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By J. W. Hickman

Most of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.' In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,~ nickel,= chromium,= copper,z tungsten,s molybdenum,3 beryllium,' uranium,' thorium,' titanium6 and zirconium6 while investigations are in progress on tantalum and columbium. The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally. Examples of solid solutions which may present difficulties are MOO* and WOp, Fe304 and FeO.CrnOa since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of loglo Kg for the several temperatures. AF"B = -RT In KR AF°R and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the the given in I 1 to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium oxide to form

Jan 1, 1949

By O. C. Ralston, F. Fraas

VIRTUALLY all commercial use of electrostatic separation has employed separators depending on differences of conductance of the broken, solid mixtures treated by them. The two main types of conductance separators have been: (1) Those in which the separating field is as near a static field between two charged electrodes as it is possible to maintain in the face of the usual leakage that takes place between electrodes with some 5 to 50 kv tension between them and spacing of 1/2 to 3 in.; (2) those in which a convective discharge of corona or spray type, but not a spark discharge, takes place between the carrier electrode and a charged electrode facing it, which is of very restricted area, such as a row of needle points or a small diameter wire parallel to the face of the carrier electrode. The present paper deals with this latter type. The principle is usable in separators where the carrier electrode, usually grounded, has the shape of a roller, a conveyor belt, a vibrating table, a sloping chute, or a nearly vertical plate. The innovation studied by us has been the use of the convective field for charging material on the carrier electrode and succeeded by a field between the carrier electrode and an electrode made of a true dielectric which cannot take on a charge by conduction but is charged by being in the radius of the corona discharge. The acquired charge is of the same sign as that of the corona but is not dischargable by contact with a good conductor. However, high-tension charge tends to leak off because of the ionization of the ambient air. The field between this electrode and the carrier electrode is as near static as it is possible to obtain. There are some differences in behavior of this electrode and that of the gas tube electrode used by Sutton, as will be discussed below. Both electrodes cause increased adhesion of nonconductive particles to the carrier roll. The particles are pinned there because they are convectively charged on their outer surfaces facing the corona electrode. The electrodes also cause increased rate of release of conductive particles tending to be pinned by corona charging but conveying the charge to the grounded carrier roll almost as rapidly as it is received by the particles. The sign of the potential on the corona-emitting electrode makes little difference in the separation. An electrode usually emits negative corona somewhat more easily than it emits positive corona, as electrons are then the fundamental particles emitted. With a positive electrode the flow of electrons involved in positive corona discharge is onto the electrode from the ambient gas. Theory In the separator illustrated in fig. 1, the nonioniz-ing electrode is a rotating, nonconductive dielectric cylinder designated as B. The ions emitted by the corona electrode, or wire F, charge both the particles on the carrier electrode, or roll A, and the surface of the dielectric electrode B. Whereas the space between roll A and wire F contains ions, the space between electrode B and roll A is a pure static field free of ions. The dielectric electrode has been described by Bullock.1 However, the corona electrode, which Bullock uses for the purpose of charging only the dielectric electrode, is adapted here to also charge the particles on the carrier roll. In operation the ionic field from the corona electrode is balanced with the static field from the dielectric electrode. The ionic field charges the particle so that it adheres to the roll. The static field intensifies the discharge of the corona charge by interfacial conduction and permits the release of the particle. The ionic and static fields therefore have opposing effects.2 The values of both fields are adjusted so that the poor conductor will adhere and the good conductor will be released.

Jan 1, 1951

By P. R. Jochens, D. D. Howat, R. B. Atmore

INTRODUCTION The Miller chlorination process has assumed a preeminent position in the refining of gold bullion, a position it has maintained for over half a century. In the early sixties considerable interest was aroused by the idea of producing a consistently high grade bullion at the mine smelthouses themselves. However, as the use of chlorine in industrial plants is associated with considerable hazards, oxygen was considered a natural alternative, apart from bing less expensive than chlorine. Partial refining at the mine smelthouses would considerably decrease the requirements made on Rand Refinery Limited as well as indicating the possibility of reducing final refining costs. An added factor would be the purer silver chloride obtainable, after prior removal of the base metals by oxygen injection, which would facilitate the production of high-purity silver. The free energies of formation of the oxides of the metals;- silver, copper, lead, zinc, iron and bismuth indicate that, with the exception of silver, these metals should be capable of removal as oxides by oxygen injection. Rose1 had shown that during injection of gold bullion, considerable loss of silver to the boraxsilver slag occurred and, furthermore, that copper removal was not efficient and oxide attack on the refractories was severe. Plant test work2 had confirmed the difficulty of copper removal, but had shown that zinc and lead were almost completely removed. The difficulty of copper removal by oxygen injection warranted further investigation. Also, the high decomposition pressure of silver oxide suggested that by suitable control of the slag composition it might be possible to reduce to very small proportions the silver carried into the slag as oxide. The oxidation of copper by oxygen injection and subsequent dissolution of the oxide in a slag may occur according to the following reactions; Reactions 4 and 5 were considered because of the relatively high solubility of oxygen in molten silver and silver alloys. Thermodynamic data indicate that there is little possibility of any reaction involving the formation of CuO occurring at temperatures above 1 000 °C. To ensure that the operative reactions 1 and 4 take place to the maximum extent, the following factors He significant. (a) an increase in the activity of the copper in the bullion, (b) an increase in the partial pressure of oxygen in the system, (c) an increase in the activity of the oxygen in solution in the metal, (d) a decrease in the activity of cuprous oxide in the slag. From practical considerations, the operative variable most easily susceptible to control is the composition of the slag. SOLUBILITY OF COPPER OXIDES IN BOROSILICATE SLAGS Very scanty information exists on systems containing copper oxides but the indications are that slags containing considerable amounts of boric oxide would possibly prove to be the best solvents for cuprous and cupric oxides. This is attributed to the fact that the activities of copper oxides are much lower in boric oxide slags than in slags in which silica is the main network former. The number of possible slags containing boric oxide was limited by consideration of liquidus temperature, viscosity, corrosive action on refractories, volatilization, and ultimately cost (for industrial application). Slags in the systems soda-boric oxide-silica and lime-boric oxide-silica were selected paying due attention to the above limitations. Additions of 5, 10 and 15 per cent cupric oxide were made to the finely ground, premelted slags. These mixtures were then reground and 2g quantities held in re crystallized alumina crucibles at temperatures of 1150°C and 1 250°C respectively for 30 minutes. The crucibles were removed from the furnace, rapidly cooled, cut in half longitudinally, and a thin section taken from one half was subjected to microscopic examination.

By R. L. Segall

AN unusual thermal etch figure in copper is described and an explanation in terms of twinning is suggested. A flat polycrystalline specimen of OFHC copper cut from a rolled sheet was electro-polished in orthophosphoric acid and annealed at 950°C in a vacuum of approximately 10-3 mm Hg for 2 hr. The specimen was found to be thermally etched, the markings on the surface being consistent with the assumption that they were the traces of the (111) planes which are developed preferentially because they have the lowest free energy. However, on one grain (the grain shown in Fig. 1) the traces formed an almost regular pentagon and at first sight it seemed unlikely that they could all be (111) traces. These traces were studied further because it was thought that they might be a type of growth spiral. A fringe pattern showed that this was not so, the grain being sensibly flat and the only features having steps were the striations and the faint curved line passing out from the center of the pentagons. To obtain some additional information, the specimen was deformed in tension. The effect of the stress was first to cause the appearance of lines running from the centers to the apexes of the pentagons and then to tilt the five segments so formed. At a much greater stress, appreciable slip appeared on the grain; these effects can be seen in Fig. 2. The micrograph was taken at a fairly late stage in the deformation and the tilting is quite marked. The magnification is the same as in Fig. 1, and although some slip can be seen it could be observed better by varying the illumination and using higher magnifications. In each segment of the grain, slip (which takes place on the (111) planes) was parallel to the side of the pentagon in that segment. The marked changes in direction of slip from segment to segment seemed to be incompatible with the presence of a regular array of subgrains. These results suggest that some of the five segments were twins. If this is so, since the twinning plane in copper is the (111) plane, the radial lines must be traces of the (111) planes on the surface. From the symmetry of the striations about the radial lines, these planes must be almost perpendicular to the surface. The angle between <III>directions in face-centered-cubic copper is 70&apos;32&apos;. If, in Fig. 3, OAB (triangle 1) is taken as matrix and OA, OB are (111) planes viewed edge on, then AB is in the correct direction to be the trace of either of the other two (111) planes on the surface. If triangle 2 is the twin (about the (111) plane perpendicular to the surface and containing OB) of triangle 1, then once again it can be shown that all lines are traces of (111) planes. Similarly, triangle 3 is the twin of triangle 2, 4 of 3, and 5 of both 4 and 1. (The sequence is, of course, quite arbitrary.) However, if this were the case there would be a discrepancy of 7&apos;20&apos; to be accounted for. It is suggested that the faint curved line passing outward from the center of the pentagon represents either a low angle boundary or a sixth small twin. The slight step shown by the fringes at this line might be an indication that the former is the case. This explanation does not account for the coincidence of obtaining a grain whose surface must be so close to (110) and obtaining the curious twinning described previously; it would be of interest to find a specific mechanism for this.

Jan 1, 1958

By O. C. Ralston, F. Fraas

VIRTUALLY all commercial use of electrostatic separation has employed separators depending on differences of conductance of the broken, solid mixtures treated by them. The two main types of conductance separators have been: (1) Those in which the separating field is as near a static field between two charged electrodes as it is possible to maintain in the face of the usual leakage that takes place between electrodes with some 5 to 50 kv tension between them and spacing of 1/2 to 3 in.; (2) those in which a convective discharge of corona or spray type, but not a spark discharge, takes place between the carrier electrode and a charged electrode facing it, which is of very restricted area, such as a row of needle points or a small diameter wire parallel to the face of the carrier electrode. The present paper deals with this latter type. The principle is usable in separators where the carrier electrode, usually grounded, has the shape of a roller, a conveyor belt, a vibrating table, a sloping chute, or a nearly vertical plate. The innovation studied by us has been the use of the convective field for charging material on the carrier electrode and succeeded by a field between the carrier electrode and an electrode made of a true dielectric which cannot take on a charge by conduction but is charged by being in the radius of the corona discharge. The acquired charge is of the same sign as that of the corona but is not dischargable by contact with a good conductor. However, high-tension charge tends to leak off because of the ionization of the ambient air. The field between this electrode and the carrier electrode is as near static as it is possible to obtain. There are some differences in behavior of this electrode and that of the gas tube electrode used by Sutton, as will be discussed below. Both electrodes cause increased adhesion of nonconductive particles to the carrier roll. The particles are pinned there because they are convectively charged on their outer surfaces facing the corona electrode. The electrodes also cause increased rate of release of conductive particles tending to be pinned by corona charging but conveying the charge to the grounded carrier roll almost as rapidly as it is received by the particles. The sign of the potential on the corona-emitting electrode makes little difference in the separation. An electrode usually emits negative corona somewhat more easily than it emits positive corona, as electrons are then the fundamental particles emitted. With a positive electrode the flow of electrons involved in positive corona discharge is onto the electrode from the ambient gas. Theory In the separator illustrated in fig. 1, the nonioniz-ing electrode is a rotating, nonconductive dielectric cylinder designated as B. The ions emitted by the corona electrode, or wire F, charge both the particles on the carrier electrode, or roll A, and the surface of the dielectric electrode B. Whereas the space between roll A and wire F contains ions, the space between electrode B and roll A is a pure static field free of ions. The dielectric electrode has been described by Bullock.1 However, the corona electrode, which Bullock uses for the purpose of charging only the dielectric electrode, is adapted here to also charge the particles on the carrier roll. In operation the ionic field from the corona electrode is balanced with the static field from the dielectric electrode. The ionic field charges the particle so that it adheres to the roll. The static field intensifies the discharge of the corona charge by interfacial conduction and permits the release of the particle. The ionic and static fields therefore have opposing effects.2 The values of both fields are adjusted so that the poor conductor will adhere and the good conductor will be released.

Jan 1, 1951

The industrial relations handbook, by A. Pons. Juta (P.O. Box 14373, Kenwyn 7790). 1989. "&apos;"250 pp. Looseleaf binder. R180 + GST. Industrial laser materials processing. World Business Publications Ltd (4th Floor, Britannia House, 960 High Road, London N12 9RY, England). 1989. 180 pp. £310. Mining 1990. Longmans, Financial Times International Year Books, 1989. 592 pp. £90.00. Innovations in materials processing using aqueous, co/oid and surface chemistry, by F.M. Doyle, S. Raghavan, P. Somasundaran, and G.W. Waren (eds.). 300 pp. $125. Light metals 1989, by P.G. Camp bel (ed.). No. of pp. not available. $150. Process control and automation in extractive metalurgy, by R. Partelpoeg and D.C. Himmesoete. 225 $98. Process mineralogy VIl, by D.J. Carson and A.H. Vassiliou (eds.). 4oopp. $150. Super plasticity and super plastic forming, by C.H. Hamilton and N.E. Paton (eds.). 700 pp. $140. Supera/oys 1988, by S. Reichman, D. Duhl, G. Maurer, S. Antolovich, and C. Lund (eds.). 880pp. $99. Surface modification technologies, by T.S. Sudarshan and D.G. Bhat (eds.). 305 pp. $49. World survey of nonferous smelters, by J .C. Taylor and H.R. Traulsen (eds.). 365 pp. $90. Second Parsons International Turbine Conference. London, The Institute of Metals, 1989.270pp. £40. Mineral processing in the United Kingdom. London, Institution of Mining and Metalurgy, 1989. £25. Today&apos;s technology for the mining and metalurgical industries. London, Institution of Mining and Metalurgy, 1989. 623 pp. £60. 1989/1990 E&MJ international directory of mining. Chicago, Mining Information Services (P .0. Box 6500, Chicago, IL 60680, USA). 620 pp. US$95. Advances in project scheduling, edited by R. Stowinski and J. Weglarz. Amsterdam, Elsevier, 1989. 540 pp. Dfl. 270. Proceedings of the 3rd International Conference on Molten Slags and Fluxes. London, Institute of Metals, 1989. 335 pp. £38. Brochure on industrial screens. Obtainable from Philippe Lavernhe, Johnson Filtration Systems S.A., Z.I. Availes-en-Chatelerault, 86538 Naintre, France. 16 pp. Free. Numerical techniques, edited by P. Spiling. London, The Institute of Metals, 1989. 226 pp. £25. Phase diagrams of ternary iron aloys, Part 2, by V. Raghavan. New Delhi, Indian Institute of Metals, 1988. 360 pp. £95 (from the Institute of Metals, London). cas publications These publications are available from the Centre for Resource Studies, Queen&apos;s University, Kingston, Ontario K7L 3N6, Canada. Economic aspects of gold exploration: How much is too much, by B.W. Mackenzie and M. Dogget. 30 pp. $10.00. Mineral exploration and mine development potential in Ontario: Economic guidelines for government policy, by B.W. Mackenzie, M. Bilodeau, and M. Dogget. 180 pp. $25.00. Economic potential of base metal and gold mining in Newfoundland: Assessing the impact of regional developmentpolicy options, by B.W. Mackenzie, M. Bilodeau, and M. Dogget. 188 pp. $25.00. Publications of the AusIMM The folowing publications are available from The Australasian Institute of Mining and Metalurgy, P. O. Box 122, Parkvile, Vic 3052, Australia. Prepayment is required with al orders. The AusIMM 1989 Annual Conference 1989. $A 50. Mineral fuel alternatives and the greenhouse efect. July 1989. A$ 35. NQ gold &apos;89. Apr. 1989. $A 50. Second Large Open Pit Mining Conference. Apr. 1989. $A 50. Explo &apos;88. Nov. 1988. $A45. Mineral deposits of New Zealand, edited by Dr D. Kear. Monograph 13. 244 pp. $A 60. Field geologists&apos; manual, compiled by D.A. Berkman. 3rd edition. 1989. : 350pp. $A45. The rocks speak. Essays in geology-some personal responses of a wiling listener, by Haddon F. King. 300pp. $A45.

Jan 1, 1990

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By J. B. Hess, R. L. Dietrich

IN the mechanical twinning of magnesium on the {1012} planes the crystallographic deformation is such that, in the direction of the hexagonal axis [0001], twinning is possible only under tension stress, while in the directions perpendicular to the hexagonal axis, twinning is possible only under applied compression. Thus in extruded magnesium and magnesium alloys where the extruded textures are best described as either [1010] or [ 1120] fibers,1 the basal planes are all nearly parallel to the extrusion axis and such material is susceptible to {1012 } twinning by compression in the direction of the extrusion axis. In order to explain the results of cyclic stressing in alternate tension and compression upon the tangent elastic modulus in such material, Dorn and Thomsen2 have postulated that, following twinning under applied compression, a retwinning or untwinning occurs as a result of residual microtensile stresses immediately upon removal of the applied compressive force. Recently, Carapella and Shaw3,4 have used this supposition of untwinning in magnesium in discussing their results on indentation hardness and on cold drawing of MI sheet. In trying to confirm this hypothesis by suitable direct experiments, the authors have been unsuccessful in detecting any evidence whatsoever that untwinning follows the release of applied compression and are forced to conclude that this hypothesis is improbable or, at least, that the quantity of material involved is small. For the experiments, small cylindrical specimens 0.040-in. diam. X 0.120- to 0.140-in. long were etched from 0.0625-in. extruded rod. The ends of the specimens were accurately faced off parallel in a jeweler&apos;s lathe. The compression jig was simply an ordinary set of micrometer calipers with an anvil interposed between the spindle and the specimen. The anvil was free to move axially but restrained from rotating so that the rotation of the spindle would not introduce a twisting stress on the specimen. With this arrangement the compressive strains could be estimated to 0.0001 in. and X ray pinhole photographs could be taken with or without load as required. Fig 1 is the pattern of an uncompressed specimen of AZ31 alloy, showing the approximate [1010] extrusion fiber. The X ray beam is normal to the extrusion axis; in this position it is particularly sensitive in detecting twinning if one directs his attention to the diffraction ring from the basal plane. Since twinning on {1012} planes produced an 86° reorientation of the crystal lattice, the original basal reflections occur at the 3 and 9 o&apos;clock positions while the (0002) reflections from any twinned material will occur at the 6 and 12 o&apos;clock positions. Fig 2 shows the same specimen compressed 3.0 pct, photographed while still under load. This strain has been just enough to produce a detectible amount of twinning and the sensitivity is roughly indicated by the fact that no alterations were produced in the intensities or maxima of the other diffraction rings. A strain of

Jan 1, 1948

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By T. G. Lovering

Nonparametric statistical tests have practical application to many geological problems because, unlike the standard statistical tests, they do not require assumptions regarding the form of the population frequency distribution. Many of them do not even require that the variable be susceptible to numerical measurement. These tests are useful either 1) for geological data representing population distributions of unknown form, or otherwise not meeting the requirements for standard parametric tests; or 2) for sample attributes that cannot be measured but only ranked in order of relative magnitude. The application of two such tests will be illustrated. The Kolmogorov-Smimov test will be used to test for significant differences in copper distribution in samples of two rock types; the Spearman rank-correlation method will be used to determine whether there is a significant association between intensity of rock alteration and copper content of the rock. Nonparametric tests are, in general, quicker and easier to perform than the corresponding parametric tests, and they may be applied to a greater variety of data. They are not as powerful as the standard tests if used on data to which the latter are applicable, and computer programs utilizing them are not generally available. The use of standard or parametric statistical procedures for the interpretation of measured geological data is familiar to most mining engineers and explora- tion geologists. The computation of product moment correlation coefficients on sample assays for more-than one component is already standard procedure in some company operations, as is the use of Student&apos;s F test and Snedecor&apos;s F test for the comparison of means and variances of sample groups. The application of these three tests is limited by the prerequisites that the samples must be random, independent representatives of normally distributed populations and that the variables involved must be measurable. If such tests are applied to data which fall short of fulfilling these prerequisites, then the probability level attributed to the computed statistic is invalid and the conclusions based thereon may be erroneous. A number of nonparametric, or distribution free, statistical tests have been developed for use with data which are not amenable to standard parametric procedures. These tests have been widely used in the behavioral sciences such as psychology and sociology for some time, but their application to geologic problems is relatively new. Nonparametric tests may be grouped into two main categories: those which test for significant differences in a single variable by comparing either sample values with a standard value or representative values between two or more groups of samples; and those which test for significant association between pairs of variables in a single group of samples. The versatile chi square test, the Kolmogorov-Smirnov one and two sample tests, the Wilcox matched pairs signed ranks test, the median test, the Mann-Whitney U test and the Cochran Q test are examples of nonparametric tests with demonstrated or potential geological applications that belong in the first category. The contingency coefficient, Spearman rank correlation coefficient, Kendall rank correlation coefficient and the

Jan 1, 1963

By Ward C. Smith

The industry of producing and processing boron compounds is called the borax industry because the chief product is borax, the decahydrate of disodium tetraborate. For the same reason, it is common to speak of borax mining. Reference to borate mining also is common, and while appropriate where it emphasizes the diversity of borate minerals that are mined in various countries, it is rather unsatisfactory where used in a general sense, because it seems to exclude the important production of borax from brine at Searles Lake, California, and of boric acid from steam vents in Tuscany, Italy. The terms "boron industry" and "boron mining" might seem more comprehensive, but are little used, and this is fortunate because they would be misleading-the element boron is manufactured only in small amounts for special uses, and it is not found free in nature. In most occurrences, boron is combined with oxygen and is in a borate or borosilicate material. The history of the modem borax industry starts with the introduction into Europe of borax from Tibet in the 13th century, about the time of Marco Polo, if not actually by him. The discovery that borax has unique value as a flux in metal soldering and ceramic glazing must have been made at some unknown time much earlier. As a rule, any mineral that has been used so long that its early history is lost must occur in deposits that are easily recognized and worked, and this is undoubtedly true of borax in Tibet. According to meager accounts,9 the borax occurs there in arid mountain basins as surficial crusts that coat the ground about thermal springs and seeps of mineralized water, and as coarser crystals in the bottom muds of shallow pools and lakes. Much the same essential features of surface exposures and minerals easy to recognize and recover characterize most of the deposits later found and worked elsewhere. The borax industry at the present time is faced with rising demands for its products, and consequently is increasing its productive capacity and appraising its borate resources.18 The areas that contain the known borate deposits are most likely to yield additional production, hence their distribution in the world is of interest, and is summarized later in this chapter. Mineralogy The mineral raw materials used by the borax industry include various borates mined in several countries, borax extracted from brines at Searles Lake in California, and boric acid extracted from the steam of vents in Tuscany in Italy. The hydrated borates[$] of chief commercial importance are listed in Table 1, which also shows their chemical composition. The properties of only the four most important borates are summarized here, but detailed descriptions of the borates and the minerals commonly found with them can be found in mineralogy textbooks.41 Ulexite generally forms clusters of silky fibers rather than large individual crystals. A

Jan 1, 1960

By A. M. Gaudin, C. S. Chang

Adsorption was measured for barium ion and laurate radical, using radioactively marked agents, over wide range of concentrations. Laurate adsorbed in absence of barium fails to float. With barium, flotation-effective laurate coating needs not exceed 5 pct of monolayer. Barium adsorption then is several fold larger. No barium laurate coating is obtained. IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.&apos;-&apos; The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods."-" In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba" to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,&apos; were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand-picked quartz, washed free of stains, were reduced in size to —20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This —200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.&apos; The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74-micron quartz particles, using a surface factor of 1.96; is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1953

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 E. R. Morgan, J. C. Shyne, V. F. Zackay

NITROGEN used as an alloying element in steel has received increased attention in recent years. Its merit as an austenite stabilizer and hot strengthener has long been recojinized, particularly by European investigators.&apos; Recent work&apos; indicates that nitrogen contents of 1/2 pet or more allow the addition of several percent of ferrite-forming hot strengtheners, such as molybdenum, without subsequent austenite decomposition at elevated temperatures. The room temperature properties of such alloys are characterized by high yield and tensile strengths with excellent ductility, even after cold working, as shown in Tables I and 11. The 1350°F creep-rupture properties of Cr-Mn-Mo-N steels are comparable to those of commercial alloys such as Timken&apos;s 16-25-6, containing 16 pct Cr, 25 pct Ni, and 6 pct Mo, as shown in Table 111. Cr-Mn steel containing 1/2 pet N must be made under pressure if ingot gassing is to be avoided. However, there are difficulties attendant to this practice. Pressure melting restricts the ingot size, and the equipment required is costlier and more complicated than comparable air melting facilities. An effort was made, therefore, to determine more economical methods of adding nitrogen. The pressures generated in centrifugal casting usually range from 5 to 10 atm and are sufficient to prevent the gassing of high nitrogen Cr-Mn steels. A centrifugal casting was made of an alloy containing 16 pct Cr, 18 pct Mn, 2 pct Mo, and 0.73 pct N. A risk, 8 in. diam and 11/2 in. thick, was cast at 1000 rpm. It has been calculated that a pressure of 9 atm was developed at the periphery of the disk at this speed. Metallographic inspection of specimens taken from the disk revealed no gas holes or other defects. The elevated temperature properties of radial and circumferential specimens taken from this casting are given in Table IV. The creep-rupture life of this cast nickel-free austenitic steel was equivalent to that of the wrought Cr-Mn-Mo-N steels. Although centrifugal casting appears to lend itself to the manufacture of high nitrogen austenitic steels, its applicability is limited to relatively small sizes. A process applicable to the production of large ingots of high nitrogen steels is suggested by low carbon rimming steel practice. Gas holes formed during ingot solidification are not detrimental so long as they weld shut during hot rolling. An economic advantage of gassing ingots is the increased ingot-to-slab yield, especially if the ingots are mechanically capped. Also, it is probable that higher nitrogen levels can be achieved with mechanically capped ingots than with hot-topped ingots. A series of gassy heats was made under both atmospheric and higher pressures, as indicated in Table V. Several of the air melted ingots were mechanically capped by chilling the molten ingot tops with a steel plate. The ingots were allowed to freeze in steel molds without hot-tops unless otherwise indicated. A comparison of Table 111 with Table V shows no significant difference in the creep-rupture properties of the gassy and the nongassy ingots after hot work- ing nor between the gassy ingots produced under different conditions. References 1 F. Rapatz: Application of Stainless and Heat Resisting Steels Alloyed with Nitrogen. Sinhl and Eisen ( 1941) 61, pp. 1073-1078. &apos;V. I?. Zackay, J. F. Carlson, and P. L. Jackson: High Nitrogen Austenltlc Cr-Mn Steels. Trans. ASM 119551 48, PP. 509-523.

Jan 1, 1957

By L. D. Wooddy, W D. Moore

Water drives may be natural or artificial. For the case of a natural water-drive reservoir, the volume of water influx corresponding to reservoir pressuve-production history may be calculated by means of the material bal-ance-unsteady state equation. For the artificial water drive or pattern injection water flood, the material balance equation is sufficient to determine the reservoir pressure-production, injection history. However, for both cases to reliably predict reservoir performance, it is necessary to calculate the saturation distribution of the reservoir fluids at different stages of depletion. This paper consolidates the various equations used to determine the performance of water-drive reservoirs into one approach that is applicable to any reservoir that has a natural water drive or is to be produced by water injection. The numerical procedure has been simplified considerably, and the solution is adaptable to either hand calculations or digital computer operation. INTRODUCTION A water-drive reservoir is one in which the predominant source of energy for production of oil results from the encroachment of water into the oil zone. The water drive may be either natural or artificial. Water invasion takes place by expansion of water in the aquifer as a result of the pressure decline transmitted from the oil reservoir. Because water is practically incompressible, a natural water drive requires an extensive aquifer containing a volume of water many times the volume of oil in the reservoir. Provided the permeability of the formation is reasonably high, a moderate decline of reservoir pressure usually causes adequate water influx. If the reservoir pressure decline becomes excessive because of low permeability or a high rate of production, part of the oil production may result from the liberation of dissolved gas which may cause excessive quantities of free gas to be produced along with the oil. In extreme cases, reservoir pressure may decline so rapidly as to cause the oil to be produced predominantly by dissolved gas drive, leading to abandonment of the reservoir before the advancing water has had a chance to flush the entire reservoir. In reservoirs that are not connected to extensive aquifers, an artificial water drive may be created by injecting water into or around the lower edges of a reservoir. Sometimes water is injected within the reservoir through wells interspersed among the producing wells. When injection is carried out in such fashion, the reservoir is in effect subdivided into a number of separate producing segments, in each of which the displacement of oil is simultaneously taking place, and the shapes of which are fixed by the well patterns employed. Because of the natural tendency of oil and water to segregate according to their relative densities, water will tend to migrate downdip regardless of where injected. Accordingly, the injected fluids can be retained within the intended reservoir segments only when conditions are unfavorable to their migration under the force of gravity. Pattern injections are usually confined, therefore, to reservoirs having low structural relief, or low permeability, or when production and injection rates are such that fluid movements in the reservoir are dominated by the pressure gradients rather than by the force of gravity. In the case of natural water-drive reservoirs and artificial water-drive reservoirs in which the water is in-

Jan 1, 1958

By J. D. Price, W. M. Bertholf

Making maximum possible use of available equipment and material, CF&I placed a high-efficiency, high-capacity washery unit in the existing buildings to gain simplified operation, reduced manpower requirements, raised efficiency, and boosted production. THE central washing plant of the Colorado Fuel & Iron Corp. was first operated in 1918 to furnish coal for two 60-oven batteries of Koppers design. Prior to that time the coke for the blast furnaces had been secured from a number of beehive operations, some with their own washeries. The original washery had four Elmore jigs, which did not do as well as had been expected. In 1923 the jigs were taken out and replaced by Deister Plat-O tables, with various changes in auxiliary equipment. In 1936 the throughput of the plant was considerably increased by the installation of vibrating filters for recovery and drying of fine coal, thereby reducing a large recirculating load of fine coal which passed through the screens of the Carpenter driers. In the late 1940&apos;s it became evident that something would have to be done to keep the washery abreast of progress at Pueblo and other washeries. Coal requirements were nearly two and one-half times the original requirements of the 120 small ovens, as additional ovens had been built in 1930, 1938, and 1945, whereas no additional coal washing capacity had been added since the 1936 modifications. Much of the equipment, moreover, had seen better days. One answer to the problem was to build a new and completely up-to-the-minute plant, with sep- arate sections for coarse, medium fine, fine, and very fine coal. On the other hand, it might be financially more profitable to place a high-efficiency, high-capacity unit in the existing buildings. The washing problem at Pueblo is not unique, but it is approached differently. There are no established specifications for coke ash and sulphur. The plant is operated on the principle that if it is more economical to wash it out than to slag it out, wash it out; otherwise, send it on to the blast furnaces. With coals at the Pueblo plant costing what they do, the benefits of washing at a low gravity are questionable. Hence the primary problem is to eliminate the high-ash components and retain all the low and medium-ash components. Sulphur is no problem at all, averaging 0.6 pct in the coke. Since a good proportion of the free impurity in the coals is as large as the coal or bone or larger, it appeared that it would be safe to go to jig washing and discontinue crushing the coal before washing, as had been the practice with the tables. This would boost the throughput. It might also decrease manpower requirements and washing costs considerably. It was assumed at the start and has been demonstrated in the first year of operation that a jig will do as well on the fines as the tables had been doing. It would not be necessary to discount any gains due to increased efficiency in washing the coarse material because of incapacity to wash the fines. By washing at —2+0 mesh it would be possible to dewater, by screening, a considerable tonnage satisfactorily, for example, at —2 + % or —2 + l/4, and then crush it in a hammer mill. The —?+20 could be dewatered in centrifugal driers and the remain-

Jan 1, 1955

By J. M. Smith, D. Kunii

Effective thermal conductivities of sandstones filled with stagnant fluids were measured using a steady-state technique. Data were obtained for seven sandstone samples, taken from four different locations and ranging in permeability from 18 to 590 md. The measurements with gases (helium, nitrogen, air and carbon dioxide) covered a pressure range from 0.039 psia to 400 psig. Data were taken for four liquids — n-heptane, methyl alcohol, 79.8 weight per cent glycerol-water solution and pure water at atmospheric pressure. The experimental results were used to evaluate the theoretical equations for predicting stagnant conductivities developed earlier 4 The low-pressure measurements permitted evaluation of the consolidation parameter bpDp/ks (necessary to utilize the theory) for the various types of sandstones. Using these characteristic values, the tbeoretical equations correlated well with the experimental conductivity data for the several fluids and rock samples. INTRODUCTION An aspect of heat transfer in solid-fluid systems of considerable current interest is the effective thermal conductivity of porous media. The stimulus for study of the subject arises from the need for sound procedures for designing thermal methods of petroleum production. The general system occurs when there exists a flow of fluid through the pores of the solid material. However, a logical starting point in developing a theory for predicting the effective thermal conductivity in the general system is to attack the special case when the porous solid is filled with stagnant fluid. Since the flow rates anticipated in thermal production processes are very low, such stagnant conductivities k,O are also of practical significance. Kunii and Smith4 recently reviewed the existing data for stagnant conductivities and proposed a theory for heat transfer in porous rocks. This leads to equations for predicting the stagnant conductivity as a function of the properties of the fluid and solid phases. The existing experimental information1-3,5,7,8 covered a range of porosities and agreed well with the theory. However, the available data were insufficient to examine critically the effects of two important properties on koe, — the thermal conductivity of the fluid and the pressure. The objectives of the present study are twofold: (1) to measure the effect on koe of (a) the pressure for gases, and (L) the thermal conductivity of the fluid kg for bloth gases and liquids; and (2) to determine for rocks of different porosities and permeabilities the apparent solid conductivity ks and the consolidation parameter bpDp/ks required in applying the theoletical equations. Measurements extrapolated to zero pressure are helpful in evaluating ks and the consolidation parameter. However, the extrapolations must be based upon data obtained at low pressures because in small pores the molecular conductivity of the fluid may be unusually depressed. This occurs when the mean free path of the molecules is of the same order of magnitude as the pore diameter, that is, in small-diameter pores at low pressures. The phenomenon has been studied recently by Schotte6in beds of unconsolidated fine particles. With particles in the size range of 45 to 200 microns, a significant reduction of kg with pressure was found even at absolute pressures greater than 1 atm. In the sandstones employed in the present investigation, pore diameters lower than those experienced by Schotte are likely, so that the effect would presumably be greater. SCOPE OF MEASUREMENTS Stagnant conductivities were measured for four types of sandstones using a total of seven samples. The characteristics of the samples, including porosity and permeability values, are given in Table

By P. E. Baker

Approximate solutions are presented for the heat-flow equations in a loss-free linear system with a moving source and with heat transfer by convection and conduction, representing in situ combustion in an oil reservoir. The rate of heat generation and the velocity vf of the source (flame front) are assumed constant. A cold front or convection front caused by the cooling effect of in-jected air develops behind the flame front and moves with velocity vc, which is determined by the thermal properties of the air and rock. Because of thermal conduction the fronts are not sharp; i.e., they do not represent temperature discontinuities. The following solutions apply after a sufficiently long time. where Q is heat generated per unit volume of formation, k is thermal conductivity, CF is volumetric heat capacity, a is thermal diffusivity, and subscripts 1 and 2 refer to values behind and ahead of the flame front, respectively. The parameter CF2 is contained in v . Te is initial reservoir temper- . C2 e ature and air-injection temperature. Other mathematically possible solutions are presented. The different solutions result from the use of different values for various physical parameters. The solution just presented is thought to be most commonly applicable. INTRODUCTION In this paper, approximate analytical expressions are derived for the temperature profile developed in the underground combustion method of oil recovery. A qualitative description of the process may be found in a paper by Tadema.1 The flame front is regarded as a moving source with a constant rate of heat generation. Heat transfer is by conduction and convection. Previous publications, of which a few are cited here, 2-5 have also attacked this problem and have presented solutions pertaining to different methods of approximating or idealizing the process studied. The present paper also treats an idealized case: linear flow is assumed for heat and fluids, and vaporization and condensation effects are neglected. The results obtained are similar to those derived by Bailey and Larkin,3 but are obtained by an entirely different procedure. The method used here should give considerably greater insight into the physics of the in situ combustion process. Four types of cases are considered, distinguished by thermal and fluid-flow properties of the system. A constant rate of heat generation and constant rate of flame-front advance are assumed. Flame-front temperature is determined for each case using a heat balance which involves the entire temperature profile. The applicability of the different solutions to real systems is discussed after they are all presented. Again, this is done for the purpose of understanding better the physics of the process. Consideration of the nonapplicable solutions and of the reasons for their not applying is significant. In a paper by Cooperman,4 the only case solved is one considered here as not applicable. Fluid flow, as such (pressures, saturations, oil recovery, etc.), is not treated. This subject has been covered in a paper by Wilson, et al.6 Also, we are not concerned with requirements for continuance of the process; we only attempt to determine the temperature history for cases where the process has continued for some time. PHYSICAL SYSTEM AND APPROACH TO PROBLEM A linear flow (heat and fluid) system is assumed and the x-axis is taken parallel to the flow direction. The combustion zone (flame front) is vertical,

By L. Zwell, H. A. Wriedt

X-ray Lattice parameter and bulk density measurements were made at room temperature on solid solutions of nitrogen in purified a, iron, containing from 0 to 0.053 wt pct N. When nitrogen is dissolved in a, iron, the fractional increase in unit cell volume (X-ray diffraction) and the fractional increase in volume per gram of iron (bulk density measurement) are the same within experimental error. The two sets of results when averaged show that the unit cell edge of a, iron increases linearly by 3.2 X 10-2 A per wt pct N dissolved and that the partial gram-atomic volume of nitrogen at infinite dilution in a, iron is the same as it is in nitrogen-martensite, that is, 5.90 cm3. RECENT reviews17&apos; of literature dealing with the lattice parameter of ferritic iron-nitrogen alloys indicate that the dilating effect of dissolved nitrogen on the bcc unit cell of a iron is not known with confidence. Five investigations3-7 either revealed no effect of nitrogen or were inconclusive. Among other investigations, where quantitative data were obtained, the results of Osawa and Iwaizumi8 indicate too large an effect, and those of Eisenhut and Kaupp9 show the lattice parameter of ferrite varying with the nitrogen content at concentrations far beyond the known solubility limit. It is not clear in Burns&apos;10 data what value should be used for the lattice parameter of nitrogen-free ferrite in calculating the dilation. Burdese11 shares with Burns the shortcoming that the iron-nitrogen alloys were solution-treated and quenched with undissolved nitride present. The consequence is that the un- certainties in the solubility limit1 are added to those in the lattice parameter measurements when the variation of lattice parameter with nitrogen content is computed. For a system of such widespread interest, we felt that a new investigation was merited. Both X-ray diffraction and bulk density measurements were used to determine the dilation of the , a iron lattice by dissolved nitrogen. EXPERIMENTAL PROCEDURE Material. The bulk density and X-ray diffraction experiments were both made with specimens of a purified iron (denoted as "B iron")- from Battelle Memorial Institute. The impurity contents were as follows: As, C, Cu and Pb—50 ppm; Ag, Al, Co, Ga, 0, Ti-11 to 50 ppm; B, Be, Ca, Cd, Cr, Mg, Mn, Mo, N, Ni, S, Sb, Si, Sn, V, W-10 ppm or less. The vacuum-cast ingot was hot-forged and annealed. Pieces of the forged stock were machined and cold-rolled to give strip stock 0.08 and 0.002 in. thick for density and for X-ray measurements, respectively. Preparation of Specimens. Starting with a piece of the cold-rolled iron stock, the general sequence of operations, after an initial recrystallizing anneal, was to measure the density or lattice parameter, nitrogenize, remeasure the property, age or denitrogenize, and again measure the property. Duplicate analyses for nitrogen were made by a modified Kjeldahl method on portions of the actual density specimens and on pieces nitrogenized to equilibrium alongside the X-ray specimens. Annealing of the density specimens was performed by sealing the pieces with the as-rolled surfaces removed by filing into evacuated "Vycor" capsules and treating for 1 hr at 750°C followed by furnace cooling. (TO check the effect, if any, of annealing procedure, a specimen also was

Jan 1, 1962

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

Warren and Averbach&apos;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