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By Robert E. Bush, E. S. Mardock

The objective of this paper is to present practical methods of applying radioactivity logs to problems of interest both to those engaged in evaluating fundamental reservoir data as well as to those engaged in subsurface structural work. The basic theories underlying the operation of radioactivity logging methods are briefly discussed along with some of the problems arising in the interpretation of the log. Relative methods of quantitative interpretation are described, with a discussion of relative reference lines and specific examples are given showing the application of these relative quantitative interpretation methods. To show the variation of the methods described, specimen wells penetrating formations widely divergent in point of geologic age were selected to demonstrate the application. A relative reference line is determined for the Neutron Curve and by comparison to known petrophysical data such as porosities from diamond cores, a direct quantitative relationship is developed. The application of this relative calibration curve to logs of unknown wells will permit a reasonably accurate determination of porosity in limestone and dolomite formations. Specific examples are given showing the application of these relative methods of interpretation to logs of the Smackover limestone in Louisiana, the Edwards limestone and dolomites of South Texas, and Permian dolomites of West Texas. Radioactivity logs have been used extensively by the petroleum industry for a number of years and recognition of their value has grown steadily, not only as tools to aid in the solution of specific stratigraphic problems, but also as potential sources of the basic data necessary for the estimation of net pay and reserves. The value of radioactivity logs for stratigraphic work has been pointed out in the literature,1,2,4,5,6 and now has long been recognized by the industry, but the quantitative application of the logs has advanced but little beyond the stage of a strong conviction that radioactivity logging curves will some day provide the information on such important quantities as the porosity and the liquid saturation of the formations. During the past few years the staffs of the Lane-Wells Company and Well Surveys, Incorporated, have devoted a great deal of time, thought, and experimentation to the relationships existing between radioactivity curves and the lithologic conditions encountered, and this paper is, in a manner of' speaking, intended as a progress report of this work and includes suggestions which the authors have found useful in the interpretation of radioactivity logs. The section on theory is not intended as a complete exposition of the physical processes involved, but rather as a brief introduction to the reader of these processes so that he may acquire a better understanding of the behavior of the radioactivity curves under the varied conditions encountered in normal well logging. Three relative methods for using neutron logs for the quantitative estimation of porosity in limestone or dolomite are presented. These methods are based on the comparison of logs and porosity data from wells in Louisiana, South Texas, West Texas, and New Mexico. These areas were selected because not only were there more core data available from these areas but also the majority of these data were from limestone or dolomitic zones. The correlation between core data and logs is simpler for limestones and dolomites than it is for sandstones due to the fact that sandstones are more complex than limestones and differ more widely among themselves as to composition of cementing materials, siltiness, etc. When data applicable to the various types of sandstones are available, the authors hope to present a discussion similar to this paper covering sandstones or possibly a more general discussion covering all types of reservoir rocks. The relative methods for estimating porosity which are presented in this paper fall short of the absolute method sought. However, these methods possess the advantage that they can be applied to almost any neutron log as long as the range of application is held within the limits imposed by the local lithologic conditions which prevailed during calibration, i.e., these methods are for short range application only. THE THEORETICAL BASIS FOR RADIOACTIVITY LOGGING The two redioactivity logging curves commercially available today are the

Jan 1, 1950

By Thomas Read

AMONG the large number of deep mines in the world there are several which do not differ much in depth. The St. John del Rey mine, in Brazil, has reached a vertical depth of 6726 ft. below the top of its shaft; miners enter it, however, through an adit which intersects the shaft 324 ft. below its top, wherefore it might be said that the mine is really only 6400 ft. deep. In the Kolar gold field of India there are a number of deep shafts, one of which reaches to a vertical depth of 6140 ft. below surface. In South Africa also there are a number of deep shafts, the Village Deep being 6100 ft. early in 1921. The City Deep, Ltd., proposes to sink to a depth of 7000 ft. but pre-sumably by the time it does so the St. John del Rey will be deeper than that, since it has been increasing in depth at an average rate of about 150 ft. per year. The deepest shaft in the United States, the Tamarack No. 5, although it is only 5308 ft. deep, actually approaches nearer to the center of the earth (4100 ft. below sea level, as against 3958 ft. , at St. John del Rey). The deepest workings in the Calumet & Hecla go down to 4600 ft. below sea level. The St. John del Rey is not only the deepest, mine in the world, but it also is worked by the oldest registered English mining company, which was organ-ized in 1830 to work a mine at a considerable dis-tance from this one. That mine proved unprofitable, and in 1837 operations were transferred to the. deposit now under discussion, where operations have been prac-tically continuous ever since.

Jan 6, 1923

By S. M. Purdy

Under certain conditions of hot rolling and air cooling from the hot-rolling temperature, bars of a high carbon (0.40 pct C) chrome-nickel austen-itic alloy were found to show magnetism even though no ferrite or martensite could be detected by microscopic or X-yay methods. The appearance of magnetism in such alloys may come from chromium impoverishment of the austenite grains near the precipitated carbide particles. SPORADICALLY, hot-rolled bars of Silchrome 10, an exhaust valve steel, have been found to be magnetic. Because of the analysis of the alloy—0.40 pct C, 18 pct Cr, 8 pct Ni, 3 pct Si —magnetism is unexpected. Preliminary investigation showed neither martensite nor ferrite to be present; only austenite and Cr23C6. Since a literature search was fruitless, a brief study was made of the appearance of magnetism in this alloy. The only basic difference between the two heats is the nitrogen content. Permeability was measured using a Severn magnetic gauge. This instrument consists of a magnet mounted on a counterbalanced arm. A set of calibrated plugs is placed in contact with one pole of the magnet. The specimen is placed close to the other pole of the magnet. If the specimen pulls the magnet away from the plug, it has a permeability greater than that marked on the plug. This technique is swift and reproducible. Previous experience has shown that the permeabilities obtained corresponded to those obtained on a permeater with a field strength of 100 oe. Specimens from both heats were annealed at temperatures between 1700 and 2300°F. One set of specimens was water cooled and another furnace cooled. All the water-quenched specimens were non-magnetic; the furnace cooled ones were magnetic as shown in Table I with no difference being observed between the two heats. Microstructural examination of the specimens showed the expected increase in carbon solubility with increasing temperature. Carbide solution was complete at 2200°F. The specimens heated to 1900°F or below showed some carbide precipitation from the hot-rolled structure. A furnace cooled specimen from a given temperature showed less carbide out of solution than the water-quenched specimen from the next temperature below; e.g., the specimen furnace cooled from 2100°F showed less carbide out of solution than the water-quenched specimen from 2000" F. These studies indicated that the appearance of magnetism was not related to the quantity of carbon in or out of solution and it was related to precipitation at temperatures below 1700" F. A set of samples annealed and water-quenched from 2100° F was aged for 4 hr at temperatures between 1000" and 1600°F; all were non-magnetic. A second set of samples, similarly annealed, was aged 1 to 24 hr at 1200°F with the results shown in Table II. None of the latter set of specimens showed magnetism until they had been aged about 8 hr. Magnetism was quite strong after aging 24 hr. X-ray diffraction studies on several of the magnetic specimens showed that the austenite had a lattice parameter of 3.58A and that the carbide was Cr23C6. Several of these samples were electrolytically digested in 10 pct HCl in ethanol, with a current density of 0.1 amp per sq cm. None of the particles in the residue were magnetic. Accidentally, one cell was run at 1 amp per sq cm; e.g., magnetic particles were found in this residue. After careful separation, the magnetic particles were mounted on a quartz fiber and their diffraction pattern determined using a 5.73-in. Debye-Sherrer camera with CrK radiation. These particles showed a fcc structure with a lattice parameter of 3.57A. Prolonged exposure, up to 16 hr, produced no other lines on the film. The following facts seemed to be established at this time: 1) Austenite was the magnetic phase. 2) Neither ferrite nor martensite could be detected. 3) Magnetization could be produced by aging at 1200°F. One explanation of these data is that the carbide precipitation impoverishes the region immediately around the carbide particle of carbon and chromium and increases the proportion of nickel. All of these serve to increase the Curie temperature of the region around the carbide particle. If the composition change is enough, the Curie temperature will rise above room temperature. If the volume of the affected region is great enough, the magnetism will become detectable. At low aging temperatures, composition changes are great enough but the overall volume of impoverishment is quite small

Jan 1, 1962

By Philip Davidson, Wm. B. Price

The object of this paper is to present, a survey of some of the physical properties of sheet nickel silver when subjected to cold rolling and when annealed at temperatures extending from 350" C. throughout the coininercial annealing range.. A number of alloys were taken from stock and analyzed. Four of these, representing low nickel and high nickel both with and without lead, were chosen for the tests. The analyses were as follows: Alloy Copper, Lead. Iron. Nickel, ManGanese, Zinc, PeR Cent. Per Cent. Per Cent. Per Cent. Per Cent. PEr Cent. A................ 64.68 Trace 0.194 6.73 0.06 remainder B................ 65.82 1.27 0.227 6.17 0.06 remainder C................ 65.44 Trace 0.345 17.83 0.08 remainder D................ 65.60 1.08 0.238 17.77 0.06 remainder These alloys were lolled in accordance with regular mill practice to approximately No. 6 R. & 6. gage. The bars (which were then coiled) were annealed together in a mill muffle and afterwards pickled in a 10 per cent. sulfuric-acid solution and cold rolled in stages of approximately one number (B. & S.) at a time to No. 18 B. & S. gage. After each stage, suitable samples were set aside for physical tests. Additional samples were chosen for tests after the bars were rolled to Nos. 8, 10, 12, and 14 gage. These samples were annealed together in the mill muffle and, after pickling, were finished on 0.050-in. gage, yielding a series of specimens 2, 4, 6, and 8 numbers hard for the subsequent annealing tests. Tensile test pieces 9 by 1 in. (22.9 by 2.5 cm.) were cut from both lots and the central portion was milled to give a test section 2 1/2 in. long by 1/2 in. wide. A distance of 2 in. was marked off on the edge of each specimen with light punch marks. In the case of the annealed alloys, Erichsen test pieces 4 by 235 in. were also taken.

Jan 1, 1921

By Wm Price

THE object of this paper is to present a survey of some of the physical properties of sheet nickel silver when subjected to cold rolling and when annealed at temperatures extending from 350° C. throughout the commercial annealing range. A number of alloys were taken from stock and analyzed. Four of these, representing low nickel and high nickel both with and without lead, were chosen for the tests. The analyses were as follows: ALLOY COPPER, LEAD, IRON, NICKEL, MANGANESE, ZINC, PER CENT. PER CENT. PER CENT. PER CENT. PER CENT. PER CENT A 64.68 Trace 0.194 - 6.73 0.06 remainder B 65.82 1.27 0.227 6.17 0.06 remainder C 65.44 Trace 0.345 17.83 0.08 remainder D 65.60 1.08 0.238 17.77 0.06 remainder These alloys were rolled in accordance with regular mill practice to approximately No. 6 B. & S. gage. The bars (which were then coiled) were annealed together in a mill muffle and afterwards pickled in a 10 per cent. sulfuric-acid solution and cold rolled in stages of approximately .one number (B. & S.) at a time to No. 18 B. & S. gage. After each stage, suitable samples were set aside for physical tests. Additional samples were chosen for tests after the bars were rolled to Nos. 8, 10, 12, and 14 gage. These samples were annealed together in the mill muffle and, after pickling, were finished on 0.050-in. gage, yielding a series of specimens 2, 4, 6, and 8 numbers hard for the subsequent annealing tests. Tensile test pieces 9 by 1 in. (22.9 by 2.5 cm.) were cut from both lots and the central portion was milled to give a test section 2 ½ in. long by ;Z in. wide. A distance of 2 in. was marked off on the edge of each specimen with light punch marks. In the case of the annealed alloys, Erichsen test pieces 4 by 2 1/2 in. were also taken.

Jan 10, 1920

Furnace Builder. Engineer with extensive experience in furnace building. Position with well-established firm, branching into new fields. Location Ohio. 11-1343. Erecting and Operating Engineer to take charge of erection of gas-producer equipment and to teach customers how to operate such equipment. Location Ohio. Salary $250 per month. R-1339. Assistant Professor in Mining School, for instruction work; must have had experience in ore dressing and metallurgy. Location Missouri. Salary $1500-$2100 per school year (8 mo.). R-1332. Consulting Engineer, familiar with construction of artesian wells to act in a consulting capacity. Location New York City. R-1324. Mining Engineer and Investigator to do non-metallic mineral investigations in both field and office for United States Government. Position will last at least a year, and may become permanent. Location Washington, D. C. Salary $1800-$2700 depending on qualifications of appointee. R.-1317. Crushing Plant Superintendent, cement mill and construction experience essential. Prefer man who has had limestone crushing experience. Location New York. R-1314. Assistant Professor of Coal Mining, must be a graduate of mining engineering and have had some coal mining experience. Location Philadelphia.. Salary $2200 for school year of 10 months. R-1312.

Jan 9, 1919

By D. A. Koss, R. O. Gordon

Changes in the ultrasonic attenuation in steel specimens have been observed during tensile tests. Samples of AISI 1020, 1045, and 1095 steel quenched and tempered to a spheroidized condition have been used. Both attenuation and microstrain measurements fail to reveal preyield dislocation motion in the as-tempered specimens. Upon reapplication of the load to samples in the strain-aged condition there is a large preyield attenuation increase but no observable micvostrain up to 90 pct of the flow stress. These and other observed changes can be related to changes in the free disloca-tion density and the average dislocation segment length. The results show that the increase inflow stress in the strain-aged condition is caused by increased fric-tional stresses rather than by dislocation pinning. Strain aging is found to proceed through three distinct stages. The second of these follows the t2,3 law and is characterized by an activation energy of 20 kcal per mole. RECENT years have seen substantial progress in the understanding of the sharp yield-point phenomenon in metals; the influence of solute atom pinning of dislocations, of dislocation multiplication, and of the stress dependence of dislocation velocity on the stress-strain curve has been investigated. Evaluation of the relative importance of these factors in the various metals and alloys is not complete, however, because observation of the stress-strain curve alone is not sufficient to determine the yield mechanism. In the experimental study of the sharp yield point it would be desirable to be able to directly observe the dislocations in a bulk specimen. Ideally, the observations should be made during deformation because of the rapidity of recovery processes in lightly strained metals. While direct observation of dislocations under these conditions is not possible, certain physical properties sensitive to the dislocation structure can be observed while a test specimen is undergoing deformation. Of these properties, one of the most useful is the ultrasonic attenuation. The total observed attenuation, a, is due to a number of causes: acoustic diffraction, scattering by inhomogeneities in the structure, heat flow, magnetostriction, and dislocation damping. Satisfactory measurements of the absolute a are difficult to make because all of these factors cannot be evaluated in any given specimen, but changes in a due to changes in the dislocation contribution alone can be reliably observed by appropriate technique. Because dislocation damping is sensitive to small concentrations of long, free dislocation segments, observation of acoustic attenuation due to dislocations is particularly useful in the study of the early stages of plastic deformation. In the experiments to be described, acoustic-attenuation measurements have been made on steel samples as these were pulled through their yield in tension. While many details of dislocation-damping phenomena in the bee metals remain obscure, the main characteristics of this type of internal friction are established. At low strain amplitudes and at frequencies well below that of dislocation resonance (the conditions of these experiments) the dislocation contribution to a is given by1 where A is the density of freely oscillating dislocation segments, L is the average segment length, B is the damping constant for a moving dislocation, w is the frequency, O is an orientation factor, C is the dislocation line tension, and t is a numerical factor relating average segment length to the distribution of lengths. Because of its fourth-power dependence on L, a is highly sensitive to changes in dislocation free segment length such as might arise from unpinning, recovery, jog formation, or dislocation intersection. The above equation is not valid near the resonant frequency of dislocations, but the segment length in steel is believed to be much too short to cause over-damped resonance near 10 Mc; this will be discussed later. In the present experiments plastic-strain measurements with a sensitivity of 2 x 10-5 were also made during the early stages of loading in order to detect preyield strain. The general plan of the experiments is to observe

Jan 1, 1967

By R. K. Iyengar, G. C. Duderstadt

An investigation was carried out to determine the effect of Ca-Si additions on the dissolved oxygen content of liquid steel. An apparent equilibrium was reached after holding the melt for some time when the total oxygen content of the melt was identical with the dissolved oxygen. Results of the investigation show that for deoxidation with silicon and manganese the apparent equilibrium is reached after 8 to 12 min and the oxygen content of the melt is in good agreement with values reported in the literature for similar steel compositions. Ca-Si additions decrease the dissolved oxygen content appreciably below that obtained with Si-Mn deoxidation. It is postulated that some calcium dissolved in liquid steel at the time of its vaporization combines with dissolved oxygen to form CaO which then fluxes the manganese silicate, thereby lowering the activity of the deoxidation products. Slow flotation of calcium silicate inclusions is attributed to their slower growth rate. An addition of aluminum (to yield <0.005 pct Alsol) prior to introduction of Ca-Si improves the kinetics of removal of resulting deoxidation products. WITH the introduction of continuous casting of billets and blooms, application of calcium-containing alloys for deoxidation purposes has gained new interest. More so than in conventional ingot casting, the degree of control of the dissolved and total oxygen contents in steel for continuous casting can determine the success or failure of the operation because these affect both surface (pinholes) and internal quality of the billets. Of the available deoxidizers, only silicon has so far found wide application. However, in the typical range of application (0.20/0.30 pct Si), it is too weak a deoxidizer to suppress pinhole frequency to the level desirable for all but the least demanding appli-cations (approximately 10/50 pinholes per sq ft, de-pending on degree of subsequent reduction). On the other hand, Vincent&apos; has shown that it requires ap-proximately 0.007/0.008 pct A1 soluble in the steel to suppress pinhole formation to <10 pinholes per sq ft. In view of the difficulty of consistently maintaining this aluminum level and the associated problem of tundish nozzle constriction2 when aluminum is added to the ladle, steelmakers have searched for other de-oxidation alloys to circumvent the problem. Calcium-containing alloys offer such a possibility. When employed as a partial substitute for silicon, CaSi (30 pct Ca/60 pct Si) additions are reported to yield adequate pinhole contro1.3 Its use simultaneously preserves the "fluidity" of the steel and ensures good castability.4 Oxygen contents as low as 0.007 to 0.014 pct have been obtained with CaSi additions varying between 3 to 8 lb per ton.5-7 Due to the high degree of vaporization of calcium at the temperature of molten steel and the different methods used to introduce it into the liquid, the reported results show considerable scatter and lack of consistency. According to several investiga- deoxidation tors, the flotation characteristics of CaSi products are not as favorable as those found for alumi-num but are similar to those established for silicates with low alumina content.678 Thus, cleanliness ratings were improved when CaSi was replaced by a com-bination of Si + A1 followed by CaMnSi additions.5,9 In view of the lack of a comprehensive description of the deoxidation potential of CaSi alloys, a study was undertaken of the effect of CaSi additions on oxygen content in comparison to Si + Mn and Si + Mn + Al. The alloy chosen for this study contained 63 pct Si, 32 pct Ca, <3 pct Al, and 2.5 pct Fe. EXPERIMENTAL PROCEDURE The experiments were divided in three groups as shown in Table I. In each group, the CaSi addition was increased successively while maintaining the melt composition constant. The experiments in the third group were designed to determine the effect of prede-oxidation with small amounts of aluminum. Ingot iron, containing 0.02 to 0.03 pct C and 0.03 to 0.05 pct Mn, was melted in a 100-lb magnesia crucible. Pig iron was added to the melt under air in an induction furnace to attain the desired carbon content of 0.05 to 0.15 pct and thereby control the initial oxygen content of the melt between 0.04 and 0.015 pct. After removal of the slag, the furnace was sealed and argon was introduced through an opening in the graphite cover, Fig. 1. When the desired temperature was reached, electrolytic manganese was added to the melt and pin samples were taken (7 mm silica tubing) to establish initial oxygen content. To obtain maximum efficiency, CaSi and metallic silicon were introduced in a sealed steel pipe into the bath. This procedure assured minimum loss of calcium through vaporization as the deoxidants were always released at the bottom of the melt. Samples were taken at regular intervals and quenched in water. Temperature of the bath was measured with a Pt/Pt-10 pct Rh thermocouple. Portions of the pin sample were used for oxygen analysis; five determinations per sample were made to obtain average oxygen content. Oxygen analyses were made by the inert carrier gas fusion method with frequent cross checks with the vacuum fusion method.

Jan 1, 1970

By E. W. Mehal, R. H. Cox

A planar Gunn oscillator was developed for use in a monolithic microwave integrated circuit. The device was designed to operate in the frequency range of 20 to 30 GHz with a continuous wave output. Selective epitaxial deposition was used to form the n+n-n+ device structure in (111)-B semi-insuluting GaAs. The active n- region was about 5 µ thick and was doped to about 2 x 1015 electrons per cu cm by the reactor background. The mobility was -5000 sq cm v-1 sec-1. The n+ epitaxial deposits were doped to 1 x 10" electrons per cu cm using S2Cl2. Planarity of the three DURING the past few years, new microwave devices in discrete form have been developed utilizing GaAs. The next logical step is to combine these devices in a successive deposits was quite good; total overgrowth was less than 1 µ. Metal ohmic contacts were applied to the n+ or n- regions using a Ag-In-Ge alloy. The n+n-n+ devices had symmetric IV characteristics and could be operated C. W. for both directions of device bias. Metal ohmic contacts made directly to the n-region always Produced asymmetric devices. C. W. operation was obtained over the 22 to 28 GHz frequency range. The best performance obtained was 1.5 mw C. LV. output at 28 GHz. microwave integrated circuit. A potential application would be a radar receiver operating in the millimeter wavelength region. The key component in such an integrated circuit is a microwave oscillator, recently described by Gunn.1, 2 Under the influence of a large electric field, high-resistivity GaAs exhibits a bulk negative resistance, and high-frequency current oscillations result. Since relatively high voltage and

Jan 1, 1969

C. W. WASHBURNE; New York; N. Y. (communication to the Secretary *).-It has long been known that sulphur and oxygen react upon crude oils, removing hydrogen and thereby creating unsaturated hydrocarbons which unite with each other, producing heavier forms. Dr. Rogers now finds that the percentage of sulphur in the oils of several fields in California is roughly proportional to the specific gravity of the oil. This additional proof is most welcome. It is rather surprising, , in that the impression had prevailed that practically all the reacting sulphur escaped from the oil as hydrogen sulphide, and did not remain in combination with the oil. It would be interesting to know what part of the sulphur-plotted by Dr. Rogers is in solution as free sulphur and hydrogen sulphide, and what part is, in more complex compounds, such as thiophanes, etc.

Jan 10, 1917

THE CHAIRMAN (H. W. MORSE, Los Angeles, Cal.).-I would like to open this meeting for a little while to the general subject of leaching. We ought not to hold back if we have any new schemes for the future. I know that those of us who are tangled up with this lei thing work will appreciate any suggestions that will make us work harder and, scheme, harder to pull through these past difficulties on leaching. F. S. SCHIMERKA, Clifton, Ariz.-Under the direction of J. W. Bennie, General Manager of the Shannon Copper Co., Clifton, Ariz., &apos;it has been my valued privilege to cooperate in the elaboration of a hydrometallurgical process aiming at the recovery of copper in mill tailing resulting from a gravity concentration of a low-grade semi-oxidized sulphide ore occurring in a porphyritic gangue. The experimental work which has been carried on with a 25-ton plant is completed, and the company is building at present a leaching plant on a larger scale, the first unit consisting of a 150-ton roasting furnace and accessories for leaching the calcine.

Jan 12, 1916

By R. N. Orava

TO the author&apos;s knowledge, only one satisfactory high-resolution technique for etch-pitting dislocations in Cu-Zn alloys has been published.&apos; In that account, pits in 70/30 brass single crystals were produced by etching electrolytic ally in a 30 pct orthophosphoric acid bath. Thereafter, observations were made from surface replicas by electron microscopy. The method of pitting and observation permitted the high resolution necessary for the distinction of individual dislocations in arrays of pile-ups. However, no comment was offered concerning the possibility of obtaining pits which are amenable to optical resolution. Moreover, for adequate results, the electrolytic pitting process is invariably preceded by a polishing stage which could obscure the surface features of interest. Consequently, it would be desirable to be able to delineate, by solely chemical means, dislocations which could be detected by both optical and electron metallo-graphic techniques. This was achieved by the simple expedient of modifying two etchants reported by young2 to reveal dislocations on the (100) planes of pure copper. Single crystals of 70/30 a brass, described previously,3 were sectioned to provide a surface parallel to a set of {100) planes, mechanically polished, and subsequently electropolished at 2.4 v in a solution comprised of 2 parts H3PO4, 4 parts ethanol, and 3 parts water. The inclusion of ethanol tended to inhibit nonuniform surface attack. Etch-pitting was effected by a 2 to 3 sec immersion in a 70 pct aqueous solution of HNO3. The samples were then washed in a fast-flowing stream of water, and rinsed further in distilled water, and ethanol, before drying. It is important to note that this reagent should be either used immediately after mixing, or, if allowed to cool, reheated to about 35°C prior to use. No pitting was obtained at room temperature. Typical results are shown in Fig. 1 where (a) is an optical view of the pitted surface and (b) is an electron micrograph of a silicon monoxide replica shadowed with tungsten oxide. The former is characteristic of a somewhat longer etching time (-6 to 8 sec) which varied with bath temperature. Similar pits accrued from a 1/10 aqueous dilution of another of Young&apos;s solutions2—2 M FeC1,6H20 and 7.8 M HBr.

Jan 1, 1968

By A. C. Fraker, H. H. Stadelmaier

WIENER and Bergerl reported the existence of the nitrides Fe3NiN and Fe3PtNwith a cubic L1&apos;2 structure. The present note shows that a similar nitride Fe3PdN can be observed and that the composition range between the iron nitride Fe4N and the nitrides Fe3NiN, Fe3PdN, and Fe3PtN is occupied by single-phase cubic nitrides with structures intermediate between L1&apos; and L1&apos;2. The materials used in this investigation were electrolytic iron of 99.9 pct purity, carbonyl nickel of 99.7 pct purity, sponge platinum of 99.95 pct purity, and palladium sheet of 99.8 pct. purity. Binary alloys of the transition metals were induction-melted in a crucible of fused alumina, powdered, and screened to a particle size of - 200 mesh. The powders were nitrided at 600°C in a gas mixture of ammonia and hydrogen, and the crystal structure was determined with the aid of a Wilson powder camera. The results are compiled in Table I together with information from the paper of Wiener and Berger.1 The compound at the nominal composition Fe3PdN has a diffraction pattern with prominent reflections of a face-centered cubic lattice (h2 + k2+l2 = 3, 4, 8, 11, 12, 16) and weaker superstructure lines (h2 + k2 + 12 = 1, 2, 5, 6, 9, 10, 13, 14). With decreasing palladium content the superstructure lines become weaker and approach the intensity of those of Fe4N. No analysis was made of the intensities, but it can be assumed that the structure is that found by Wiener and Bergerl in Fe3NiN and Fe3PtN, namely L1&apos;2 (perovskite structure) with both palladium and the interstitial nitrogen fully ordered. The dependence of the lattice constant upon the solute atom (Ni, Pd, Pt) content can be explained tolerably well by simple lattice expansion due to subsequent work confirms this suggestion, it will be of significance to order-disorder theory. The author is grateful to Lester Guttman for discussions on this topic.

Jan 1, 1961

By S. K. Nowak

The lithium solubility limit in solid aluminum was determined by the use of micro-graphic techniques. The solubility limit thus established was shown to be a true equilibrium by checking the reversibility of AlLi phase precipitation and dissolution around the equilibrium temperature. The experimental results fit a straight line by plotting log N(LI) against 1/T. The metallurgical reasons explaining the lack of agreement among previous investigations are discussed. THE solubility limit of lithium in solid aluminum was determined by Shamray and Saldau1 by micrography and by Grube et al.&apos; and also Voss-Kiihler- by measurement of electrical resistivity. Since the addition of lithium induces extremely small changes in the aluminum lattice, X-ray techniques could not be employed for this purpose; in fact, the addition of lithium does not cause an expansion of the lattice as might be expected from a consideration of atomic radii, but causes a small contraction from 4.040 to 4.037A3, 4 when the solvent aluminum is saturated with this element. An analysis of the results from previous investiga-tions&apos;" shows that with improvement of investigation techniques the solubility limit tends toward a lower lithium content. Again, some of the author&apos;s own experimental results on the action of atomic hydrogen on A1-Li alloys seemed to indicate that the solubility of lithium should be much lower, i.e., about 0.3 pet at 300°C: instead of 1.15 pet, the lowest published value.4 For the foregoing reasons it was decided to investigate this problem. The aluminum and the lithium used for this purpose were of the highest purity. The lithium solubility limit was determined by metallographic techniques, in particular by the use of a reagent especially developed for the purpose of revealing the AlLi phase. The solubility limit thus determined was shown to be a true equilibrium by checking the reversibility of AlLi phase dissolution and precipitation around the equilibrium temperature. All of the experimental work was carried out in 1951 at the Centre d&apos;Etudes de Chimie Metallur-gique at Vitry, France, under the direction of Georges Chaudron.

Jan 1, 1957

By A. L. Hornbaker, S. D. Schwochow

Industrial minerals are becoming increasingly important in Colorado&apos;s mining industry, not only in production value but also in the variety available and in their potential development for both conventional and new uses. Fluorspar, building stone, fire clay, and pegmatite minerals have been historically important but are not now extensively mined. Aggregates (sand, gravel, and crushed stone), cement materials, metallurgical limestone, and common clays currently are the highest valued commodities. Those offering the greatest future potential include diamonds, nahcolite and dawsonite associated with oil shale, alunite, potash, zeolites, and rare earths.

Jan 1, 1982

By F. W. Glaser, W. Ivanick

A pressure-sintering method was used to produce binder-free and very dense TiC specimens. Some physical properties of these TIC bodies were determined and found to compare favorably with those of certain cemented Tic grades. It was also observed that the hot transverse rupture strength of TiC bodies remained substantially the same regardless of the amount or type of binder material used. STUDIES of the structure and physical properties of refractory materials have been intensified recently because of the urgent need for nonstrategic materials that retain their strength at high temperatures. Research aimed at determining and improving the physical properties of cemented carbides and borides has been accelerated with a view toward possible use of such materials in connection with turbine blades, rocket nozzles, and other high temperature applications. On the hypothesis that the strength requirements in connection with some of the above applications could be met only by proper choice of cementing agents for such refractory materials, the literature describing the physical properties of borides or carbides was reviewed. However, with a few exceptions,&apos;-" references were found only to compositions containing at least one or more auxiliary binder metals. Cobalt and nickel are among the most frequently employed cementing agents. The melting point of Tic (approximately 3250°C) and therefore the sintering temperature, at which notable densification of a cold pressed Tic powder compact could be expected in the absence of a liquid binder phase, is relatively high. The present study makes use of a high temperature, pressure-sintering procedure, recently described by one of the authors in connection with the sintering of binder-free ZrB,," to produce dense bodies of sintered Tic—free of any cementing agent. During the course of this sintering study, some physical properties of dense Tic bodies produced by this method will be discussed. Materials, Preparation of Samples, Testing Methods The procedure for the forming of Tic powder consisted of mixing graphite and TiH, powders in stoi-chiometric proportions, and heating this mixture in a H, atmosphere and carbon crucible by high frequency, to temperatures ranging between 1900° and 2100°C (3452" and 3812°F). The powdered carbide was then comminuted and screened to the desired particle size. Table I shows the chemical analysis of the two grades that were employed for the production of samples during this work. Bodies of Tic, approximately 2.5xlx0.5 cm were produced in graphite molds that were heated by direct conduction. Sintering was carried out at temperatures for time intervals ranging from approximately 0 to 30 sec under a constant pressure of about 1.3 tons per sq in. An alternate method for the production of samples consisted in cold pressing the individual Tic grades at pressures ranging from 4 to 10 tons per sq in. and sintering in a hydrogen atmosphere in graphite crucibles heated by high frequency induction. Sintering temperatures ranged from 2600° to 2900°C (4715° to 5255°F). Electrical testing was done by measuring potentiometrically the voltage drop over a length of 1.5 cm for a current of 10 amp at room temperature. Cross-sectional areas as well as densi-

Jan 1, 1953

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,&apos; 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

New Jersey Zinc Co. - The Plants Canon City Palmerton Depue

Jan 12, 1953

By Murray F. Hawkins

Horner1 and van Everdingen8 ave shown that the pressure drop within the wellbore, as a result of having produced the well at a constant rate q for time t, where t is sufficiently large, is: van Everdingen observed that better agreement between theory and well performance can be obtained if, instead of assuming the permeability is kc everywhere about the well, it is assumed the permeability near the well-bore is substantially reduced as a result of drilling, completion and/or production practices. In order to account for the additional pressure drop he introduced the dimensionless quantity S, the skin effect factor, so that Eq. 1 becomes: Eq. 2 might have also been obtained as follows. Assume a zone of altered permeability k, exists about the well out to a radius r and beyond that the unaltered, external permeability k. The additional pressure drop required to overcome this skin of reduced permeability may be calculated with sufficient accuracy using the incompressible flow equation; for Browns-combe and Collins1 have shown almost no difference between compressible and incompressible steady-state flow, in the vicinity of the wellbore, and the small volume of fluid in the vicinity of the wellbore makes unsteady-state mechanics unnecessary. Then. The sign of this skin pressure drop will be positive or negative depending upon whether the altered permeability k, is smaller or larger, respectively, than the external permeability k... Adding the pressure drop of Eq. 3 to Eq. 1 to find the total pressure drop: Comparing Eq. 4 with Eq. 3 it is seen that the skin effect may be defined by: be determined from pressure build-up tests1,3,4,5,6,7,8 The average permeability kavg including the altered and external permeabilities, can be determined from PI tests, and may be defined approximately on the basis of steady-state flow, as was done by Thomas&apos; in defining the damage factor, by: The productivity ratio is the ratio of the average to the external permeability, kavg/ke or This equation shows that the productivity ratio and the skin effect are not uniquely related, because of the uncertainty in the drainage radius, and also, in many instances, the wellbore radius. Fortunately, they enter in the logarithm. The curves of Fig. I are plots of Eq. 8 for values from 100 to 50,000. The points represent the skin effects and corresponding productivity ratios from a large number of well tests, taken from Fig. 15 of Ref. 5 or Fig. 13 of Ref. 9. While some of the data

Jan 1, 1957

By M. J. Sinnott, J. C. Tobin

A technique for collecting and analyzing the small quantities of gases desorbed on heating metal powders has been developed. The gases collected from copper powders of various types of manufacture have been analyzed and found to contain H2O, CO2, and SO2. The quantities of gas evolved vary from 0.05 to 1.0 milliliter, under standard con-ditons of temperature and pressure, per gram of powder. The source of the gas has been traced to surface films on the powder. IN the powder-metal industry it is recognized that the presence of gases in the powders affects the processing and resulting properties of the sintered product. Several sources for these gases are possible; namely, chemical reactions with the sintering atmospheres, inclusion. of gases during compacting, dissolved gases in the metal powder, and sorbed gases on the metal-,powder surfaces.1, 2, 3 Since the quantities of the gases are relatively small, no direct attempt has been made to collect and analyze them nor to isolate their source. The work that has been done has been concerned with the dimensional stability of the product., its porosity, density, or mechanical and physical properties. Conclusions are drawn on the basis of studies of this type as to the probable effect of gases on these properties. 4, 5, 0 In the present investigation an attempt has been made to obtain quantitative data on the analysis and quantities of gases associated with copper powders manufactured in different ways. Apparatus was constructed to collect gases evolved from loosely packed powder samples on heating to various temperatures under a reduced pressure of helium. The powders were outgassed thoroughly in a vacuum prior to starting the collection operation in order to eliminate mechanically entrapped gases and to prevent the possible reaction of the powder with these gases. Experimental Procedures Materials—The major portion of the investigation was carried out on a single heat of water-atomized, oxygen-free, high-conductivity copper. A relatively coarse fraction of this powder, 20 to 100 mesh, was tested as a mixed powder and as various graded size fractions. The microstructure of this powder showed equiaxed grains and was clean and free from oxides and oxide eutectic. The particle size, as determined

Jan 1, 1959