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By G. H. Alani, H. T. Kennedy

One of the major difficulties in predicting the performance of oil reservoirs from their early pressure history lies in the uncertainty of estimating the volume of the liquid hydrocarbons contained in them. As a first step in filling this need, an equation was developed to determine the Inolal liquid volume of pure hydrocarbons over a wide range of temperature and pressure. The second step consisted of adapting the equation to apply to mixtures, with the heary hydrocarbons expressed as c The equatious are similar in form to van der Waals equation. hut the constants a and b tire considered as furnctions of temperature. In addition to the gas constant R, there are four constants characteristic of each hydro- When comptired with experimental values jound in the literal the. the average absolute deviation in the calculated molal volumes is found to be a Maximum of 0.33 per -cem for any of the pure liquid hydrocarbons studied. This maximum deviation was that found when comparing the calculated and observed values over a temperature range of 86° to 482°F and a pressure range from the bubbl-point ro 10,000 psis. The equations expressing the correlation for. mixrurrc were developed from 647 experimental measure-rilents of volume on 47 bouom-hole samples covering ; temperature range of 72" to 250°F and a pressure znge from bubble-point ro 5,000 psig. The average absotute deviation was found to he 1.6 per cent with the maximum for any measurement of 4.9 per cent. INTRODUCTION Accuratc information of the pressure-volume-temper-iiture behavior of hydrocarbon liquids is of considerable importance in the field of both applied and theoretical science and, especially, in the solution of petroleum reservoir engineering problems. These PVT relationships can be expressed graphically, in tabular form or as equations of state. Equations of state for gases have been developed based on the ratio of pressure, temperature and volume to the pressure, temperature and volume at the critical points of the hydrocarbons. These equations have been successful in yielding values fairly accurate for reservoir engineering purposes. For liquids, however, relations of this type are more complex and have not yielded useful results. The composition of reservoir liquids is normally expressed in terms of the moles of hydrocarbons C,? C,. C,. elc, per mole of mixture. The composition must include the fraction of a mixture such as C,,, which cannot be separated with reasonable time and effort into specific hydrocarbons. Although there are several equations of state having variable degrees of accuracy applicable to pure liquid hydrocarbons, none includes a means for estimating the volume of mixtures as a function of temperature. pressure and composition expressed in this manner.

By Akinobu Kasami, Keiji Maeda, Makoto Naito, Masaharu Toyama

Gap electroluminescent diodes have been prepared by the vapor phase diffusion of zinc into n-Gap crystals which were grown from a gallium solution (10 wt pct Gap) doped with tellurium and Ga203. A marked improvement in the efficiency of the red electrolumines -cence has been achieved by heat treatment after diffusion. External quantum efficiencies of diodes annealed under optimum conditions are 0.2 to 0.6 pct at room temperature, or about 200 times higher than the efficiencies of diodes quenched after diffusion. The optimum dopant concentrations in the gallium melt from which the crystals were grown are 3to6 x at. pct Te and 4 to 8 x 10-2 mol pct Ga203. The efficient diodes are characterized by linearly graded junctions with an i-layer 0.1 to 0.2u thick. Annealing increases the emission intensity by a factor of 20 to 50 and decreases the current density to 1/3 to 1/8 that of quenched diodes at a given bias. The decrease in current is attributed to an annihilation of deep recombination centers in the depletion layer. The increase in emission intensity is interpreted in terms of an increase in lifetime of minority carriers and an increase in the relative intensity of red-to-infrared emission. The dependence of these quantities on the tellurium and oxygen doping levels is also discussed. A number of studies have been made of the red light emission from for ward-biased Gap diodes.' At room temperature this emission band is centered at 7OOO? with a spectral width of nearly 1000?. Low-tempera-ture photoluminescence indicates that this emission is due to either the radiative annihilation of an exciton bound to a pair of zinc and oxygen atoms substituting on nearest neighbor lattice sites2,3 or the radiative recombination of an electron bound to this Zn-O pair with a hole bound to an isolated zinc shallow acceptor.3 An emission band is also observed with a spectral peak at 9800?. This infrared emission has been shown to be due to the recombination of an electron trapped at an isolated oxygen deep donor with a hole trapped at an isolated zinc acceptor.4 The red emission from Gap diodes is fairly efficient at room temperature because the nearest neighbor Zn-0 pair forms a deep electron trap at 0.3 to 0.4 ev below the edge of the conduction band.2'4 In diodes grown by liquid epitaxy an external quantum efficiency of 2.1 x 10-2 (photon/electron) has been attained by heat treatment at relatively low temperatures.5 This heat treatment was found to increase the efficiency by a factor of 3 to 6. However, no detailed studies have-been reported on the effects of heat treatment. We can only cite Onton and Lorenz's work6 on the change ; in the relative intensity of red-to-infrared emission. Heat treatment has also been tried on junctions built in during growth, but contrary to expectations the efficiency decreased. In-diffusion is a simple and controllable method of fabricating p-n junctions. For Gap, zinc is generally used to form a p-type layer on n-type crystals. The emission efficiencies of in-diffused diodes are, however, extremely low in comparison with liquid epitaxial diodes.' Although efficiencies as high as 2 x 1O-3 have been reported, values from 10-6 to 10-4 are generally obtained by typical diffusion techniques. Out-diffused diodes are known to be a little more efficient than in-diffused diodes. Nevertheless, the quantum efficiency is at most 7 x 10- 3 and ordinarily of the order of 10-4.8 NO results have been reported on heat treatment of either in-diffused or out-diffused diodes. This paper reports a marked improvement in the efficiency of the red emission observed for in-dif-fused diodes as a result of heat treatment after diffusion. The method described reproducibly yields diodes with external quantum efficiencies of 2 to 6 x 10-3. The observed dependence of efficiency on annealing time and on doping level will be discussed in terms of the lifetime of minority carriers and the formation of Zn-O complex pairs. EXPERIMENTAL A) Diode Fabrication. The n-Gap crystals used in this study were grown from a saturated gallium solution by a slow cooling method.8 The Gap content in the gallium melt was fixed to 10 wt pct corresponding to a growth temperature of about 1100 Tellurium was chosen as the n-type dopant and added to the melt in concentrations ranging from 0.001 to 0.06 at. pct. Oxygen was added in the form of Ga2O3, whose concentration was varied from 0.004 to 0.2 mol pct. The resulting crystals were platelets with well-developed (111) surfaces. Typical electrical properties were Hall mobilities of 130 to 30 sq cm per v-sec and carrier concentrations of 1016 to 10" cm-3 at room temperature. Diodes prepared from crystals with relatively low doping levels, in which u = 130 to 100 sq cm per v-sec and n = 0.6 to 6 x 1017 Cm-3, were examined in detail. The p-n junctions were produced in these n-Gap crystals by the diffusion of zinc from the vapor phase by the following procedure. The platelets were carefully lapped on both sides to a thickness of 150 to 200 u while maintaining the (111) orientation. After being etched in hot aqua regia, the crystals together with the zinc were sealed in an evacuated 12 mm ID quartz ampoule 20 cm long. The crystals and the zinc were then separated from each other at opposite ends

Jan 1, 1970

Jan 1, 1905

By J. G. Thompson

Determinations of the hydrogen content of irons and steels invariably are subject to two serious difficulties: (I) the determination of amounts of 0.001 per cent or less of any constituent requires an analytical procedure of unusual precision and accuracy, and (2) the hydrogen content of many samples is dccidedly not stable; i.e., there is no assurance that the content at the time the analysis is made is the same as it was when the sample was taken or at some previous time in the history of the piece. In respect to both the precision and speed of the determination, the vacuum-extraction procedure for the determination of hydrogen possesses advantages over the vacuum-fusion procedure, which has been the recognized standard for the detcrmination of other gaseous elements in sted-— oxygen and nitrogen for example. The basic facts upon which the vacuum-extraction procedure is based—i.e., the evolution of gas from solid steel when it is heated in vacuum, and the fact that the evolved gas is rich in hydrogen—were observed by Graham1 many years ago. Subsequent investigations have shown that hydrogen exists in steel chiefly as interstitial solid solution (i.e., in atomic dispersion) and perhaps to some extent as hydridcs that are unstable and decompose to form atomic hydrogen. In either case practically all of the hydrogen in steel at elevated temperatures exists in the atomic condition and consequently is able to diffuse readily through the metal. In contrast to this, other gaseous elements, such as oxygen and nitrogen, normally are present in steel chiefly in the form of relatively stable compounds such as oxides or silicates and nitrates; i.e., the oxygen and nitrogen atoms are fixed in stable combinations and are not free to migrate. The only oxygen or nitrogen that can diffuse in steel is the small amount in solution (atomically dispersed) and the rate of diffusion of these atoms is much less than that of hydrogen because of their greater atomic volume and lower mobility. Consequently, it is possible to extract most or all of the hydrogen from solid steel in a reasonable time at moderately elevated temperatures, but the procedure is not applicable to the determination of oxygen or nitrogen. It is only within the last decade that these observations have been developed into an analytical procedure for the determination of hydrogen. Apparatus and Procedure The apparatus used at the National Bureau of Standards,6 for the determination of hydrogen by the vacuum-extraction procedure, is shown schematically in Fig. I. The specimen, freshly cleaned and dried,* is suspended on a fine wire within the quartz furnace tube that is connected to the reservoir system and analytical train.

Jan 1, 1945

By R. T. DeHoff

A new approach to the measurement of the size distribution of particulate structures imbedded in opaque bodies is developed. The method is based upon the assumption of a general two-parameter distribution curve, and the estimation of these two parameters from three well-known counting measurements made upon metallogvaphic sections. The total number of particles in the system is also a product of the analysis. Application of the method with the assumption of the logarithmiconorma1 disfribution function is developed in detail. A complete description of the geometry of a particulate structure requires the determination of the size distribution of particles. The problem of estimating the size distribution of particles of a particular phase in a multiphase system, or the grain-size distribution in a homogeneous system, has been approached by many investigators.'-'0 All of the solutions proposed by these investigators share the following characteristics. a) A minimum of several hundred particle sections in the microstructure must be examined, and some characteristic dimension recorded, such as area,3'5 intercept length,6"9 or diameter.1'2'4'10 b) The resulting data must undergo a series of fairly complex calculations to generate the empirical histogram which describes the size distribution in three dimensions. c) In order to manipulate the result, the histogram must be fitted to some assumed mathematical formula, using the attendant statistical procedures. d) With two notable exceptions,8,10 the particles must be spherical. The measurements and calculations involved are in general very tedious and time-consuming, with the logical result that much effort has been expended in the development of equipment which will perform these tasks automatically and semiautomati-cally.9,11-15 considerable success has been achieved in this area, but the equipment is in general expensive, and usually places stringent requirements On the quality of microstructure which can be reliably analyzed. In laboratories which do not possess such equip- ment, the analysis of geometry is usually limited to measuring total properties of the microstructures, such as volume fraction and interfacial area, because the measurements required are much simpler to make. The determination of size distributions rarely is undertaken. The development which is presented in this paper permits the estimation of size distributions of three-dimensional structures from the same simple counting measurements which are required to determine the surface area and volume fraction of the particulate structure, and one other counting measurement. The basic approach that is used is to assume a general mathematical form for the distribution, which is described by two parameters (as the normal distribution is described by assigning values to the mean and the standard deviation), and then estimate these two parameters from the results of the counting measurements. The introduction of a third counting measurement also permits the evaluation of the number of particles per unit volume, Nv.

Jan 1, 1965

By G. W. Healy, L. F. Sander

was investigated by reacting thin discs of calcium oxide with gas mixtures of CO2, CO, and Son. Its value was 19,300 * 300 cal independent of temperature in this range. No solid solubility of sulfur in calcium oxide was detected within the limits of the experimental method and it is estimated to be below 0.025 pct by weight. The importance of lime in desulfurization is well-established but complete information on the pure phase equilibrium: CaO + 1/2 s2 = CaS + +02 [11 is not yet available. The goal of this work was to evaluate solid solubility of CaS in CaO and to determine the free-energy change associated with Reaction [I] at temperatures of 1400" to 1650°C. The equilibrium constant for Reaction [1] can be written: It is convenient to rewrite Eq. [2] in the form: where A = {Ps /PqJ1'2 has been referred to' as the "sulfurizing power' of a gas mixture. In this work, thin discs of CaO were suspended in a vertical tube furnace and exposed to CO + CO2 + SOz gas mixtures having known values of A. The samples were then analyzed for sulfur. As expected, X-ray diffraction confirmed that CaS was the only sulfur-bearing phase formed at the relatively low oxygen pressures used. EXPERIMENTAL PROCEDURE Reagent-grade CaCO3 was pressed in a 3/8-in.-diam pill die and prefired in air to produce CaO discs weighing between 0.004 and 0.01 g. Several discs were used to provide a suitable weight for chemical analysis while maintaining a large surface area to react with gas mixtures. These were placed in a platinum mesh basket and suspended in the gas stream in the hot zone of a vertical tube furnace. Desired gas mixtures were prepared from cp grade CO and CO2 and anhydrous grade SO2. The method of soap bubble displacement was used to calibrate capillary flow meters. While this gave excellent results with CO and Con, some problems with bubble insta- bility and soap film "drag" arose with the use of SO2 at low flow rates. Hence, frequent sampling and analysis of gas mixtures was carried out to insure proper control of the ingoing SOZ. The furnace used for gas:solid equilibration was a vertical mullite tube externally wound with 60 pct Pt-40 pct Rh wire having a diameter of 0.028 in. An inner tube of $ in. ID served as the reaction chamber having Pyrex ground joints sealed to the mullite to provide gas-tight connections at top and bottom. A Pt-Pt 10 pct Rh thermocouple was inserted into a protection tube adjacent to the sample basket to measure sample temperature during a run. Constant-temperature control to 2C was observed at any desired set point within the range of this investigation. This was accomplished by a control thermocouple imbedded in the furnace windings which served to actuate an electronic controller wired for high-low operation. The sulfur analyses of the solid samples were carried out using a stoichiometric combustion technique based on the method of Fincham and Richardson. Some analyses were done using a modified evolution method3 but these were used primarily to check the results of the combustion method. The results were in good agreement but the combustion technique of-ferred an advantage in economy of time and material. CALCULATION OF GAS EQUILIBRIA Heating a given mixture of CO + CO + SO2 to high temperatures gives rise to a large number of product species. The details of calculating the partial pressures of these products of interaction and dissociation can be found in several references4,5 and need not be repeated here. The thermodynamic data selected for the major species in the gas mixtures are shown in Table I. Equilibrium constants from these reactions were combined with oxygen, carbon, and sulfur balances and a computer program written to facilitate the calculations. Some early difficulties in reproducing experimental results were finally traced to the effect of atmospheric pressure changes. No reference to consideration of this question had been found in the

Jan 1, 1969

By J. L. Taylor, P. Duwez

PARTIAL phase diagrams of titanium with iron, cobalt, and nickel have been established by previous investigators.1-3 These diagrams seem to be reliable, at least for concentrations of titanium ranging from 0 to about 50 at. pct. More recently, Long and his collaborators have presented a tentative titanium-nickel diagram covering the titanium-rich side.' These various studies indicate that in each system three intermediate phases exist and correspond to the compositions Tia, TiX, and TiX2 (or TiX3). The purpose of this paper is to review the available information on the crystal structure of these phases and to give the results of additional X-ray diffraction studies. Previous Work A summary of the work of Wallbaum and his collaborators"-' is presented in table I. The first intermediate phase on the titanium-rich side of the three systems, with iron, cobalt, and nickel, is of the Ti2X type and has a face-centered cubic structure. Although it is stated that the unit cell contains 96 atoms: no lattice parameters are given. The second phase is centered around the compositions TiX for the three systems. The crystal structure of this phase is mentioned in a short note" as being body-centered cubic (CsCl type), but no parameters are given. The analogy between the three systems, which is perfect as far as the two phases of the type Ti2X and TiX are concerned, disappears at the titanium-poor end of the diagrams. In the system titanium- iron, TiFe2 has an hexagonal (MgZn2 type) struc-ture with the parameters given in table I. The existence of TiFe3 has also been reported8 (table I) but was questioned by other investigators2 and is also refuted by the present study. In the system titanium-cobalt, a phase corre-sponding to the composition TiCo2 has been investi-gated by Wallbaum and Witte6 who claim that the structure is cubic (MgCu2 type) for alloys slightly deficient in cobalt and hexagonal (MgNi2 type) for alloys slightly deficient in titanium. The parameters of the two phases are given in table I. In the system titanium-nickel, the nickel-rich phase corresponds to the composition TiNi3 and has been described as hexagonal7 with the parameters given in table I. The present investigation was initiated for the purpose of filling in the gaps in the knowledge con-cerning the structure of the various phases sum-marized in table I. Since the titanium used by Wallbaum and his collaborators was only 95 pct pure,' it was found desirable to redetermine the lattice parameters of the alloys prepared with a

Jan 1, 1951

By Frederick Prime

In this second supplementary list no titles to which an * is pre fixed hare been seen by tlie compiler; and he will be most thankful to have any omiesisne or inaccuracies in the list sent to hiin to be ptiblisi~cd as a third supplement in the next volume of the actiotra. The author is indebted to Prof. J. J. Stevenson, of New Tork, Prof. P. R. Uhlcr and John 'CV. M. Lee, Esq., of Balti more, and Lloyd P. Smith, Esq., of Philadelphia, for valuable assistance. office, allkntorn iron compaxy, 30 South Third Street, Philadelphia, September 5th, 1881. Alabama. Geologiml Survcy of Alabama. report of Progress for 1879 and 1880, by Eugene A. Smith, State Geologist. Montgomery, 1881. 8vo., 158 pp., and 2 maps. California. Omit Report of Hon. T. Butler Ring, iu sopplemeut I. For Trask's Geology and Illdustrial honrecp, etc., in Supplenlvut I., read Tyson's, etc. Fremont's Menloir on Upper Califijrnia, is also published as XXXth Congress, lat Session. Senate Ms. Doc., No 148, and has a map. For Randall's Report in Supplement I, rend Report of the Special Committee in favor of a Geological Snrvey, subrn-itted by Mr. Randall, April 24th, 1861. n.d., 1851. 8cWo., 19 yp. XXXIst Congress, 1st Session, Sen. Ex. Doc., No. 47, Part 2 [Part 1 is Tyson's Report.) RejW of the Secretary of War in further compliance with the Resolution of the Senate?, calling for Colbies of

Jan 1, 1881

By Fred C. Bond

AN improved method of measuring the surface area of a comminution product down to any desired particle size has been developed. The method is largely graphical, and requires relatively little calculation. It can be used with materials containing large amounts of clay, or excess fines of any kind. The surface area S is expressed in terms of square meters per 100 c.c. of solids. This expression is based upon volume rather than weight, and is considered to be more suitable for crushing and grinding problems, where the machines ordinarily are operated under constant volume conditions. It has the advantage that surface areas of different materials can be compared directly, even though their specific gravities may be unknown. The "specific surface" of a material, or the number of square centimeters of surface area per gram, is equal to 100S divided by the specific gravity. Particle diameters are expressed in microns, K being the diameter of the largest particle present and L the grind limit, or lower size limit of the particles formed directly by grinding. The value of K does not always coincide exactly with the diameters of the largest particles retained on the coarsest testing sieve, since the largest particles formed in crushing and grinding are often slabby, or have other irregular shapes. L has been chosen as 0.700 microns, or number 27.5 in the size number series, for reasons to be explained later. S is the total surface area of all particles larger than L microns in diameter. When a homogeneous comminution product is separated into fractions whose diameters bear a constant geometrical relationship p to each other, and the log per cent weight retained upon each size and passing the next larger size is plotted against the log diameter, a straight line results, which is called the distribution line, and which has a slope in called the distribution modulus. The distribution line can be extended to any desired limiting size, and the total surface area of all particles larger than that size can be calculated. The equation of the distributi0n line is [w = Cx" [I]] where w is the per cent weight retained on each successive sieve; x is the particle diameter; and C is the per cent weight retained on an opening of unit diameter.2 Theoretically, the distribution line can be extended to include infinitely small particles. When it is so extended, and the assumption is made that no fine particles are present other than those accounted for by the equation; the log per cent cumulative weight passing any series of sizes, plotted against the log diameter passed, will result in a straight line lying parallel to and above the plotted distribution line.

Jan 1, 1941

By E. P. Hindes

The total amount of oil produced in the state of Oklahoma during the year 1928 was 242,286,400 bbl., as compared to 273,372,650 bbl. in 1927; 177,650,000 bbl. in 1926; and 167,900,000 bbl. in 1925. The year 1928 ranks second to 1927 in which more oil was produced in the state than in any previous year. The large in in 1927 and 1928 was due principally to the development of the Greater Seminole district. The decrease of approximately 31,000,000 bbl. in the 1928 production as compared with the production in 1927, was caused by a drop of nearly 8,500,000 bbl. in the Seminole district production and a more or less normal decline in the production of practically all the other older and more settled fields. During 1928 approximately 1800 producing wells were drilled in Oklahoma, which yielded during the year approximately 90,000,000 bbl. of oil. The average initial production of these wells was 850 bbl. per day, and the average daily production per well for the year was 137 bbl. The average daily production per well of the total number of wells producing in 1928 was 10.9 bbl., which is a 13.5 per cent. decrease from the 1927 average of 12.6 barrels. At the close of 1928 a total of 95,400 producing wells had been drilled in the state, and approximately 61,000 were still producing. The grand total amount of oil produced in the state from the time the first well was drilled up to and including 1928 was 2,553,000,000 bbl. The production in 1928 was 9.5 per cent. of the total oil produced in the state. Texas led all other states in 1928, with a production of 251,835,200 bbl. Oklahoma was second with 242,286,400 bbl., and California was third with 231,982,600 barrels. Fields outside Greater. Seminole District Practically all the old settled fields in Oklahoma experienced a normal and expected decline during the year 1928. The fields showing the most, pronounced decline as compared to 1927 were: Burbank, which dropped from 15,230,400 to 11,939, 150 bbl.; Tonkawa, from 7,692,000 to 4,952,900 bbl.; Garber, from 5,056,300 to 3,139,400 bbl., and Wewoka, from 6,188,-800 to 2,450,400 bbl. There were no new extensions, discoveries of

Jan 1, 1929

By Walter McDermott

This machine is an improvement on the well-known endless travelling belt used for dressing slimes in many mills; the chief point of difference, and constituting the essential advantage of the present over the old form, is the application to the machine of a secondary agitating or shaking motion, in addition to the ordinary progressive motion of- the belt. In the machine as heretofore made, the inclined belt or apron moved slowly up against a thin stream of water and ore, depositing the concentrations carried over in a tank placed below, through which the belt travelled, of course, in a reversed position. By reference to the accompanying drawings, it will be seen that in this main principle the new modification does not differ materially; but the means by which it is carried out are essentially different. The machine consists of a substantial frame of mood, F, Figs. 41, 42, and 43, within which hang the shaking frame and rollers, B B, A, Endless apron ; B, Apron frame and rollers ; C, Driving drum ; D, pulleys; B, Shaft and connecting rods; F, Wooden frame; G, Shaft of regulating Pulley; H, Yokes. supporting the upper half of the travelling apron, A, which passes below around the driving drum, C, in the water-tank, J. On leaving the water-tank, the belt passes over the guiding and tightener pulley, G. The ends of the shaking-frame, B, are provided with iron yokes, H H, bored to admit the shafts of the end rollers, and carrying a lug, by which attachment is made to the connecting rods,

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-B alloys has been measured up to the solubility limit for the formation of boron nitride. The activity coefficient of nitrogen increases with increasing boron content in the range 0 to 7 wt pct B. From experimen -tal data, values have been calculated for the B-N interaction parameter e3 at temperatures in the range 1550" to 1750°C. A value of 0.038 has been estimated for the boron self-interaction parameter eg at 1550°C. The standard free energy of decomposition of boron nitride into the elements dissolved in liquid iron has been determined to be: ?F° = 45,900 -21.25T in the range from 1550° to 1750°C. The nitride is assumed to be of composition BN. BORON nitride has an unusual combination of properties which make it appear attractive in a wide range of engineering applications. Some of its more important and most recent applications are in the nuclear area, particularly in connection with the liquid-metal cooled reactor concept now receiving considerable emphasis. Boron nitride has a high degree of stability at elevated temperatures. It also has excellent ma-chinability and the ease with which its crystals deform suggests applications as a lubricant. These properties stem from a hexagonal layer-type structure similar to the structure of graphite. One of its primary uses to date has been for seals in liquid-metal pumping systems. It is also used in nuclear reactors as an insulating layer to separate two solid metals which are not themselves compatible under the conditions of temperature and atmosphere in which they are used. Its inertness to liquid metals has also suggested use as a mold-release agent in casting processes. In addition to its excellent machinability and reported inertness to liquid metals such as iron, silicon, aluminum, copper, and zinc, boron nitride has high thermal conductivity and excellent thermal shock resistance. This combination of properties would make it appear ideal as a refractory crucible material for refining of high-purity liquid metals, for example high-quality steels. However, since it is known that concentrations of boron as low as 50 ppm can have a marked effect on the physical properties of certain steels,' in particular on the creep and stress-rupture properties, an investigation was undertaken to define accurately the chemical equilibrium among boron, nitrogen, and liquid iron in the range of steelmaking temperatures. EXPERIMENTAL PROCEDURE Two experimental approaches to this problem were employed: a Sieverts' method and a quenching method. In the first method, the Sieverts' technique was used to measure the equilibrium nitrogen solubility in liquid Fe-B alloys of 0 to 7 pct B as a function of nitrogen gas pressure over the melt. The solubility limit of the boron nitride phase formed was determined by the point of departure of the nitrogen absorption from Sieverts' Law. This technique has been applied to liquid Fe-Ti alloys by Rao and parlee,' to liquid Fe-A1 alloys by Evans and Pehlke,3 and to solid Fe-V alloys by Fountain and Chipman.4 In the second method a melt of liquid iron was held in a crucible of boron nitride under a known partial pressure of nitrogen gas. After thermodynamic equilibrium was attained, the melt was quenched in a stream of helium and then analyzed by wet-chemical methods for boron and nitrogen. The Sieverts' apparatus used in the first method was essentially of the same design as the one described by Pehlke and Elliott.5 The charge materials were vacuum-melted high-purity iron (Ferro-vac E) supplied by the Crucible Steel Co. and -325 mesh boron powder supplied by Cooper Metallurgical Associates of Cleveland, Ohio. The boron contained less than 0.02 wt pct O, according to supplier's analysis. Recrystallized alumina crucibles were used to contain the melt. Examination of solidified melts showed these crucibles to be satisfactory with no evidence of any reaction or physical penetration of the crucible wall by the melt. The melt temperature was measured by a disappearing filament-type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diam sight hole in the crucible lid. The pyrometer was calibrated against the melting point of pure iron in the same apparatus, taking the emissivity of

Jan 1, 1964

By M. N. Short, I. A. Ettlinger

M. N. Short,? Washington, D. C., and I. A. Ettlinger, New York', N. Y. (New York Meeting. February, 1926) The Pioneer mining district, better known as the Superior district, from its principal town, is located in Pinal County in south-central Arizona about 80 miles east of Phoenix and 22 miles west of Miami. The region embraces a, confused series of mountain ranges of moderate height but precipitous slopes, between which lie irregular valleys filled with alluvial detritus. The average elevation is about 2800 ft. in the valleys and the summits of the ranges reach 2000 ft. above this. Superior is situated on the north bank of Queen Creek where it emerges from one of those ranges into a more or less basin-shaped valley. The drainage of Queen Creek is to the southwest and the flood waters spread out and lose themselves in the desert northeast of Florence, the county seat of Pinal County. The Magma copper mine (Fig. 1) is the only producer in the district. Although discovered in 1875, its production has been important only

Jan 1, 1927

THE Institute assembled in the Court-House, on Tuesday evening, May 22d, and was called to order by Vice-President E. B. Coxe. After announcement by the Local Committee of the programme for excursions, the Secretary read the following annual report of the Council The Council, in presenting to the Institute its annual report, has to record a most eventful year in the history of the Institute. Three meetings, as usual, have been held, two in Philadelphia and one in New York. At the Philadelphia meetings in June and October, there were present many distinguished foreign engineers, some of whom contributed communications to the Institute, and took part in its discussions. Sixty-seven papers have, in all, been presented to the Institute, which will be published in the fifth volume of Transactions. There has been an accession to the membership of 1 honorary member, 11 foreign members, and 162 members and associates; -8 have resigned, 6 have died, and 30 have been dropped from the roll, after due notification, for non-payment of dues. The membership now comprises 5 honorary members, 60 foreign members, and 644 members and associates, in all 699. As worthy of especial mention in the work of the year are the Discussions on Technical Education in connection with the American Society of Civil Engineers, and the report of the-International Committee appointed by the Institute to consider the nomenclature of iron and steel. The Discussions on Technical Education have been published in a separate volume, and comprise a valuable and suggestive collection of the views of practical engineers and educators. The report of the International Committee, composed of Messrs. Akerman, of Sweden; Bell, of England; Tunner, of Austria; Gruner, of France; Wedding, of Prussia; and Holley and Egleston, of the United States, has received the careful attention of engineers and metallurgists of all countries, and has met . with very general acceptance. Of the work of the Centennial Committee in Philadelphia the members are generally familiar, from personal experience, and from the detailed report of the committee at the last meeting of the Institute. But the record of the service rendered by this committee would he incomplete without mention of the numerous letters of thanks and formal expressions of obligations received by the Institute from individuals, societies, and governments abroad. The wise and generous spirit in which the work of the committee was planned, and the laborious and self-sacrificing manner in which it was carried out, call for emphatic expressions of thanks from the Institute. The gifts of Centennial exhibits to the Institute, largely as testimonials for services rendered, has necessitated the appointment of a Museum Committee for

Jan 1, 1878

By John Blatchford, H. O. Hofman

The leading antimony mineral is stibnite. In smelting stibnite ore two processes are available, precipitation and roasting-reduction. The former is suited only for high-grade ores. As low-grade ores are more common than high-grade, roasting-reduction is of greater importance than precipitation. In the roasting process the aim may be to leave the oxidized antimony in the ore, or it may be to volatilize as much of the antimony as possible, collect the volatilized oxide as a rich intermediary product and smelt it for antimony, leaving the gangue poor enough to be considered a waste product. Whichever way the roast is conducted certain difficulties inherent in stibnite are encountered. These are: 1. The low melting point of stibnite which, according to Pélabon,' is 550°C., according to Wagemann2 540°C., and according to Borgstroma 546°C. 2. The ignition temperature: According to Friedrich,4 stibnite, if heated in air, begins to oxidize at 290°C. if the size of a grain is 0.1 mm. in diameter; at 343", if 0.1 to 0.2 mm.; and 430" if 0.2 mm. 3. The fusibility of a mixture of Sb2S33 and Sb203 which in the form of kermesite (Sb2S3)z.Sbz03 melts at 517°C.6 4. The volatility of Sb2Ss and SbzOs, for which no numerical data appear to exist, although practical experience has shown that they are volatile at low temperatures. As regards the oxidation of metallic antimony, we have the experimental evidence of C. F. Plattner6 that when fused and brought to a red heat, it burns with a bluish-white flame to Sb2Oa which passes off as a

Jan 1, 1916

By William Kent

ABOUT a year ago, the writer had occasion to assist Mr. John L. Gill, Jr., of the Pittsburgh. Car-wheel Works, in making a trial of his new testing machine. A piece of Bessemer steel, of about .34 carbon, was used as a test-piece, turned to a sectional area of one square inch for a length of five inches between shoulders, and pro¬vided with large round heads, which were fitted to what is called the " Wade grip." Measurements of elongation, accurate to , 1/10000 of an inch, were made by a special apparatus containing two micrometer screws, with electric contact attachment. The machine was operated by hand-power. Readings of elongation were taken at each increment of 2000 pounds stress per square inch, up to 44,000 pounds, the elongation corresponding to the latter figure being .0088 inch. The elongations up to this point remained almost exactly proportional to the stresses, the strain diagram, as shown on the Plate, from the origin to the point A, being a straight line (the deviation of no observation from the straight line being greater than .0002 inch). There being no indication of an approach to the elastic limit, the attendant at the hand-wheel and scale-beam was told to proceed as usual and move the poise forward 2000 pounds, or to 46,000, and turn the wheel until the beam was balanced. Noticing that the beam did not rise in the usual time, and that the elongation was increasing rapidly, the writer called to the attendant to stop turning the hand-wheel and to push the poise backwards until the scale-beam balanced. Instead of balancing at between 44,000 and 46,000 pounds, as was expected, it balanced at 40,000 pounds, and the elongation had increased to .0343 inch (or more than four times that recorded at 44,000 pounds), as plotted at the point B, the dotted line between A and B showing the supposed course of the strain diagram between these two points. Immediately upon recording the elongation the writer said to Mr. Gill, who was standing alongside: "This phenomena is without a parallel in my experience, and I know of but one way to account for it. The piece must actually be broken in its interior, through a flaw or weak portion of the metal. The test-piece is now equivalent to a tube, with

Jan 1, 1880

By William Kent

About a year ago, the writer had occasion to assist Mr. John L. Gill, Jr., of the Pittsburgh Car-wheel Works, in malting a trial of his new testing machine. A piece of Bessemer steel, of about .34 carbon, was used as a test-piece, turned to a sectional area of one square inch for a length of five inches between shoulders, and provided with large round heads, which were fitted to what is called the " Wade grip." Measurements of elongation, accurate to 1/10000 of an inch, were made by a special apparatus containing two micrometer screws, with electric contact attachment. The machine was operated by hand-power. Readings of elongation were taken at each increment of 2000 pounds stress per square inch, up to 44,000 pounds, the elongation corresponding to the latter figure being .0085 inch. The elongations up to this point remained almost exactly proportional to the stresses, the strain diagram, as shown on the Plate, from the origin to the point A, being a straight line (the deviation of no observation from the straight line being greater than .0002 inch). There being no indication of an approach to the elastic limit, the attendant at the hand-wheel and scale-beam wits told to proceed as usual and move the poise forward 2000 pounds, or to 46,000, and turn the wheel until the beam was balanced. Noticing that the beam did not rise in the usual time, and that the elongation was increasing rapidly, the writer called to the attendant to stop turning the hantl-wheel and to push the poise backwards until the scale-beam balanced. Instead of balancing at between 44,000 and 46,000 pounds, as was expected, it balanced at 40,000 pounds, and the elongation had increased to .0343 inch (or more than four times that recorded at 34,000 pounds), as plotted at the point B, the dotted line between A and B showing the supposed course of' the strain diagram between these two points. Immediately upon recording the elongation the writer said to Mr. Gill, who was standing alongside: "This phenomena is without a parallel in my experience, and I know of but one way to account for it. The piece. must actually be broken in its interior, through a flaw or weak portion of the metal. The test-piece is now equivalent to a tube, with

Jan 1, 1880

By H. V. Flagg

OPERATION of a modern steel plant presents a curious anomaly. Large-scale operations, in which large volumes or heavy weights of materials are involved, are not usually subject to close control or narrow specifications. On the other hand, operations that call for a high degree of precision are usually carried out under carefully controlled conditions with delicate, precise machinery and tools, and production is made secondary to quality. In a modern steel mill both extremes are taken as a matter of course. A strip mill making auto-body sheets must supply its customers with sheets that all come within a tolerance of plus or minus 0.003 in. in gauge at any point from side to side or end to end, and without blemishes either of color or surface. Sheets that were considered par excellence as recently as ten years ago could not even find a market today. Such exacting requirements have made necessary a nicety of control that approaches the watchmaker's art. Notwithstanding this necessity for precision, the scale of operation is stupendous.

Jan 1, 1940

By J. P. Murphy, T. E. Leontis

DURING the last few years, the trend in the aircraft and automotive industries has been toward higher and higher operating engine temperatures. This has created considerable interest in the effect of temperature on the properties of alloys. In the magnesium field, it has been recognized for many years that the addition of cerium imparts high strength and good resistance to creep at elevated temperatures. Beck,1 in his treatise on-magnesium, has summarized the work of German investigators. This includes the unpublished data of Menking, showing the increase in strength and hardness of extruded alloys containing 2 to 20 per cent Ce at temperatures from 200 to 300°C. (68° to 572°F.) and the results of Vosskühler, who demonstrated the improved resistance to creep of alloys containing 6 per cent Ce plus 2 per cent Mn and 0.5 per cent Ce plus 2 per cent Mn at 150°C. (302°F.). Wellinger and Keil2 have also reported the creep properties of a forged magnesium-cerium-manganese alloy at 200° and 250°C. (392° and 482°F.). Haughton and Prytherch have determined the tensile properties of various forged magnesium alloys containing cerium, cerium plus manganese, cerium plus calcium, cerium plus nickel, cerium plus nickel plus manganese, and cerium plus cobalt plus manganese at temperatures up to 290°C. (554°F.). Magnesium-cerium alloys have been used in some commercial applications. It is reported that an alloy containing 3 per cent Ce plus 0.5 per cent Mn plus 0.5 per cent Ca is being used on a forged impeller in Great Britain. Two forged parts made from an alloy with a nominal composition of 5 per cent Ce and 2 percent Mn have been found on the German .BMW-801D aircraft engine. These two forgings consist of a supercharger impeller and a rear cam-follower guide. In this country, several types of pistons have been made experimentally in both .the cast and the forged conditions from an alloy containing 6 per cent Ce plus 2 per, cent Mn and in the cast condition from an alloy of magnesium plus 10 per cent Ce. The cast pistons have been tested in various types of internal-combustion engines, with promising results. This paper presents the results of an extensive investigation on the properties of various cerium-containing magnesium alloys in both the cast and the forged conditions. Data are presented to show the beneficial effects of increasing amounts of cerium on the mechanical properties of magnesium at elevated temperatures. The effects of heat-treatment on the properties of these alloys and the attendant changes in the microstructure are discussed. The

Jan 1, 1946

By B. Lustman

IT has been known for a number of years that the addition of certain alkaline-earth and rare-earth metals to nickel-chromium base electric resistance alloys causes marked increase in their oxidation resistance as measured in an intermittent oxidation test similar to the ASTM—B 76-39 test. However, the mechanism whereby such additions confer protection is still unknown. On the basis of the experimental observation that the increase in life in intermittent tests of nickel-base alloys is proportional to the atomic radius of the added element, Hessen-bruchl has proposed that the added metal ions occupy holes in the oxide lattice which prevent diffusion of nickel ions in the oxide. Horn2 has postulated that the effect of such additions is to accelerate the rate of diffusion of chromium atoms in the metal and thus to favor the formation of Cr2O3 scales. Hickman and Gulbransen3 concluded from electron diffraction observation that the addition of the elements in question results in the formation of a barrier to the diffusion of nickel ions to the surface. In connection with some experiments conducted to develop a test for the resistance to oxidation of alloys in massive form under conditions of intermittent heating and cooling, some features of the oxidation of nickel-chromium base alloys were revealed which may serve to elucidate the mechanism of protection conferred by rare-earth and alkaline-earth elements. Specimens of cylindrical shape 0.360 in. diam x 0.37 in. long were placed in alumina thimbles and inserted into and withdrawn from a Globar-heated furnace operating at 2150°F at 7.5-min intervals. The weight of oxygen absorbed as well as the weight of oxide spalled were measured at intervals. With the particular experimental conditions used, the specimens in a 7.5-min cycle were at temperature for 2 min which corresponds to the heating time of the ASTM test. The weight changes of similar specimens under conditions of continuous heating in air at 2150°F were also measured. The specimens after oxidation were examined metal- lographically and samples of the spalled oxide collected for X-ray diffraction identification of the phases. The specimens used were from the same lot of material used by Hickman and Gulbransen3 and had the compositions shown in table 1. Included in table I are results of ASTM life tests on the materials in the form of wires. These materials, their composition and the ASTM life test data thereon were all supplied by F. E. Bash of the Driver-Harris Co. It may be noted that alloy 13246 of 80 pct nickel, 20 pct chromium nominal composition showed the shortest life in the ASTM test; alloy 12246 with the addition of small amounts of the elements zirconium, calcium, and aluminum, intermediate life; and alloy 12046 with the further addition of silicon, the longest life. In fig. 1 are shown the results of intermittent oxidation tests made on bulk specimens at 2150°F as well as continuous tests conducted at the same temperature. Duplicate tests were made on each specimen. The ordinate scale, inches of metal oxidized, was derived from the experimentally observed weight gain of oxygen by assuming the scale to be entirely Cr2O3. It may be noted that the metal-loss curves during intermittent oxidation show a constant or continuously increasing rate of weight

Jan 1, 1951