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By John M. Bostwick

Bitumen is a general term for a group of materials composed of mixtures of hydrocarbons that are fusible and soluble in carbon disulfide. Included in the group are petroleum, asphalts, asphaltites, and mineral waxes. Asphalt is a dark-colored, cementitious solid or semisolid, which generally softens on heating and resumes a more viscous or solid state when cooled (personal communication). It is found in native form in fissures and pore spaces in rocks and as lakes. It is also obtained from the residues produced in petroleum refining. Asphaltites are black, naturally occurring solid bitumens. They are generally shiny and break with a conchoidal fracture. Common asphaltites are gilsonite (uintahite), grahamite, and glance pitch. Mineral waxes are solid or semisolid, relatively nonvolatile bitumens of various colors, having an unctuous feel and waxy luster. Of the native waxes, ozokerite is the best known. Montan wax is also classed as a natural wax, although it never occurs in the pure state and must be extracted from lignite or cannel coal (Ladoo, 1920). Mineral waxes may also be obtained by pyroprocessing of petroleum, lignite, and peat. Pyrobitumens are dark-colored, solid hydro- carbons that are infusible and relatively insoluble in carbon disulfide. They are so-called because they will yield liquid and gaseous hydrocarbons only when heated. Asphaltic pyrobitumens are defined as "substantially free of oxygenated bodies" and include wurtzilite (elaterite), albertite, and impsonite (Thrush, 1968). Nonasphaltic pyrobitumens contain oxygenated bodies; examples are coal and peat. The nonasphaltic type will not be discussed further. Petroleum Asphalts Asphalts refined from crude petroleum have almost completely replaced the native types. Refineries can produce asphalts in every desirable grade more economically and in greater quantity than the native types and with a variety of properties that meet the requirements of the various manufacturers using them. For all practical purposes, it is estimated that more than 95% of the asphalts consumed in the United States are refined from crude petroleum (private communication).

Jan 1, 1975

By D. W. Rudd, D. W. Vose, S. Johnson

The permeability of Mo-0.5 pel Ti to hydrogen was investigated over a limited range of temperature and pressuire (709° to 1100°C, 1.i and 2.0 atm). The resulting permeability, p, is found to obey the The experimental data justifies the permeation mechanism as a diffusion contl-olled pnssage of Ilvdrogen atoms through the metal barrier. 1 HE permeability of metals to hydrogen has been investigated by a number of workers and their published results have been tabulated by Barrer' up to 1951. Since most of the work on the permeability has been accomplished prior to this date, the compilation is fairly complete. Mathematical discussion of the permeability process has been reported by Barrer, smithells, and more recently by zener. From these efforts several facts are observed. First, the permeability of metals to diatomic gases involves the passage through the metal of individual atoms of the permeating gas. This is evidenced by the fact that the rate of permeation is directly proportional to the square root of the gas pressure. Second, the gas permeates the lattice of the metal and not along grain boundaries. It was shown by Smithells and Ransley that the rate of permeation through single-crystal iron was the same after the iron had been recrystallized into several smaller crystals. Third, it has been observed that the rate of permeation is inversely proportional to the thickness of the metal membrane. Johnson and Larose5 verified these phenomena by measurirlg the permeation of oxygen through silver foils of various thicknesses. Similar findings were noted by Lombard6 for the system H-Ni and by Lewkonja and Baukloh7 for H-Fe. Finally, it has been determined that for a gas to permeate a metal, activated adsorption of the gas on the metal must take place. Rare gases are not adsorbed by metals, and attempts to measure permeabilities of these gases have proved futile. ~~der' found negative results on the permeability of iron to argon. Also, Baukloh and Kayser found nickel impervious to helium, neon, argon, and krypton. From what was stated above concerning the dependence of the rate on the reciprocal thickness of the metal barrier, it is seen that although adsorption is a very important process, at least in determining whether permeation will or will not ensue, it is not the rate determining process for the common metals. A case in which adsorption is of sufficient inlportance to cause abnormal behavior has been noted in the case of Inconel-hydrogen and various stainless steels.'' APPARATUS The apparatus used in this study is shown in Fig. 1. The membrane is a thin disc (A), but is an integral part of an entire membrane assembly. The entire unit is one piece, being machined from a solid ingot of metal stock. When finished, the membrane assembly is about 5 in. long. Two membrane assemblies were made; the dimensions of the membranes are given in Table I. The wall thickness is large compared to the thickness of the membrane, being on the average in the ratio of 13 to 1. There exists in this design the possibility that some gas may diffuse around the corner section of the membrane where it joins the walls of the membrane assembly, If such an effect is present, it is of a small order of magnitude, as evidenced by the agreement of the values of permeability between the two membranes under the same temperature and pressure. A thermocouple well (B) is drilled to the vicinity of the membrane. The entire membrane assembly is then encased in an Inconel jacket and mounted in a resistance furnace. The interior of the jacket is connected to an auxiliary vacuum pump and is always kept evacuated so that the membrane assembly will suffer no oxidation at the temperatures at which measurements are taken. The advantages of this configuration are: 1) there are no welds about the membrane itself, so that the chance of welding material diffusing into the membrane at elevated temperatures is remote. 2) It is possible to maintain the membrane at a constant temperature. Since the resulting permeation rate is very dependent upon temperature, it is advisable to be as free as possible from all temperature gradients. 3) It is possible to obtain reproducible results using different specimens. The only disadvantage to this configuration is the welds (at C) in the hot zone. The welding of molybdenum to the degree of per-

Jan 1, 1962

By A. U. Seybol

Eight binary iron alloys were examined after ion nitriding experiments to determine the behavior of the following elements: Al, Mo, Mn, Si, Ti, V,Cr, and C. Only Al, Cr, Ti, and V additions caused hardening in binary iron alloys. A few steels were examined to see the effect of Cr, Cr + Al, Cr + Ti, and Cr + V. It is suggested that a useful new class of ni-triding grade steels might be those containing about I pct V. The nitriding of steel, first described by Fry1 about 45 years ago, rapidly attained commercial application with very little knowledge of the fundamentals involved. While Fry,' in describing the status of nitriding in 1932, apparently correctly postulated hardening by precipitated nitrides, the details of the nitriding process were not understood, nor has the situation changed much since that time. It is also interesting to note that the compositions of some typical nitriding steels given by Fry at that time have changed little in the intervening years. Currently used nitriding steels owe their surface hardening to either chromium (as in 4340 steel) or aluminum plus chromium as in the Nitralloy grades, where both CrN and AlN appear to contribute to harden ing. Titanium additions have been studied experimentally, but thus far titanium steels have not won wide commercial acceptance. This subject will be expanded later. The orthodox ammonia nitriding process has been reviewed very adequately many times as in Jenkins3 and Case and VanHorn,4 and their is no need to outline the process here. Ion nitriding is not as well-known, although there have been several descriptions5-9 of the process given, sometimes with comparisons with the ammonia process. Most of these papers are primarily concerned with a description of the equipment, or of the physics or electrical engineering aspects of ion nitriding, but Noren and Kindbom9 gave the results of a metallurgical investigation using both processes. In brief, ion nitriding is carried out in a vacuum chamber from which the air is exhausted and replaced by a N2-H2 mixture, typically containing 10 to 20 pct N2, at about 5 to 10 torr pressure. While ammonia gas has also been used in ion nitriding, there is no evidence that ammonia makes any improvement in the ion nitriding process. A few hundred volts dc is applied between the grounded container wall (positive) and an insulated center post supporting the work (negative) to be nitrided. A glow discharge is created in the ionized gas, accelerating positive nitrogen ions to the work. These ions contain enough energy to form the normally unstable Fe4N "white layer", thus establish- ing surface nitrogen solubility characteristic of the a Fe/Fe4N equilibrium. This creates a substantial concentration gradient, driving dissolved nitrogen into the steel. The temperature employed is in the same range (around 500" to 550°C) as in ammonia nitriding, but because of factors which are not understood at present the nitriding time is ordinarily considerably reduced in ion nitriding. Other advantages have been cited,9 but it is not the purpose of the present work to contrast the two processes. The present objective was to examine the behavior of binary iron alloys during ion nitriding with respect to the microstructure, hardness level, and depth, and to examine some of these factors in steels as well. In this way it was hoped to be able to find out something about the individual role of these elements in steels. While all the work was done by ion nitriding, there seems to be no reason why any conclusions reached would not equally apply to ammonia nitriding, excepting only the kinetic aspects of the process. Another objective was an exploration of the critical-ity of the ion nitriding variables: gas composition, pressure, temperature, and time. EQUIPMENT AND MATERIALS The equipment used was substantially as described by Jones and Martin.8 The vacuum tank was about 12 in. in diam by about 18 in. high, and consisted of water-cooled stainless steel, with a single small window at the top for viewing inside. This sat on a heavy mild steel base equipped with the main pumping port, pressure control port, and vacuum gaging. A series of variable resistances was interposed between the glow discharge and a large-capacity -40 amp variable primary transformer feeding a 1000-v transformer, but 600 v were about the maximum ordinarily used. With the small l-in.-round, 4-in.-thick discs used for nitriding, the electrical load was usually about 500 v at 0.8 amp. The specimen temperature was controlled by a stainless-steel sheathed chromel-alumel couple, whose junction was in the steel stool upon which the flat discs were placed. These were ground through 400 Sic paper. Cycling of the temperature controller caused -0.2 amp variation in ion current, providing an ample control band. The binary iron alloys were made from vacuum-melted hydrogen-deoxidized electrolytic iron and alloys of 99.9 pct purity. Cast ll-lb-square tapered ingots were forged and hot-rolled to about 11/4-in.-diam rounds. Discs of 1/4 in. thickness by about 1 in. diam were machined from the rods for nitriding specimens. The following alloys were prepared: 1 pct each of Mn, Mo, Cr, Ti, Al, V, Si, and an Fe-0.8 pct C alloy. EXPERIMENTAL VARIABLES Of the variables total gas pressure, nitrogen partial pressure, temperature, and time, only nitrogen partial pressure was found to be critical to the operation. A critical nitrogen partial pressure was found corre-

Jan 1, 1970

By V. Carlson, J. A. Rowe, E. O. Bennett

This report concerns the microbial flora found throughout the surface facilities of six water-injection systems in Texas and Oklahoma. Each system is described in detail and water quality data are presented when available. Pseudomonads and sulfate-reducers (Desulfovibrio) were the predominate organisms found in the systems. The genera Sphaerotilus, Bacillus, Achromobacter, Minococcus, Clostridium, Flavobacteriurn, and Sarcina were also isolated in significant numbers. Molds, iron bacteria, sulfur bacteria and soil bacteria were found less frequently in the systems. It is concluded that a complex microbiological flora exists in oilfield water-injection systems. A tendency for waters to deteriorate in passage through solid bed filters is also noted. INTRODUCTION The injection of water into a subsurface formation is often accompanied by numerous problems, the origin and nature of which are only partially understood. During the past few years, investigators have indicated that bacteria are involved in some of these problems even though very little specific information is available concerning this matter. It is surprising that investigators working on microbiological problems in water injection have never made a complete study of the flora of these systems. The logical course to pursue is that of identifying the microbial flora and then examining each organism individually and in combination with others to determine if they produce a particular problem. The objective of the present investigation is to identify the microbial flora in water-injection systems. In addition. the quality of the water in most of the systems was determined and some observations made on the extent to which passage through surface-handling facilities affects water quality. The information derived from this study can serve as a foundation for additional basic investigations. EXPERIMENTAL PROCEDURE The microbial flora of six water-injection systems were studied at 50 sampling points. These systems are experiencing problems which may be attributable to micro-organisms, and two were being treated with antimicrobial agents at the time of this study. The samples were obtained by inoculating 1.0 ml of the water onto the different media at the sampling point. The media used for primary isolation included nutrient agar, Strokes agar, M-10-E medium and semi-solid thioglycollate medium. The cultures were returned to the laboratory, incubated at 30°C until growth occured; then, pure cultures were obtained from individual colonies. The pure cultures were identified according to standardbacteriologica1 procedures. Those organisms not fitting identification criteria exactly, even though exhibiting close similarities to known species, are listed as unidentified organisms. Membrane filters were used to make water-quality tests at intervals before and after collection of the microbiological samples. The filter discs were 47 mm in diameter with a 0.45-micron particle-size retention, and the tests were done under closed conditions at 20) psi. Membrane flow rates are plotted as increasing filtrate volumes, and the total solids contents arcs given when available. An effort was made to sample at each place in a system where a change in environment occurred. In this manner, the effect of passage through filters, tanks, hay sections, etc., on the microbial flora and water quality could be observed. RESULTS SYSTEM A This waterflood system (Fig. 1) is about four years old and daily pumps approx&ately 110,000 bbl of oil-free sour water from a 3,700-ft deep reef. The

By W. P. Evans, R. W. Buenneke

Warren and Averbach's multiple order, Fourier method was applied to solid specimens of SAE 1045 steel. The material was hardened to three hardness levels and specimens of each hardness were shot peened to three intensities. Particle size, root-mem-square strain, mean strain, md macro residual stress were determined for each. Microstrains caused by either hardening or peening varied markedly over microregions. In general, increasing the hardness or peening intensity increased the rms strain and decreased the particle size. Similar effects were observed by varying hardness and peening intensity independently. At a Rockwell hardness of C 50, peening had little effect on line broadening, but both mean strain and macro residual stress increased. Mean strain was independent of column length. Induced macro residual stress by peening was affected most by initial hardness, but not by specific peening intensity. The purpose of this work is to establish the state of residual strain and particle size by X-ray diffraction in hardened and cold-worked plain carbon steel and attempt to relate these X-ray measured parameters to fatigue performance. X-ray line broadening (and its micro implications), along with X-ray residual stress (and its macro implications), may be basic indicators of the inherent fatigue resistance of the material. X-ray line broadening is caused by variable lattice strains and small particle size. Both are a result of plastic deformation which accompanies hardening or cold working processes. Therefore, X-ray line broadening is a good measure of both. warren1 has recently reviewed the Warren and Averbach2,3 Fourier analysis of line broadening. Strain and particle size effects can be separated because broadening due to particle size is independent of order of the diffraction peaks, while broadening due to strain is not. Microstrain is obtained as a root-mean-square strain averaged over discrete distances within the crystals causing diffraction. These distances are quite small, varying from 10 to 10081, and may be interpreted as the gage length over which the strains are averaged. Because of their variable nature, the X-ray line is broadened. The plot of rms strain vs distance (or column length) within the specimen gives a measure of their variability. Small particles also cause X-ray line broadening as already mentioned. A particle is interpreted as a region within a crystal or grain which diffracts X-rays coherently. This region is one of given orientation and may be bounded by a small angle grain boundary, dislocations, a twin boundary, or a stacking fault. The present work covers measurement of X-ray line broadening and macro residual stress on an SAE 1045 steel, quenched and tempered to various hardnesses. Various amounts of cold working were produced by shot peening the surfaces to various Almen intensities. Particle size, root-mean-square strain, and mean strain were calculated from the Fourier coefficients of the X-ray diffraction profiles in a direction normal to the peened surface. No effort was made to separate the various causes of particle size broadening. Macro residual stresses were reported in directions parallel to the peened surface. I) X-RAY METHOD The Fourier coefficients were determined for the 110 and 220 X-ray profiles. They were corrected for instrumental broadening by the method of Stokes,4 using an annealed reference specimen of similar geometry presumed to be free from broadening due to small particles and distortions. The nth Fourier cosine coefficient, A,, is related to a particle size coefficient, Ap, and a distortional coefficient, ADn, by the equation:

Jan 1, 1963

By S. A. Braley

THE first commercial production of bituminous coal in the United States was in 1820, and formation of acid in the areas from which the coal was removed began at that time. Thus it is 130 years since the development of mine acid began. The coal operator has had to deal with the acid water produced in his mines, and his losses from corrosion of pumps and equipment have been tremendous. Other industries and the public have been forced to spend large amounts for their water requirements because of the acid discharge from the mines. There are many contradictions in the literature on this subject probably because of variations in the analytical procedures followed and differences in the methods of calculation and reporting. The opinions previously expressed may be summarized as follows: The production of mine acid has been looked upon as a simple chemical reaction wherein the oxygen of the air has reacted with pyrite to produce ferrous sulphate and free sulphuric acid. This reaction appears in many chemistry texts and generally has not been considered worthy of further study. Since the measurement of hydrogen ion concentration or activity was developed and expressed in terms of pH, indicator and instrumental methods for pH determination have become readily available, making it natural to think of it as a measure of acid content. Special purpose analytical methods applicable to potable waters, sewage effluents, and boiler waters, based in general upon the determination of what may be regarded as impurities, have been applied to more concentrated solutions constituting mine discharges, without reference to the fact that these specialized procedures had been developed to serve as operating guides for water-treatment plants. It has been assumed that the pounds of acid deliv- Table I. Showing pH and Titratable Acid of Varying Concentrations of Ferrous and Ferric Sulphates Ferric Ferrous ion Acldfty Ion Acidity (Fe+++) ppm CaCO3 We++) ppm CaCOa ppm PA equiv. PPm pH equiv. 11.200 1.80 30,000 11,200 3.98 20,000 5,600 2.01 15,000 5,600 4.15 10,000 2,800 2.21 7,500 2,800 4.41 5,000 1.120 2.48 3,000 1,400 4.68 2.500 560 2.60 1,500 140 5.00 250 280 2.65 750 28 5.00 50 112 2.81 300 56 3.07 150 28 3.38 75 ered by a mine was roughly a constant varying with the number of acres mined, and that the concentration of the acid in the drainage was inversely proportional to the volume of flow. Increased flow was thought to result in a dilution of the acid produced. When the Sanitary Water Board of the Commonwealth of Pennsylvania established a fellowship at Mellon Institute, the first approach to the problem was to review some of the chemical reactions involved and their relation to acid production. Since the sulphates of iron were among the principal constituents of coal-mine drainage, the first studies were based upon solutions of chemically pure ferrous and ferric sulphate. These are both neutral salts, that is, the iron and the sulphate are equivalent, but they produce acid reactions in water solution because as salts of strong acids with weak bases, they hydrolyze to form acid solutions. Solutions of each salt, of varying concentrations, were prepared and the pH, titrable acidity and iron and sulphate

Jan 1, 1952

By K. M. Busen, J. Lindmayer

A heterojunction model is suggested for descrihzng the electronic conditions at oxide -semiconductor interfaces. Detailed study of the silicon oxide-silicon interface shows that the heterojunction model explains many experimental facts; however, it is necessary to assume that a transition layer exists at the interface. It will he demonstrated that ionic contrbution way also he present. Extended low-temperature heating stabilizes the oxide to a charge carrier density in the order of 10' cln-: determined by the heterojuncton model. OXIDIZED semiconductor surfaces are widely used, since they offer technological advantages and "passivate" the surfaces of semiconductor devices. However, it has been recognized that there are always n-type inversion layers formed in the silicon oxide-silicon system, which must be regarded as a definite disadvantage. An added complication is the "instability" of these inversion layers;' the inversion layer appears to vary with the processing and they change at temperatures as low as 100" to 200°C This paper will point out that the inversion layer is a result of the dissimilarity of the contacting materials and therefore must always be present. The dissimilarity is the essence of the heterojunction or electronic model and involves directly the structure of the materials involved. In addition, one finds the contribution from ions; this disturbance, however. can be eliminated for the case of silicon oxide-silicon interface. The strength of the inversion layer or channel will be expressed in terms of the density of elementary charges per square centimeter, N*, maintaining the channel. The next section contains the formulation of the heterojunction model by assuming a contact between two homogeneous materials. This calculation should not imply that silicon oxide is homogeneous; it serves only to point out the general properties of the electronic model. Following the electronic model, the practical case of the silicon oxide-silicon interface will be discussed. I) THE HETEROJUNCTION MODEL Contacting an oxide with a semiconductor, a work-function difference must be accommodated. Fig. 1 represents the oxide and the semiconductor before and after contact. When the contact has been made, one finds that qVi + qV, = A@; i.e., the work-function difference is distributed between the oxide and the semiconductor. Normally, the work-function difference appears on the wide-bandgap material, but in the present case the oxide is thin and far from being a single crystal. Accordingly, a significant fraction of the work-function difference must appear on the semiconductor. The work function of silicon2 is about 4.8 ev, but we shall not assign any particular work function for the oxide as it may vary. However, oxides usually have lower work functions and therefore the potentials must build up in the manner shown in Fig. 1. Such an argument predicts that the inversion layer must be n type, as opposed to the clean surface which is p type. Another important factor to be considered is that the oxide is disorderly and therefore contains many trapping levels. As a result, the charges in the oxide arise primarily from the change in trap occupation, while on the semiconductor side the space charge is composed of mobile free electrons. The consequence of this fact is that a change to another thermal equilibrium will require some time, dictated by the traps in the oxide. The conditions can easily be calculated on the semiconductor side. Assuming an intrinsic semiconductor, Poisson's equation is

Jan 1, 1965

By F. V. Lenel, G. S. Ansell, J. A. Dromsky

The growth of aluminum oxide particles in a nickel matrix was studied eve?. the temperature vange of 2140° to 2470°F. The instability of the dispersed alumina was shown to be independent of the crystal structure of the alumina. The activation energy for the growth of the dispersed alumina was found to be 84.7 1 2.0 kcal. The particle radius increased as a function of time. These results indicate that the growth is not diffusion controlled. It is believed that the rate controlling mechanism is the dissolution of the aluminum and oxygen atoms into the nickel lattice. THE strength properties of alloys which consist of a finely dispersed second phase in a metallic matrix depend upon the spacing between the second phase particles. It is therefore desirable to achieve very fine dispersions in these alloys. Furthermore, to retain the properties these very fine dispersions must be stable during fabrication and service of the alloys. The best known of the dispersion strengthened materials, the SAP type alloys, which consist of a dispersion of aluminurn oxide in aluminum, have exceptionally good stability up to the melting point of aluminum. There is evidence, however, that other dispersion strengthened alloys, even those consisting of refractory oxides in a metal matrix, may be less stable. This investigation is concerned with the stability of Ni-Al2O3 alloys in the temperature range in which these alloys are usually fabricated. The mechanical properties of Ni-Al2O3 alloys at elevated temperatures have been previously investigated by Crelnens and rant,' and Gregory and Goetzel.2 The behavior of these alloys in stress rupture tests appears to indicate that at temperatures below 1800°F they are highly stable. There is some doubt, however, as to their stability at the higher temperatures used during the conventional fabrication. Cremens and Grant, in preparing their test alloys, cousolidated, by powder metallurgical techniques, nickel powders as fine as 0.13 µ diam and alumina powders as fine as 0.018 µ. Metallo- graphic examination of the alloys following fabrication revealed that none had interparticle spacings of less than 2 µ. Considering the size of the original component powder particles, it is likely that the dispersions coarsened during fabrication. Gregory and Goetzel, in their studies of extruded alloys of 80 pct Ni—-20 pct Cr matrixes with nonmetallic dispersion, observed a definite coarsening of the alumina dispersions in alloys sintered at 2280°F as cantrasted to those sintered at 2000oF. Similar observations on the spheroidization and growth of thoria particles finely dispersed in a nickel matrix were made by D. K. Worn and S. F. Marton.3 As a result of such coarsening, much of the effort expended in the preparation of very fine powder mixtures would be lost. The mechanical properties of the alloys which had experienced coarsening would be expected to be poorer than if the original dispersions had been retained. EXPERIMENTAL PROCEDURE Ni-Al2O3 alloys were produced from powder prepared by a coprecipitation technique. Aluminum hydroxide and nickel hydroxide were coprecipitated from chloride solutions of the metals. The mixed hydroxides were calcined to form metal oxides and the nickel oxide in the mixture was selectively reduced to nickel by treating it in hydrogen. Specimens were compacted from the resultant powder which consisted of a fine, uniform mixture of aluminum oxide and nickel particles. The compacts were sintered by resistance hot pressing4, a densification technique which requires exposure times of the order of only a second or less at elevated temperatures. A conventional sintering process was not used, since the temperature required for densification would have to be in the region in which the stability of the dispersion was to be studied. A series of hot pressed specimens were treated in hydrogen at temperatures from 2140o to 2470°F (1171o to 1355oC, for times up to 120 hr. Changes in the microstructures were studied by electron microscopy using the two-stage preshadowed carbon replica method.5 In performing a lineal analysis on a series of micrographs from each specimen it was found more convenient to determine the mean free path between alumina particles rather than particle radii as the parameter of growth. Although these quantities are directly proportional for only spherical particles, the alumina particles in these alloys

Jan 1, 1962

IT has been discovered by skilled bell founders, more through experience than from geometrical calculation (although calculation does enter), that a certain relationship of dimensions in both large and small bells makes the tone and the weight almost certainly what is desired. This is in addition to the customary shape which is, according to the historians, perhaps that found by the first discoverers of bells. Among themselves bell founders have made a rule of these measurements and have called it the bell scale. Beginning with the small ones weighing ten pounds, it increases by degrees to a point where, as I have seen, they are able to make them even twenty-five and thirty thousand pounds. This scale is of great enlightenment if one does not have a bell already made for comparison.

Jan 1, 1942

G. B. WATERHOUSE,* Buffalo, N. -Y. (written discussion?).-One of the most essential features of rail manufacture is the production of rails that will give good service and be free from failures. To this end rails are made to careful specifications and their manufacture is controlled by rigid inspection on the part of both the producing mill and the railroad or its representative, such as the Hunt special inspection referred to in the paper. Captain Hunt refers to the crescent-shape base failures and describes them as ruptures in the rail flanges extending from the outside inward toward the web. This is hardly correct and may be misleading. It has been shown, over and over again, that the base breaks originating in seams invariably start at the center of the rail base; and run longitudi-nally in varying lengths from 3 to 12 in. and sometimes longer. Most of them are from 5 to 8 in. long and then curve outward to the edge of the flange. The split at the center of the base may exist for an indefinite time and not be discovered until the break shows on top of the flange or the piece of flange breaks off. The. stresses that cause the break are explained in two ways: (1) by the eccentric bearing of the rail base, that is taking contact at one side or edge and bringing excessive strain at the center of the base which starts fracture in any seam that may he present at that point; (2) the split may be due to cross strain in the base where this member is thrown into. compression, as happens where a pair of trucks are on opposite sides of the cross tie or rail-base hearing, and the head is put in tension. A careful study of "split base breaks" shows that fully 95 per cent. occur on the tie bearing, which is further evidence that the above de-scribed causes for the initial break are probably correct. These split base breaks are almost invariably progressive, but always start at the center of the rail-base running longitudinally.

Jan 12, 1919

By L. J. W. JONES, B. H. Bennetts

THE removal and disposition of large quantities of slag from blast-furnaces is a question of great importance in the design of works, and various methods have been devised, from time to time, in order to take the best advantage of local conditions. In blast-furnaces treating copper-ores or lead-ores, it is necessary to use a fore-hearth, or matte-settler, in order to collect, if possible, every particle of valuable matte which, otherwise, would be carried away with the out-flowing slag. In all of these cases, the slag overflowing from the fore-hearth is caught in pots and then conveyed to the dump. If the slag is of no value and the necessary water-supply, grade and dumping-space be available, the disposal of the slag by granulation is by far the cheapest and best method. It involves a minimum of labor, both at the furnace and at the dump; and it permits a continuous outflow of slag from the furnace- or settling-pot, thereby avoiding frequent tapping and plugging. When the conditions of water-supply, grade and dump-area will not permit slag-granulation, there are three other methods in common use. Large steel or cast-iron pots, or ladles, supported by trunnions on heavy cars which are moved by steam-, air-, or electric locomotives; some type of mechanical conveyor; and small pots or buggies moved by hand. The pots on the slag-cars are generally circular or oval in shape, and each one contains from 15 to 40 or more en. ft. of molten material. The mechanism for tipping them is more or less elaborate; and, as a general rule, the slag is dumped alongside, and quite close to, the track. They are more or less costly to construct and to keep in repair, and, in order to use them to best advantage, it is necessary to have a good elevation of track above the dumping-ground; furthermore, the rails must be of heavy weight, and well-supported on heavy ties. Other disadvantages of the slag-pots are-1, that the slag cannot be removed continuously

Mar 1, 1905

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid cobalt and a number of dilute cobalt alloys Was measured in the temperature range 1550" to 1700°C at nitrogen pressures to 1 atm. At 1600°C and 1 atm nitrogen pressure, the solubility in pure cobalt is 0.0047 wt pct [3.8 cu cm (stp) per 100 g Co]. The standard free- energy change for the solution reaction 1/2 N,(g) = gout pct in Co) is iF - 10,000 + 5.24 T cal per g atom N. The alloying elements Cv, Cu, Mo, Nb, Tu, W, and V increase the nitrogen solubility, while Al, Fe, Ni, and Si decrease the nitrogen solubility. THE solubility of nitrogen in cobalt was studied previously by Sieverts, Busch and Dodd,2 and Schenck, Frohberg, and Graf.3 Sieverts investigated the solution below the melting point of cobalt, and Busch and Dodd worked with the liquid metal; however, neither study found any solubility for nitrogen in cobalt. Schenck et al, reported a solubility of 0.005 wt pct N in cobalt at 1600°C. Seagle et al. 4 reported residual nitrogen in cobalt after electron-beam melting, although no reasons were ventured for the presence of this interstitial impurity. This investigation was undertaken to clarify these inconsistencies, and to provide additional data on atomic interactions in dilute metallic solution. EXPERIMENTAL PROCEDURE This study was well-suited to the Sieverts' method, which has not changed significantly since its introduction by Sieverts. 5 The apparatus was of the same design as that described by Humbert and Elliott, 6 with a reaction bulb similar to that reported by Weinstein and Elliott. 7 The buret was not water-jacketed, but the measured gas volumes were corrected for small changes in room temperature. The melt temperature was measured by a disappear ing-filament optical pyrometer sighted through a prism onto the melt surface. Temperature calibration was made based on a measurement of the melting point of pure cobalt taken as 1495°C. The difference between the reciprocal of the observed and the true temperatures was assumed to be a constant, neglecting the changes in emissivity with small additions of alloying elements. The total error in gas-volume measurement caused by accuracy limitations in reading the mercury level in the buret, variation in ambient temperature, and variation in melt temperature was about 0.5 cu cm. This represents approximately 10 pct of the total solubility, and is a larger relative error than in previous studies6-' because of the small nitrogen solubilities encountered in the present investigation. The source and purity of the materials used are listed in Table IA. Recrystallized alumina crucibles were used throughout the investigation. Examination of the crucibles after solidification of the melts showed no reaction or penetration. Alloying of the cobalt melt was accomplished with the dropping technique described by Humbert. 6 The investigation was started using cobalt from African Metals Corp. in shot form, but this material was not of sufficient purity and did not yield consistent solubility results. Sherritt Gordon Mines Ltd. cobalt was then used throughout the investigation. In experiments involving alloying elements which could react with oxygen dissolved in the melt, the cobalt was further refined by annealing at 1400°C in a dry-hydrogen atmosphere. This treatment, described by Woolley and Pehlke, 8 markedly reduced the oxygen content. The oxygen and nitrogen analyses of the cobalt used in this study are presented in Table IB. RESULTS Hot Volume. The hot volume was measured prior to each run and was 50 to 55 cu cm (stp) at 1600°C. It increased linearly with increasing pressure and decreasing melt temperature. Pure Cobalt. Measurements of the solubility of nitrogen in pure cobalt and the temperature coefficient of solubility are summarized in Table 11. At 1600°C and 1 atm nitrogen pressure, the solubility was found

Jan 1, 1967

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By A. H. Daane, W. J. Wunderlin, B. J. Beaudry

The solid solubility of holmium in copper, silver, and gold, determined using metallographic techniques, was found to be a maximum of 0.06, 2.4, and 3.2 wt pct, respectively, nt the eutectic temperatures. The temperatures of these eutectic horizontals, determined by differential thermal analysis, were found to be 868", 787", and 778"C, respectively. The first compound on the silver-rich side of the Ag-Ho system was found to be A&Ho2. In a study by Gold et al.,' on the effect of small amounts of soluble impurities on the electrical resistance and thermoelectrical properties of copper, traces of iron were shown to have drastic effects on the thermoelectric power due to the magnetic scattering of the conduction electrons. Since little is known about the state of the iron ion when dissolved in copper, Gold had hoped to repeat these experiments using certain rare earths as the magnetic scattering centers; because of the tightly bound 4f electrons it is not expected that their spectroscopic state would be affected by alloying. In such an experiment the sole role of the trace rare-earth impurity would be to magnetically scatter the copper conduction electrons without producing appreciable distortions in the otherwise pure copper matrix. Since holmium was chosen for such a study because of its high magnetic moment, it was necessary to establish precisely its solid solubility in copper. The study was extended to include the solvents silver and gold, so that an evaluation of the data using classical solubility parameters could be made. No previously reported work on the systems of holmium with copper, silver, or gold was found in the literature. Information on the solubility of other rare earths in these three metals is also very meager. The solubility limit of yttrium in copper was reported as less than 1 wt pct2 and the solubility of praseodymium in gold as 0.35 wt pct,3 while no references were found on solubility studies of rare earths in silver. EXPERIMENTAL Materials. The materials used in this investigation were distilled holmium prepared in this Laboratory, OFHC* copper, electrorefined silver (99.9 *OFHC = oxygen-free high conductivity. pct), and gold with the analyses given in Table I. Sample Preparation. Samples weighing 1 to 2 g were prepared by arc-melting the components together on a water-cooled copper plate under purified argon atmosphere. The samples, turned and remelted at least five times to ensure homogeneity, showed weight changes of less than 0.1 wt pct after melting. Samples containing less than 0.7 wt pct Ho were prepared by diluting 1 to 2 wt pct Ho alloys with the pure solvent, while samples with concentrations greater than 0.7 wt pct Ho were prepared directly from the metals. The samples were wrapped in tantalum foil, sealed in outgassed Vycor tubing under helium, annealed at the desired temperature for at least 24 hr, and then quenched by shattering the Vycor tube in cold water. Metallographic Methods. Standard mechanical polishing methods were used in preparing the silver and gold alloys for examination, while the copper alloys were electropolished using a 40 pct solution

Jan 1, 1963

By F. H. Willcox

IN Bessemer-steel practice, air is blow, through a bath of iron, or projected strongly upon its surface to burn out silicon, manganese, and carbon. Toward the end of the blow, when the iron is not protected. from oxidation by these elements and the excess of air becomes great, there is oxidation of the iron. In open-hearth practice, the same difficulty is experienced with dissolved gas and oxides in the product, though not to as great or severe a degree as in the Bessemer process because the oxidizing conditions grow less severe as the end of the heat is approached, and if the bath is allowed to boil for a time it undoubtedly frees itself from a large part of the gas and oxides which have been absorbed in the earlier part of the process. Basic open-hearth steel is usually assumed to contain a larger proportion of oxides than acid open-hearth steel, but it may be said that all steel, Bessemer and open-hearth, contains more or less oxide of iron dissolved in the fluid metal at the end of the "blow" or "heat." That certain metals are solvents for their respective oxides has been shown, in the case of copper, by Heyn, and, in the case of iron, by Law. It is indicated that the solubility of iron oxide in iron increases with the purity and temperature of the metal. This confirms what is observed and known by operating men, and these observations may be summarized as follows: 1. Cast irons is rarely subject to oxidation, as is logical from its composition. 2. Normal steel, unless deoxidizers are added, contains blow holes. 3. Steel known to be oxidized is full of blow holes. 4. The addition of deoxidizers prevents, to a greater or less degree, the formation of blow holes in normal steel. With these observations in mind, it is logical to deduce that the cause of blowholes lies in part in the presence of dissolved oxide of. iron in the

Jan 2, 1917

By Sixten Wollmar

A RESUME. of some important points regarding the life of drill steel, which have so far been learned from investigations carried out in the SKF Hofors' mines, Sweden, by L. Nordenfelt, is given below. By examining all fatigue breakages which occurred in the test it has bees conclusively proved that when a rock drill of the self-rotating type is used all break-ages of this kind start from the surface of the hole in the steel. It has further been proved that the rough hole surfaces (i.e., the marks left by the indentations of the sand core), are the starting points for the fatigue cracks and that the corrosive action of the water has .a very detrimental influence on the life of the steel. It is now a well known fact that this corrosive action concentrates at the bottom of the indentations left by the sand. The corrosive action of water has been well described by U. R. Evans in his paper, "Some Recent Work on the Corrosion of Metals," delivered on March 31, 1926, before the Liverpool Engineering Society, which is quoted in part below: "It is well known that, under ordinary conditions, most metals do not corrode in water unless dissolved oxygen is present. The strange feature of corrosion in submerged metals, however, is that the attack does not proceed mainly over those portions of the surface which could be reached readily by oxygen; deterioration takes place at certain points which are relatively, inaccessible to oxygen. When. a metal becomes pitted by corrosion, further attack usually deepens the pits, and in many cases it could be proved that there was no free oxygen at the bottom of the pits. None of the older theories of corrosion explain the fact that, although oxygen is necessary for rapid corrosion to take place, the attack actually occurs at the very points which could not be reached directly by oxygen.

Jan 6, 1928

By Howard L. Hartman

There is reason to believe that ventilation systems so far devised for use with continuous mining machines fall far short of success. This is vividly demonstrated to anyone who has observed in a continuous miner section the localized ignitions of pockets of gas and the generation of dense clouds of dust by the cutting head of the machine. The alarming frequency with which major ignitions and disasters continue to occur in modern mechanical mining and the rise in incidence of pneumoconiosis serve as reminders that our ventilation systems are far from achieving the ultimate in providing protection from either short-term explosions or long- term dust diseases, both of which take lives. Human safety is the main concern in ventilation. But in this day of high-priced labor, let us not forget human comfort, either, for this is a major factor in motivation toward high productivity. The failure or inadequacy of most mine ventilation systems in providing the kind of working conditions at the face that are conducive to productive as well as safe operation is an indictment of our environ- mental control program in mining generally.

Jan 3, 1962

By K. B. Nowels

Data pertaining to pipe line flow for both oil and gas in horizontal or nearly horizontal pipe lines are both extensive and accurate. However, the pipe formulas used to determine pressure drop for flowing fluids (liquids and gases) under conditions of horizontal flow are not generally applicable to flowing oil and/or gas wells. Except for some data developed in small laboratory set-ups, little or no information was available concerning flow of oil and gas mixtures in vertical pipes, when, in 1928, the writer began the development of a method for computing pressure drops in the pipes of flowing oil wells, as outlined in this paper. In 1929, Urenl presented some findings based on laboratory experiments in which vertical flow of an extremely heavy crude oil was induced by means of air through a 2-in. pipe, 41 ft. long. The friction factors derived from the experiment, as well as values for pressure drop per 100 ft., are not believed satisfactory in their application to flow problems in the field. Versluys,2 also in 1929, presented a mathematical development of the theory of flowing oil wells, and in 1930, gave a companion paper3 setting forth some principles governing the choice of length and diameter of tubing in oil wells. Since the termination of the study presented in this paper, another valuable contribution pertaining to the problem of vertical flow was made by Moore and Wilde.4 Although there were writings dealing with the principles of the gas-lift, a search of the available literature indicated that specific information on vertical flow was lacking with the exception of the writings of Uren, Versluys, and Moore and Wilde, to which reference has been made.

Jan 1, 1932

Weston Portable Electrodynamometer The Weston Electrical Instrument Co. of Newark, N. J., believes that problems hitherto considered impossible of solution in the designing of portable electrodynamometers have been solved in its new models. The voltmeter, Model 341, is an instrument' of precision adapted to use on alterating- or direct-current circuits, guaranteed to an accuracy of 0.25 per cent. full-scale value either on direct or alternating-current circuits of any frequency to 133 cycles per second and commercial frequencies even as high as 500 cycles per second with very slight error. The polyphase electrodynamometer, Model 329, is accurate to 0.5 per cent. under the same conditions.; Double ranges are furnished in all instruments of this model. All current ranges can be used for 100 per cent. overload indefinitely without introducing error in Models 310 and 329.

Jan 12, 1915

By Hugh R. Van Wagenen, Allen H. Rogers

There are few natural monopolies comparable with the nitrate industry. Perhaps the only other one is, curiously enough, also an essentia1 fertilizer material, viz., potash, of which the Germans have heretofore held practically a monopoly due to the existence in their territory of the most important known deposits of potash salts. And although nitrates in minute amounts are found in many desert regions, the only deposits capable of being worked commercially exist in Chile. Combined nitrogen in the oxidized form is an essential for plant life. Nature provides it mainly through the agency of nitrogen-fixing bacteria. But where lands are cropped artificially this supply is too small, and gradually the nitrogen supply becomes exhausted. In order to continue farming, it is necessary to furnish a supply of nitrogenous plant food, and this is done by putting on various substances containing combined nitrogen. These consist of various animal wastes, ammonium sulphate, the ammonia of which is obtained in the destructive distillation of coal, and Chile saltpeter. The latter is immediately available as a plant food, the nitrogen being in the required form. The other substances must oxidize before they are available. Resides its use as a fertilizer, Chile saltpeter is the source from which the bulk of the nitric acid of commerce is derived. The use of nitric acid in the manufacture of almost all modern explosives is, of course, well known. Importance of the Nitrate Industry Chilean nitrate, the existence of which was first mentioned in 1809, is said to have been first exported in 1830. Only a few thousand tons per annum were exported for some years, but the amount gradually increased until, in 1879, when the Chile-Peruvian war began, the export amounted to about 300,000 tons. This nitrate was largely produced from the Province of Tarapaca, until then, Peruvian territory. By the terms of peace with Peru in 1884, this province, as well as Tacna, became Chilean. The Bolivian Province of Antofagasta was also acquired as a result of this war, and thus Chile, with the deposits in her own territory, acquired control of the whole supply of nitrate. At the present time, exports are approximately 3,000,000 metric tons per annum,. having a

Jan 1, 1918