pay out. This is considered the norm for that field or district and the buyer and seller base their value, to greater or less extent, on their belief in the accuracy of this time. The writer long ago became convinced of the inaccuracy of the barrel-per-day method, except when greatly modified for local conditions, such as the age of the wells, their economic limit, operating conditions in the field, the future price of oil, and the persistence of the sand as a producer. When so modified, this method becomes more of an analytic or predicted probable-yield valuation. While the appraiser may not go through each step in a valuation based on future returnable revenue, his knowledge of the field and the local conditions surrounding his leases make it possible for him to estimate a fair sales value that, in many cases, will be a close approximation to the truth. This is quite different from she commonly understood barrel-per-day value, in that the conditions turrounding the sale of one lease or property at a fair market value may

Jan 1, 1923

By W. Irwin Moyer

Two methods for the rapid valuation of oil properties are in common use. The one best known and most widely used is the "per barrel" value, based on the present daily production of the well, without regard to its past performance or the history of the sand or pool from which it produces. The second method is the "time to pay out," or the lengt of time required for a well to place itself upon the credit side of the ledger, from which time the returns from its production (less the operating expenses) will be clear profit. The time basis for valuation is also commonly used in the appraisal of an undeveloped lease. In most oil fields, it is not thought good business to invest in production that will not pay out in at least 4 to 5 years. Nearly all buyers (except in certain regions of very persistent production like the deep-sand territory of the Appalachian field) expect wells to pay out in considerably less time than this. Like the barrel-per-day price, the time necessary for a well to pay out has been determined for each field, so that one frequently hears a field or district referred to as having a certain time to pay out. This is considered the norm for that field or district and the buyer and seller base their value, to greater or less extent, on their belief in the accuracy of this time. The writer long ago became convinced of the inaccuracy of the barrel-per-day method, except when greatly modified for local conditions, such as the age of the wells, their economic limit, operating conditions in the field, the future price of oil, and the persistence of the sand as a producer. When so modified, this method becomes more of an analytic or predicted probable-yield valuation. While the appraiser may not go through each step in a valuation based on future returnable revenue, his knowledge of the field and the local conditions surrounding his leases make it possible for him to estimate a fair sales value that, in many cases, will be a close approximation to the truth. This is quite different from she commonly understood barrel-per-day value, in that the conditions turrounding the sale of one lease or property at a fair market value may

Jan 1, 1923

By B. M. Larsen, W. E. Shenk, T. E. Brower

Shortly after our previous paper on this subject was printed1 we located a source of uncertainty in the results arising from the unexpected fact that hydrogen slowly reduces silica at 1100" C. in presence of iron, even when the iron nowhere touches the silica, although in absence of iron it does not do so. This difficulty has been completely obviated by the use of a small high-frequency furnace, which enables us to heat the specimen for analysis without raising the temperature of the silica vessel to a point at which any appreciable reduction of the silica glass occurs. We now describe this modification of procedure, and present some typical results obtained with it. For any given specimen of steel, the results are entirely definite and reproducible, but their precise significance is still open to some question, as indeed is true of all methods of oxygen determination SO far developed. Further elucidation of this question is to be expected from the cooperative comparison of the several methods now under way under the auspices of the Bureau of Standards at the instance of the Iron and Steel Division of the A.I.M.E. Apparatus The final form of apparatus we have used is identical with that described and illustrated in our previous paper, except for the substitution for the Globar furnace of a small high-frequency furnace actuated by a vacuum tube oscillator2 0f about 1.5 kw. capacity, and for a slight modification of the containing vessel. This transparent silica vessel is illustrated in Fig. 1 of this paper. Its enlarged portion is about 5 cm. in diameter and 13 cm. long. The silica tube for inlet of hydrogen is fused into this bulb and ends beneath the metal "bucket" holding the steel sample. This sample is in the form of fine millings. The "bucket" is suspended by a platinum wire from the cap of Pyrex glass. The high-frequency

Jan 1, 1934

By Nicholas J. Grant, Michio Yamazaki

Cast copper alloys containing 10, 20, and 30 pct Ni and 0.75 to 0.80 pct Al were machine-milled into chips, then comminuted in a rod mill to fine flake powder utilizing a number of processing variables. The powders here internally oxidized, mostly at 800°C, in a low-pressure oxygen atmosphere. The consolidated powders were hot-extruded into bar stock. Room-tenmperature tension tests, stress-rupture tests mostly at 650°C, but also at 450° and 850°C, and hardness measurements after various annealing temperature treatments to study alloy stability were perfomted. Excellent room-temperature strength, high rupture strength at 650°C, and resistance to recrystallization at 1050°C were obtained. Problems in optimizing conditions for internal oxidation of Cu-Ni base alloys are discussed. THE interesting high-temperature properties of SAP' have stimulated considerable effort in the study of more refractory alloy systems where the potential for high-strength alloys at high temperature is great.2-13 A number of methods have been utilized to produce the desired fine, hard particle dispersions, of which internal oxidation2,9,7 of dilute solid-solution systems offers considerable promise by virtue of the potential for producing ultrafine, well-dispersed oxides. While most of the published works are concerned with pure metal matrices, a number of investigators have studied the effects of solid-solution strengthening.10,19 Use of more complex alloy matrices (for example, aging systems) has been unsuccessful because overaging still occurs at high temperatures in the oxide-containing alloys.14.15 Solid-solution strengthening is, however, effective at very high temperatures9,10 and might be expected to contribute importantly to the strength of oxide-dispersion strengthened alloys. For this study, internal oxidation of solid-solution alloys of copper and nickel, containing small amounts of aluminum, was chosen as the method of alloy preparation. PREPARATION OF ALLOYS Three copper alloys containing about 10, 20, and 30 pct Ni and each containing 0.75 to 0.80 pct A1 (enough to yield about 3.5 vol pct alumina) were prepared as air-cast ingots measuring 2.5 in. diameter by 6 in. high (see Table I for the analyses). Processing steps for all the alloys were as follows (also see Table 11): 1) Homogenization of the ingot at 982°C (1800°F) for 45 hr in an argon atmosphere. 2) Machine milling of ingots into fine chips. Average thickness was about 0.1 to 0.2 mm. 3) Hydrogen reduction of chips at 593°C (1100° F) for 1 hr to reduce copper and nickel oxides. 4) Rod milling of chips to finer powders. 5) Hydrogen treatment of powders as in step 3. 6) Internal oxidation of the powders. 7) Hydrogen treatment of oxidized powders as in step 3. 8) Hydrostatic compression of evacuated powders. 9) Sintering of compacts in hydrogen. 10) Hot extrusion. Variations in processing among the alloys were made in steps 4, 5, and 10 (see Table 11). In the past, two methods were utilized to internally oxidize alloy powders. Preston and Grant3 surface-oxidized dilute Cu-Al powders to obtain the necessary amount of oxygen to oxidize the solute metal (aluminum and silicon), and then permitted the formed copper oxide to diffuse and react with the solute in an argon atmosphere. Bonis and Grant4 exposed Ni-A1 and other nickel alloys to an oxygen pressure derived from the decomposition of nickel oxide at a preselected temperature, in an argon atmosphere. Both methods are applicable and can be modified to generate a range of oxygen pressures for oxidation of the solute but not the solvent metals. Procedure I: Surface Oxidation of Alloy A3, Cu-10Ni-0.76A1. Powders of -20 to +28 mesh were surface-oxidized at 500°C (932°F) to obtain the desired amount of oxygen for oxidation of the aluminum to alumina; the powder was then sealed in Vycor and heated at 900°C (1652°F) for various times up to

Jan 1, 1965

By E. A. Holbrook

IN my thirty years of educational work in the mineral industries and other engineering fields, this past year has been the most unusual and difficult one. Contact with educators from other schools leads to the conclusion that the same situation is countrywide. The first of our difficulties came from the shortsighted policy of the Selective Service in taking out of the colleges, continuously, all engineering students as soon as they had reached their eighteenth birthday. England, Canada, and Russia, too, even in the midst of their critical war situations, had the good sense to keep their young engineering brains in college, for they realized the vital necessity of a steady flow of engineering graduates into the war industries and into the postwar peace industries. As a result of the policy of our Government, our engineering schools were left with only a handful of students who had been rejected for military service. Our colleges, faced with the prospect of several years without students and without income, hastened to give leave of absence to many of their competent teachers who quickly were taken into industry and in many instances are now being retained there at higher salaries than colleges are accustomed or able to pay their teaching personnel. We are finding it most difficult to induce these men to return to their former engineering teaching work. In my judgment, it will take us three or four years to restore our engineering departments to their former level in quality of instruction.

Jan 1, 1946

By W. J. Houk, F. C. Hull

To clarify interpretations of grain structures and to assist in calculations of spatial grain size distributions, plane distribution curves have been determined for random sections through four regular polyhedrons approximating the shapes of metal grains. The characteristics of the distribution curve for the average metal grain are predicted. IT was realized early in the history of metallurgy that metals are polycrystalline aggregates and that the size and shape of crystals affects the properties of the material. Reaumur1 in 1722 employed the microscope to examine the fractured surfaces of steel and of white and gray cast iron and suggested a polyhedral arrangement of the crystals. The first extensive investigation of the form of crystal grains was carried out by Desch.2 He examined the disintegrated grains from a ß brass sample and noted that the number of faces per grain ranged from eleven to twenty and that the number of edges per face varied from three to eight and the maximum occurred at five. While it has been found practical to examine isolated grains only in exceptional cases, it is always possible to make a plane section through the metal and examine the shape of the grain sections on the plane of polish. Desch2 tried to determine the relation between the form of a polyhedron and that of its plane sections for comparison with distribution curves of numbers of sides per grain section of actual metal samples. The polyhedrons investigated were the rhombic and pentagonal dodecahedrons and the orthic tetrakaidecahedron. However, the frequency distributions of the number of sides of plane intersections were not sufficiently characteristic to decide which polyhedron most closely approximated the average grain in a metal. Determination of Statistical Shape of Grain in Space Scheil3 was interested in the problem of calculating the distribution of grain sizes in space from the easily measured distribution of grain section sizes on the plane of polish. Assuming that the grains were spheres and using the plane distribution curve for a sphere shown in Fig. 1, he employed a successive subtraction method to calculate the spatial distribution. In order to evaluate the accuracy of these calculations, Scheil and Wurst4 determined the actual distribution of grain sizes in space in their sample of ingot iron by polishing off successive layers and following every individual grain in a series of micrographs. From curves of mean radius of intersection of a given grain vs thickness of metal removed in polishing, Scheil and Wurst attempted to derive the statistical shape of a grain in space. Their calculated plane distribution curve for this shape is compared with the distribution curve for a sphere in Fig. 1. A table of values based on this curve was prepared for calculating spatial distributions of grains. The calculated and measured spatial distributions of their sample then agreed much better than when a spherical shape had been assumed. In the present paper, an attempt has been made to learn something about the average metal grain by studying in detail the effect of the shape of regular polyhedrons on the plane distribution of areas and shapes of areas produced by random sections through them. From the data presented below, it can be concluded that the plane distribution curve for the average metal grain differs in three fundamental respects from the curve derived by Scheil and Wurst. Polyhedrons Selected for Study The polyhedrons selected for the statistical study are illustrated in Fig. 2 and consisted of a cube, a figure formed by cutting off the corners of a cube at the midpoints of the original edges, a tetrakaidecahedron, and a pentagonal dodecahedron. The length of edge on any one figure is a constant. For the above models the edge lengths were 3.50, 4.00, 2.00, and 2.08 in., respectively. A cube was selected for one of the polyhedrons because of its simple geometry, because it is a form that by repetition can completely fill space, and because it represents a convenient degree of departure from compactness beyond which the shape of

Jan 1, 1954

By G. T. Higgins

PREVIOUS workers1,2 have found evidence of exaggerated grain growth or secondary recrystallization on annealing sponge zirconium at temperatures high in the a, phase field, but no details of the orientation relationship between the secondary grains and "as-recrystallized" matrix were reported. In other hexagonal metals, namely dilute Mg-A13 and Cd-zn4 alloys, secondary recrystallization has been observed in which the secondary grains are related to the primary recrystallized structure by rotations about the c axis. These rotations are thus comparable with the rotations about the (111) axis observed in the secondary recrystallization of fcc metals. In the current work secondary recrystallization has been observed on annealing iodide zirconium at 800°C and the associated changes in crystallographic texture have been examined. The material employed was arc-melted iodide zirconium of the following composition: Impurity O H Fe Hf Pb I Ni C1 A1 ppm by wt 130 5 230 98 23 28 200 39 30 This was received as 0.25-in. plate, and, prior to the annealing studies, was cold-rolled to 0.040 in. Specimens 1 in. sq were chemically polished and annealed for various times at 800°C in a vacuum better than 5x 10-6 Torr. For metallographic examination specimens were first chemically polished and then anodized8 to enhance contrast between the grains when examined under polarized light. Changes in crystallographic orientation associated with the development of secondary grains were followed by (1011) and (0002) pole-figure determinations using a conventional Schulz goniometer in reflection. Filtered Cr Ka radiation was employed and great care was taken to avoid spurious re- sults due to the close proximity of the Bragg angles for the (1011) and (0002) reflections. Figs. 1 and 2 illustrate the change in grain structure on annealing at 800°C. After 24 hr the structure has ceased to be equiaxed due to the development of certain grains in preference to others. It is notable that the secondary grains do not grow to the extent observed in sponge zirconium.1,2 This appears to be due in part to the fact that normal grain growth is inhibited in the less pure sponge zirconium, with the result that the driving force for secondary recrystallization remains high, while at the same time the number of grains able to develop in the presence of the impurities is also smaller. As a consequence, in sponge zirconium those grains that do develop preferentially are able to grow into the fine -grained matrix without impingement, while in iodide zirconium the preferential growth of many grains leads to early impingement. The pole figures determined for specimens annealed for 5 min and 24 hr at 800°C are illustrated respectively in Figs. 3 and 4. These indicate that the dominant feature of the initial recrystallized texture consists of basal planes at an angle of 321/2 deg to the sheet surface, with a (1120) axis lying parallel to the

Jan 1, 1967

By T. A. Pollard, C. R. Sandberg, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By C. R. Sandberg, T. A. Pollard, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By Henry M. Howe, W. P. Barba

When this country went into the war, but two concerns, The Bethlehem Steel Co. and The Midvale Steel and Ordnance Co., knew how to make steel fit for great cannons and at these concerns there were relatively few men who knew the whole art. Fortunately, certain of these men put their knowledge at the service of the Government, and proceeded to instruct the metallurgists at the arsenals and at various steel works. Doctor Howe, then chairman of the Engineering Division of the National Research Council, suggested that this work might be facilitated, and the number of effective gun-steel makers thereby increased, if a detailed description of the best practice could be written, giving the reasons for the various steps, and issued with the endorsement of a committee composed of those who were evidently the most competent authorities. It was thought that something would be gained by clarification of the subject, and something by the eminent authority of the members of the committee. To that end, the Engineering Division appointed a committee, consisting of the gentlemen whose names follow, to mention on1y those who retained their connection with it. At this time there were serious difficulties in the manufacture, for the Government. of aircraft and high-speed engine crankshafts, of certain ordnance forgings, and of shells for both the Army and Navy. This Committee was asked to study and report upon these, with a view to betterment of practice. There were indications that the source of some of the difficulties went back to the melting of the steel and the production of the ingot. Hence, the committee first studied steel melting and ingot production, in order to guide the wartime manufacturers to an even larger percentage of useful production from the steel initially melted. Committee on Steel Ingots W. P. Barba, chairman, Ordnance Dept., U. S. A. (formerly Vice Pres. & Gen. Mgr., Midvale Steel Co., Philadelphia). George K. Burgess, Chief of Division of Metallurgy, U. S. Bureau of Standards, Washington, D. C. Henry M. Howe, Then Chairman Engineering Division, National Research Council.

Jan 1, 1922

By W. P. Barba, Henry M. Howe

When this country went into the war, but two concerns, The Bethlehem Steel Co. and The Midvale Steel and Ordnance Co., knew how to make steel fit for great cannons and at these concerns there were relatively few men who knew the whole art. Fortunately, certain of these men put their knowledge at the service of the Government, and proceeded to instruct the metallurgists at the arsenals and at various steel works. Doctor Howe, then chairman of the Engineering Division of the National Research Council, suggested that this work might be facilitated, and the number of effective gun-steel makers thereby increased, if a detailed description of the best practice could be written, giving the reasons for the various steps, and issued with the endorsement of a committee composed of those who were evidently the most competent authorities. It was thought that something would be gained by clarification of the subject, and something by the eminent authority of the members of the committee. To that end, the Engineering Division appointed a committee, consisting of the gentlemen whose names follow, to mention on1y those who retained their connection with it. At this time there were serious difficulties in the manufacture, for the Government. of aircraft and high-speed engine crankshafts, of certain ordnance forgings, and of shells for both the Army and Navy. This Committee was asked to study and report upon these, with a view to betterment of practice. There were indications that the source of some of the difficulties went back to the melting of the steel and the production of the ingot. Hence, the committee first studied steel melting and ingot production, in order to guide the wartime manufacturers to an even larger percentage of useful production from the steel initially melted. Committee on Steel Ingots W. P. Barba, chairman, Ordnance Dept., U. S. A. (formerly Vice Pres. & Gen. Mgr., Midvale Steel Co., Philadelphia). George K. Burgess, Chief of Division of Metallurgy, U. S. Bureau of Standards, Washington, D. C. Henry M. Howe, Then Chairman Engineering Division, National Research Council.

Jan 1, 1922

By George F. Comstock

It seems a common opinion among metallographists that all light-gray inclusions seen with the microscope in polished sections of steel are manganese sulphide. Examples of this belief are continually appearing, as for instance in the paper by Dr. Henry Fay on manganese sulphide as a source of danger in steel railsll and in Lieutenant-Commander Cook's paper on Metallography of Steel for U. S. Naval Ordnance.² Slate- colored inclusions are considered to be silicates, and dove-gray inclusions, manganese sulphide. To show the danger in the latter unqualified assumption, it should be sufficient to examine the edge of any piece of steel that is covered with a fairly thick scale, and that has been polished in such a way as to prevent the scale from breaking away entirely below the polished surface. This can be done by protecting the scaled edge of

Jan 1, 1917

By R. T. Hukki

THE accepted basis of comparisons between mills of different diameter is the percentage critical speed. If n = actual mill speed, rpm, nc = calculated critical speed, rpm, np = calculated percentage critical speed, and D == inside diameter of the mill in feet, then n, In the following analysis capacity, T, is expressed in short tons per hour, tph, and power consumption, P, in kilowatts, kw. Accordingly power consumption per unit of capacity, P will be expressed in kilowatt hours per short ton, or kw-hr per ton. In all equations D refers to the inside diameter of the mill in feet and v to the peripheral speed of the mill in feet per minute inside the liners. ' Comparison between separate mills must be based on equivalent grinding conditions, i.e., same feed, same size distribution of feed, same size distribution of product, and same percentage of solids. In addition, comparisons between separate rod mills must be based on the same rods, same type of liners, and same percentage rod load. Comparisons between separate ball mills presuppose the same balls, similar liners, and same relative ball load. The practical np-range through which the equations apply varies, being narrower for fine grinding in ball mills and wider for coarse crushing in rod mills. The Relationship between Capacity and Speed It is the general belief that the capacity, T, of a tumbling mill is directly proportional to the speed of the mill, other things remaining constant.' Mathematically this is represented by the equation T - c¹ n tph [4] where c, is a factor related with the grinding characteristics of the ore, method of reduction, and the units chosen. It is proposed here that the general equation relating mill capacity and speed should be of the form T = c¹ nm tph [5] In other words, the capacity should be proportional to the mill speed raised to power m, the numerical value of the exponent being 1 5 m 5 1.5, depending on the circumstances. Eq. 5 can also be written in the following forms: T = c, (np)m tph, and [6] T=Ca vm tph, [71 where v = peripheral speed of the mill in feet per minute. If the observed capacity of a mill at speed n¹ is = T¹ tph, the capacity T² of the same mill at speed n² should be T² = T¹ (n²/n¹)tph [8] The Relationship between Power Consumption, Mill Diameter, and Speed The only well known theoretical deduction relating power consumption, P, and mill diameter appears to be the formula of duPont introduced by Gow, Guggenheim, Campbell, and Coghill.' According to duPont, the power required to operate a mill is a function of the mass of the balls, of the lever arm of the ball mass, and of the speed of the mill. The ball mass per unit of mill length is proportional to the square of the diameter, the lever arm is directly proportional to the diameter, and the critical mill speed or any percentage thereof is inversely proportional to the square root of the mill diameter. Following this reasoning, the original duPont formula is of the form P = c4D² c D • c6D-0.5 = c7D2.5 [9] If the mill speed in the above equation is expressed in terms of Eq. 3, the duPont formula may be written as follows: P=f1(D2) f2(D) f³(—np) or [10] vD P = c np D2.5 kw [11] Eq. 11 may also be derived from the mechanical principle of force, which is equal to mass x acceleration. Power necessary to operate a mill may be considered to be an homogeneous linear function of the force developed. Ball or rod mass per unit of mill length is a function of D2. The acceleration factor of the ball or rod mass is a function of the peripheral speed of the mill. Thus P = f4(F) = /x(D2) f5(v) Indicating that v = nDn, and n = c9 np /vD, the above equation becomes P = f2 (D2) -fa (D ca np/vD

Jan 1, 1955

By Arnulf Muan, W. C. Hahn

Activities of "FeO" in "FeO"-MgO solid solutions have been determined in the temperature interval 1100" to 1300"C by equilibrating oxide samples with pure metallic iron in atmospheres of known oxygen partial pressures. The end members "FeO" and MgO form a complete solid solution series. The system shoztls a considerable positive deviation from Raoult's law. A large amount of data has been accumulated during the past 50 years on stability relations existing among various crystalline and liquid phases in oxide systems of importance in metallurgical processes. By comparison, very little is known about the thermodynamic properties within the various homogeneous phases present in the systems, particularly the crystalline phases. The present paper deals with determination of activities as a function of composition in solid solutions of wüstite ("FeO") and periclase (MgO). Such solid solutions ("Magnesiowustites") have simple sodium chloride structure and are known to be continuous between the end members at elevated temperatures (> 1000°C) and strongly reducing conditions such as prevail in contact with metallic iron. Wiistite has a defect structure in which the ratio of oxygen to iron varies and never has as low a value as 1:1 corresponding to the simplified formula FeO. Within the range of stability of this phase, the composition changes between a maximum oxygen content of approximately 25.6 wt pct (corresponding to the formula FeO.83O) and a minimum oxygen content of approximately 23.2 wt pct (corresponding to the formula Fe0-96O). The activity data to be reported in the present paper are based on using as standard state the wüstite which is in equilibrium with metallic iron at a particular temperature, i.e., "FeO" of minimum oxygen content at each temperature. For sake of simplicity, the formula FeO will be used to represent the wustite phase in the remainder of this paper. Consider the reaction 2 FeO solid solution = 2 Femeta1 + Ozgas in which FeO dissolved in another oxide dissociates to metal and gas. The activity of FeO in the solid solution, relative to "pure FeO" in equilibrium with metallic iron as a standard state, is then expressed as Here Po, and po2 * are the partial pressures of oxygen of the gas phase in equilibrium with metallic iron and the oxide solid solution or "pure FeO", respectively. The equation holds only if the metal phase is essentially pure Fe. The oxide combinations used in the present investigation fulfill this requirement. Magnesia is so much more stable than FeO that for all practical purposes aFe = 1 in the metal phase present in all mixtures used in this investigation. I. EXPERIMENTAL METHOD 1. General Procedure. The experimental method used was analogous to that developed by Foster and Welch1 and used recently by Hahn and Muan.2 It consisted of four steps: a) Determination of the equilibrium between FeO and Fe. b) Determination of d-spacing change with composition in oxide solid solutions (FeO-WO). c) Equilibration of various members of the solid solution series with a metal phase and a gas phase of known oxygen partial pressure. d) Determination of compositions of solid solutions resulting from step (c) by means of data obtained in step (b). 2. Starting Materials. General Aniline and Film Corp. carbonyl iron powder, type HP, was used as the source of metallic iron. A representative analysis was as follows: Fe, 99.6 pct; C, 0.01 to 0.04 pct; 0, 0.1 to 0.3 pct; N, 0.00 to 0.05 pct. Other elements were present as traces only. Wiistite was prepared from "Baker Analyzed" Reagent grade Fe2O3 of reported analysis as follows: Assay (Fe2O3), 98.8 pct; insoluble in HC1, 0.02 pct; not precipitated by NH,OH, 0.02 pct; Zn, 0.003 pct. Production of wüstite was achieved by a two-step

Jan 1, 1962

By R. R. Webster, H. T. Clark

I. A. Sirel—I would like to ask Mr. Sims what would the preferred hot metal analysis be as far as manganese and silicon are concerned if you used specially made iron for this process instead of basic iron. C. E. Sims (authors' reply)—A preferred composition would contain somewhat less silicon than the basic pig iron used in these experiments. High silicon requires a large lime addition. Lime must be added in sufficient quantity to neutralize the silica formed and to leave an excess for dephosphorization. Manganese presents almost no problem in operation. It is almost completely oxidized and, in burning, develops considerable heat. The evidence indicates, however, that, in continuous commercial operation, there will be an excess of heat produced, and the bath will need to be cooled in some manner as by the addition of scrap or by utilizing the energy for the direct reduction of ore. There do not seem to be any serious limitations on composition of pig iron. One heat was made with an iron containing 2.27 pct silicon and the phosphorus finished at 0.007 pct. In another, the iron contained 0.45 pct phosphorus which was lowered to 0.019 pct. This indicates considerable leeway in composition. D. R. Loughrey—We are all very much interested in the recent discovery of very large deposits of iron ore both in Labrador and in Venezuela. I would like to ask Mr. Sims if the iron ore at either or both of these places is such that it would lend itself to the manufacture of iron suitable for use in the turbohearth. C. E. Sims-—According to my information, those ores are not essentially different from ores now used in this country for making basic pig. They should, therefore, be adaptable to this process. D. I. Brown—You have spoken about the leeway, or spread in analysis of the various irons you can use in the vessel. I would like to have you tell us, if you can, about the different kinds of steels which can be made in such a vessel. The turbohearth process, or it might more aptly be called pneumatic openhearth, is a little different from that used in most Bessemer shops and in the one in which I worked. If we had a blow in the air over 10 min, the boss was in the pulpit in a hurry

Jan 1, 1951

By R. V. Smith, M. H. Cullender

Rigorous equations for calculating subsurface pres.tures in flowing and static gas wells, and pressures along horizontal pipelines are presented in this paper. These general equations, based on the mechanical encrgy balance, contain no assumptions regarding temperature and can be used with either straight-line or curved temperature gradients. The friction factors recommended in this report are based on an absolute roughness of 0.0006 in. Flow is always considered to he turbulent. Although these general flow equations are solved by numerical means, the methods are as convenient as many of those used today to calculate pressures in gas wells and pipelines. These numerical methods are illustrated for flowing and static columns of gas in wells and for flow in pipelines. The authors believe that the use of these methods will result in more accurately calculated pressures in gas wells and pipelines and that [he methods are more flexible than any in use at the present time. Also, the methods are easily adaptable to automatic computers. INTRODUCTION The problem of calculating subsurface pressures in gas wells and along flowing pipelines has been studied by many investigators with the results that two widely-used methods have been presented in technical literature. One approximates conditions in a gas well or pipeline by assuming that temperature and compressi- bility are constants tor the entire gas column. The other method assumes that temperature is constant at some average value but permits compressibility to vary with pressure at the constant temperature. While these approximations may be justified for relatively shallow and low-pressure wells, they become more and more unrealistic as the calculations are applied to the deeper high-pressure wells. In wells or pipelines where there is an appreciable change in temperature between the inlet and outlet ends of the flow string, it is equally as important to consider the change in compressibility with temperature as it is to consider the change with pressure. Consequently, the methods presented in this paper were developed to provide a workable procedure for calculating pressures in gas wells and pipelines which makes no assumptions regarding either temperature or compressibility. The friction factors recommended for use with the equations were the result of study of published literature and extensive experimental work with gas wells. The F,. values in Appendix IV which contain the friction factor are equivalent to an absolute roughness of 0.0006 in. as calculated by the Nikuradse equation. The absolute roughness of 0.0006 in. was previously published by Cullender and Binckley2 for gas wells; it is in agreement with 0.00065 in. of Smith, Dewees, and Williams1 for gas wells and 0.00065 in. of Baker and Swerdloff4 for pipelines; it is in reasonable agreement with 0.0007 in. reported by the Bureau of Mines and the American Gas Assn.5 for large transmission lines. However, any type of friction factors may be used in the equations by a change in the F, values in Appendix [V].

Jan 1, 1957

By R. M. Leibrock, C. W. Ziemer, R. P. Vincent

The Stanolind flowmeter, which employs a hot-wire anemometer connected in a Wheat-stone bridge circuit, has proved useful for determining the relative productive ability of individual sand members of gas wells. The operation of this instrument in measuring gas velocities in the well bore above each producing member has provided both a direct and accurate means of analyzing reservoir performance. Results of tests conducted with the well flowmeter in the Hugoton gas field of western Kansas have indicated some rather unusual production characteristics. In two cases it was found that all or the greater part of the total gas produced was coming from one section in wells where four "pay" sections had been perforated individually. These actual measurements contradict in many instances the indications of data obtained from electric logs and from core analysis; the fact that these latter sources often give incorrect results, demonstrates the necessity of a method, such as is provided by the well flowmeter, for accurately determining the amount of gas coming from each producing member. Introduction In any gas well where a number of pay sections have been perforated individually and are producing to a common outlet, the question arises as to the relative amounts of gas being passed through each set of perforations. In the past it has been the policy to depend on core analysis to estimate relative productivities, or, where the sections were not cored, to obtain some idea of production characteristics from electric-log studies. The weaknesses in these methods are readily apparent and indicate the need for more reliable means of measuring gas flow from each zone. The Stano-lind flowmeter* was developed for this purpose. Preliminary tests were made with the instrument in the Katy gas field near Houston; however, the bulk of the routine work with the well flowmeter has been confined to the Hugoton gas field in western Kansas, where results obtained have been encouraging. A description of the instrument, the field technique employed in testing, and a few of the results obtained in the Hugoton area are discussed in this paper. Description or Instrument The well flowmeter is 1¾ in. od and 7 ft long; it is entirely self-contained, can be run through tubing as small as 2 in. id in wells with high pressure (4500 psi) and temperature (210°F) and is lowered on a wire line commonly used for other instruments of the bottom-hole type at falling rates up to 500 ft per minute. It will detect gas flow as low as 10 ft per minute linear velocity, and yet withstand and record velocities of 1000 ft per minute without damage to the detecting element. Killing the well is not required nor desirable for running a production profile when using the instrument, and it is necessary to stop flow for only a short time. The detecting element of the instrument is a hot-wire anemometer connected in a

Jan 1, 1948