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By F. J. Plecity, J. T. Michalak, W. C. Leslie

Isothermal recrystallization and grain growth in zone- and vacuum-melted irons and Fe-Mn alloys, up to 0.60 pct Mn, were studied in the range 480° to 650° C, after 60 pct cold reduction. In initial stages, rate of grain growth and rate of recrystallization of iron decrease with time. The recrystallization is typical of a growth-controlled process, and rate of growth is determined by the extent of recovery. Mn decreases rates of growth and of recrystallizatzon. The recrystallization process changes at about 0.30 pct Mn and nucleation may become time-depetzdet~t. In recent years, considerable effort has been expended in determining the effects of solute elements on recrystallization and boundary migration in fcc metals. The results have indicated that the effects produced by single solute additions are dependent upon both the element added and its concentration.'-' In contrast, there have been very few attempts to determine the characteristics of recrystallization and boundary migration in high-purity bcc metals, especially after heavy deformation, and the effects thereon of single solute elements.9-11 This study was undertaken to determine the recrystallization characteristics of various "high-purity" irons and the effects of manganese additions at two levels of base purity. It was hoped that the information obtained would improve our understanding of the recrystallization of pure metals and aid in formulating a theory for the effect of solute elements. The interest was not entirely academic, for the annealing of low-carbon steels, which is of very great commercial importance, is but poorly understood. MATERIALS The compositions of the irons and iron-manganese alloys used are listed in Table I. The zone-melted iron and Fe-Mn alloys were made by Battelle Memorial Institute. Iron S-1 was arc-melted in a water-cooled steel mold in an argon atmosphere. The ingot was forged into a bar, then given two horizontal zone-refining passes in an alumina boat. Iron V-4 was treated in a similar manner, but was not zone-refined. The iron for the zone-melted Fe-Mn alloys was induction melted in vacuum in MgO crucibles and cast into alumina molds. The ingots were forged into bars, machined to shape, and a groove milled down one side of each. The best available electrolytic Mn was placed in the grooves, and the bars were zone melted. The vacuum-melted Fe-Mn alloys were induction melted in this Laboratory in MgO crucibles and poured into cast-iron molds. Iron V-5 was purchased from National Research Corp. in the form of a small vacuum-cast ingot. The low-carbon steel was made by induction melting in air at the U.S. Steel Corp. Applied Research Laboratory. The history of the materials prior to the final cold reduction differed; these details are given in the Appendix. The penultimate grain size of the principal materials was kept in the range ASTM 2 to 4, except for the low-carbon steel. PROCEDURES The cold work prior to the final recrystallization anneal was kept constant at 60 pct. It is known that rolling procedure can influence the kinetics of recrystallization of ironI2; therefore, all specimens were rolled in one direction only, between clean,

Jan 1, 1962

By G. L. Schroeder

Investigations were conducted at two underground locations, foreman's room and 5702 area, of the Kermac Nuclear Fuels Corp. uranium mining installation, Ambrosia Lake, New Mexico. The rock environment is stratified sandstone. Pressures were varied from minus 0.4 an Hg to plus 3.8 cm Hg with respect to barometric pressure, and were maintained for periods ranging from several hours to 21 days. One cm Hg overpressure (-1.5% of normal barometric pressure) produced a 20-fold decrease in Rn flux into the foreman's room as compared to the Rn flux observed during dilution ventilation. The 5702 area experienced a 5-fold decrease in Rn flux for a similar overpressure. During 21 days of continuous 1 cm Hg overpressure in the 5702 area this reduced Rn flux was maintained. The smaller reduction in flux for the 5702 area results in part from the proximity of the foreman's room to a non-pressured area and the presence of an impermeable shale lens overlying the ceiling of the 5702 area. A 0.4 cm Hg underpressure of the 5702 area increased the Rn flux into the area by 3-fold over the non-pressured value. A barometric pressure influence on Rn flux into the mine and on air Rn concentrations in non-pressurd areas of the mine was measured. A falling barometric pressure causes an increase in the flux of interstitial gas into the mine; a rising barometric pressure decreases this flux. These effects are not seen in overpressured mine areas. Radon concentrations in rock interstices show, during overpressure, decreases of all locations monitored except in the immediate vicinity of the shale lens above the 5702 area ceiling. These reductions are the result of air flowing from the mine into the rock interstices under the influence of the pressure gradient induced by the overpressure. The relative humidity of the 5702 area was reduced after 2 days of 1 cm Hg overpressure from a pre-overpressure value of 96% to 81%. The control of harmful or noisesome gases which emanate into underground mining areas from surrounding rocks is often a costly necessity. In uranium (U) mines this problem is presented by the high interstitial concentrations of radon-222 (Rn), a radioactive noble gas of 3.82-day half-period, formed in the decay scheme of U238, and the relative ease with which this noble gas diffuses from its parent rock into the interstices of the rock and then to a working area. Long-term exposure to moderate concentrations of Rn (3000 µµc per 1) and its short-lived alpha-ray emitting daughter products, RaA (Po218) and RaC (po214), has been found to result in an increased incidence of bronchial carcinomaa2 The acceptable limit of Rn daughter products in a mine atmosphere is presently set at a concentration of short-lived radon daughters which would be in equilibrium with 100 ppc of Rn per 1 of air. Ventilation of mines is conventionally accomplished by continuously diluting the mine air with fresh air brought in by fan or natural convection from above ground surface. The diluted air is allowed to vent freely to the atmosphere. This process does nothing to retard the rate at which gases (including Rn) diffuse into the mine from surrounding rock. It merely reduces the concentrations of these gases within the mine. It is suggested that in a sufficiently permeable rock environment a slight pressurization of the mine air may induce air flow from the mine into the interstices of rock surrounding the mine. The convective flow of comparatively fresh air will reduce the concentration and the concentration gradient of undesirable gases in the rock interstices adjacent to the mine. Radon will diffuse counter-current to this convective flow at a rate proportional to its concentration gradient. In time, a steady state of convection and counter diffusion will be established. The Rn flux into the mine will never be reduced to zero, and will only asymptotically approach zero as the overpressure (and hence the convective velocity of purging air) approaches infinity. During 1963 and 1964, an investigation into the effect which such applied pressures have upon the Rn characteristics of a mine atmosphere was conducted at the Kermac Nuclear Fuels Corp. uranium mines, Ambrosia Lake (near Grants), New Mexico.

Jan 1, 1967

By R. Grierson, L. J. Bonis

The high-temperature Strength oF TD nickel has been observed to be dependent upon the previons thermal and mechanical history of the material. Variations in both the level and the anisotropy of strength have been observed. 01 this paper- these variations are correlated with the storing of annealing resistant elastic strain energy in the matrix of the TD nickel. An x-vay line -broadening tecknique is used to measure the maLrTis elastie strain. THE inclusion of a finely dispersed second phase into a ductile matrix has long been recognized as an extremely effective method of strengthening the matrix both at high and at low homologous temperatures. It has been found, however, that the factors which determine the high-temperature strength are not the same as those which are important at low temperatures. Below 0.5 Tm the size and distribution of the second phase particles are of prime importance in determining the strength,')' while above this temperature the strength is mainly dependent upon the previous thermal and mechanical history of the alloy,3-7 This paper is primarily concerned with explaining the response of the high-temperature mechanical strength of one of these alloys (DuPont's TD nickel) to various thermo-mechanical treatments. It will be shown that this response is not associated with the occurrence of any form of dislocation substructure within the matrix of the alloy. It has been found, however, that a correlation does exist between the elastic strain level in the matrix and the previous thermomechanical history of the alloy and that the observed changes in elastic strain level parallel the measured changes in high-temperature strength. It therefore must be concluded that variations in high-temperature strength are a direct result of the variations in elastic strain level. MATERIAL TD nickel contains approximately 2 vol pct of Tho2 in an unalloyed nickel matrix. It is formed, as a powder, by a chemical technique and this powder is compacted to form ingots which are then extruded to give 21/2-in.-diam rod. Rod of smaller diameter is prepared from the as-extruded rod by swaging. In the studies reported in this paper, 1/2-in.-diam rod was used. This rod received an anneal of 1 hr at 1100°C prior to being used in any of these studies. EXPERIMENTAL TECHNIQUES Two methods were used to examine the structure of the nickel matrix of the TD nickel. These were: 1) transmission electron microscopy; 2) the analysis of the position and profile of X-ray diffraction lines obtained using the nickel matrix as the diffracting media. To prepare thin foils for electron-microscopical examination, slices of TD nickel approximately 0.050 in. thick were cut from the as-received 1/2-in.-diam rod. These were then chemically polished down to 0.045 in., rolled to 0.009 in., given a predetermined heat treatment, and thinned, using a modified Bollman technique, to provide the foils for observation. All observations were carried out at 100 kv, using a Hitachi HU-11 electron microscope. Specimens of the undeformed rod were prepared by grinding down the 0.050-in.-thick slices to approximately 0.015 in. and then thinning chemically and electrolytically to give the thin foils. The X-ray specimens were prepared by rolling 0.375-in.-thick rectangular blocks down to 0.075 in. The surfaces of the rolled material were ground flat, chemically polished to remove the layer disturbed by the grinding, and given a predetermined anneal in an inert atmosphere. They were then ground lightly to check their flatness and given a final chemical polish prior to being examined. The X-ray diffraction line profiles were measured using an automated Picker biplane diffractometer. A special specimen holder was built to allow a more accurate and reproducible positioning of the specimen. The line profiles were determined by carrying out intensity measurements at intervals of either 1/30 deg or 1/60 deg over a range of 3 deg on either side of the nickel peaks of interest. A piece of pure nickel which had been recrystallized to give a large grain size was used as a standard to give the X-ray line profile generated by a strain-free matrix. The analysis of the X-ray diffraction line profiles is a modification of that due initially to Warren and Aver-bach8and has been described elsewhere.3 This analysis gives a measurement of two parameters associated with the structure of the nickel matrix. These parameters are: 1) the size of the coherently diffracting domains within the nickel matrix; 2) the magnitude of the elastic strains in these domains. Both of these parameters are first determined in terms of a Fourier series. These series are obtained from other Fourier series which describe the measured profile of the X-ray diffraction lines. Thus, for both the coherently diffracting domain size and the elastic strain level, it is possible to plot Ft (the Fourier coefficient) against t (the term in the Fourier series), where t can be expressed in terms of a distance L and the Fourier coefficient Ft(S) (associated with elastic strain level) can be expressed in terms of the root mean square strain (e2)1/2. Thus a plot of (F 2)1/2 vs L can be obtained. Plots of this type are shown graphically in Figs. 6 and 8. Interpretation

Jan 1, 1968

By M. H. Caron

BASIC U. S. Patent 1,487,145 on ammonia leaching of nickel ores was issued to the author on March 18, 1924. Equivalent patents in other countries were obtained later. The Dutch Syndicate Brikcarbo became interested in the process in 1935; and a couple of years later the late Dr. H. Foster Bain sent samples of Surigao laterite iron ore to Delft and witnessed tests made there on this material for the Philippines Commonwealth. As a result, the author was asked in April 1940 by Dr. Bain to go to the Philippines to erect and take charge of a pilot plant for the process. The World War prevented carrying out this proposal. The Dorr Co. also became interested in the process at about the same period. The investigations by the Freeport Sulphur Co. on the process as applied to the Cuban nickeliferous laterites, which resulted in the Nicaro enterprise, and the results of this operation have been well described elsewhere.1,²,³,4,5 This Nicaro plant was, in operation for almost two years, and during this period produced about 10 pct of the world nickel production from laterites containing 1.35 pct nickel. This plant and its operation were war measures and, in view of this, activities were suspended in April 1947. The results obtained fully demonstrated the technical feasibility of the process and its economical aspects on a commercial scale. In this respect, it should be understood that it is probable that improvements may be made by further development, and that there are possibilities for advantageous application of the process to garnierite and similar ores with higher values in nickel than the laterite iron ores at Nicaro. While the articles cited above have given a certain amount of information, no general article containing all the important process data has been pub- lished. Since the process is of more than local interest, a fuller knowledge of the fundamental and practical factors of the method may be welcome to those interested in this new field of metals technology. The author, accordingly, takes pleasure in submitting this article to the AIME as it represents in a condensed form the results of many years of research. The brief outlines of the fundamental and other factors and the explanation of observed phenomena are presented with as little discussion of details as possible, consistent with clarity. It is a special satisfaction to the author to make some contribution of his own in return for the benefits of the many valuable publications issued by the Institute during his thirty years of membership. Ores Adapted for Ammonia Leaching: All nickel and cobalt ores which originate from weathering of peridotites or similar basic rocks having sufficient values are suitable for treatment by the ammonia leaching process after a preliminary reduction under proper conditions. The formation of these deposits was probably as follows: In the course of time the basic rocks were attacked by atmospheric agencies; MgO and SiO2 were gradually leached out, and secondary nickel minerals formed, such as garnierite, a hydrated silicate of nickel and magnesia. These secondary products are, however, not stable. They decompose in a further stage of weathering and ultimately only a relatively small residue of insoluble oxides remains, known as laterite iron ore with a small nickel content and very little cobalt. Under these mantles of laterite, richer nickel values may be found, usually indicated by the occurrence of garnierite. The more the ore is disintegrated by nature, the higher the iron content and the better the nickel extractions that may be expected therefrom. Table I shows extractions that may be expected from different types of ores, assuming treatment of -200 mesh products and that all precautions have been taken for obtaining maximum extractions. As for the distribution of the various nickel minerals and compounds that may be present, great variations may occur from locality to locality as well as vertically in a deposit. From such "run of

Jan 1, 1951

By B. C. Allen

Grain-boundary gvoocing was studied irz chronziu?n. molybdenum, tungsten, and the solid-solution alloys, Cr-35Re. Mo-33Re, and W-25Re at 0.6 to 0.9 of the absolute liquidus temperature under an inevt atmosphere , foveign nzetal zlapor, and liquid metal. The controlling mechanism of matter transport was deduced frolr groove size and shape. kinetics of growth, and cotnparisoz with theoretical relatiotzships derived by Mullins. Grooves in chowzizon formed prittzarily by volume diffusion tkrongk kelium or argon at 1 atm pressure and by e1)apovation-condensatiotz in a static vacuum. Groozles in the other nzetals and alloys forrned priniarily by sirface diffusion, the coefficients of which were calculated. Carbon was found to decrease the acti7:ation energy for surface diffusion on molybdenun. Sitrface diffusizities weve sinzilav for iWo-0.0ZC and Mo-33Re. The presence of about 1 -?nm pressure of silver or tin vapor did not affect the neckanis)n of grooz;e formation. In liquid titz or silz:er, pain bolindary gvooves formed by zolume diffusion in the liquid. BASED on theories of ullins," the mechanisms of grain-boundary grooving have been determined for low-melting metals such as copper in an inert atmospheres or in liquid lead.4 The purpose of this investigation was to study grain-boundary grooving in the refractory Group VI-A metals, chromium, molybdenum, and tungsten, and the bcc solid-solution alloys, r-35e, 0-33e,= and -25e,' at 0.6 to 0.9 of included to see whether Mullins' theories were applicable to them as well. EXPERIMENTAL WORK The materials chromium, molybdenum, tungsten, Cr-35Re, Mo-33Re, and W-25Re were in the form of 0.050-cm-thick sheet assaying 99.98 pct or better. The nominal carbon level was generally 30 ppm. The oxygen + nitrogen + hydrogen content was -50 ppm. Mo-33Re and W-25Re were prepared by powder-metallurgy methods and supplied by Chase Brass and Copper Co. The remaining materials were arc-cast. Chromium and Cr-35Re were prepared at Battelle by arc melting, extruding, swaging, and rolling. Mo-0.003C was supplied by Climax Molybdenum Co., and Mo-0.02C and tungsten by Universal Cyclops Corp. As a source of liquid metals, tin and silver granules assaying 99.98 pct were used. Spectrographic analyses indicated the presence of -100 ppm each of iron and silicon. Vacuum melting reduced the combined gas content to c5 ppm (2.60,, 0.9N2, 0.4H2 in tin and l.602, 0.7N2, and c0.04H2 in silver). Specimens were prepared for grain-boundary grooving. Coupons 0.5 by 1.5 cm with a small hole in one end, or substrates 1.5 by 1.5 cm, were cut from sheet. The specimens were annealed in containers of the same material to provide a vapor-solid equilibrium as well as to protect them from gaseous impurities. Outgassing was done at 2 x 10"5 mm for 15 to 30 min at 1150°C for chromium and Cr-35Re, 1750°C for molybdenum and Mo-33Re, and 2600°C for tungsten and W-25Re. Then recrystallization to a stable grain size of about 0.5 mm was accomplished by annealing at least 1 hr at 1600°C for chromium, 1800°C for Cr-35Re, 2350°C for molybdenum, and 2300°C for Mo-33Re in a rhenium-element resistance furnace under 1 atm of static argon or helium. The atmosphere was gettered by tantalum radiation shielding. Tungsten and

Jan 1, 1967

By Francis Cameron

Gloomy predictions that domestic mineral reserves are approaching exhaustion are unwarranted and may be harmful, this author contends. Specific mineral forecasting errors in the Paley Report are cited to support this contention, and steps that can be taken to insure a progressive mineral industry capable of keeping pace with the major raw material needs of the nation through advancing technology are suggested. Mining is both exciting and rewarding —although at times somewhat frustrating— and we all can have real pride in our industry, in its people, and in its accomplishments. It is, however, with concern that I have noted a deterioration in this Country in what might be called mining's stature and in the growth of a belief in many quarters that our mineral reserves are rapidly approaching exhaustion. In other words, there is a popular image that we are fast becoming a "have not" nation in many respects and that the domestic mining industry can no longer be considered, in the vernacular of Wall Street to offer much in the way of "growth potential." I do not subscribe to this hypothesis, nor do I be-li4ve that the record of the mining industry bears this out. However, let me add that we can, in time, talk ourselves into this frame of mind and we can hasten the day when this very well might come about by unnecessary and unwise legislation or regulation. My remarks today are basically designed to give my reasons for refuting this negative philosophy and to review our record. With your help, I know we can improve our image, and the public's recognition of our industry's peculiar problems. The progress of our civilization over the centuries has been fundamentally based upon proper use of raw materials, both agricultural and mineral, and upon energy, human or otherwise. As the standard of living has progressed century by century, the demands for mineral raw materials have increased in an irregular, but steadily rising progression. Fortunately, those minerals on which we depend most, i.e., iron, coal, petroleum, copper, aluminum, lead, and zinc have been neither too difficult to find nor to process into useful form. Iron, the most useful of all metals, is present in various amounts in most rock types and soils. Gold, seemingly the most generally desired (but certainly not the most useful of all metals), occurs in sea water in a far greater total tonnage than has been won from all of the world's known gold mines. If the latter is true, then why do we not see large installations treating sea water for the recovery of its gold content? The answer, of course, is that even the French, who seem, from their recent actions, to value gold above all else, have not devised a way of doing this at a profit. Theoretically, it is possible, but not with today's technology at a cost which would justify the effort. Man has exploited only those mineral concentrations which accidents of nature have placed within his so far limited means of finding and utilizing. What we geologists and engineers refer to as an orebody is nothing more than a concentration of minerals, exploitable with available knowledge, that will yield a value greater than the value attached to the energy and capital required to produce it. What is "ore" and what is not "ore" is, in the end, a matter of economics. The economic problem stems from the physical and chemical character of mineral deposits. The good Lord stacked the cards heavily in favor of rising costs by limiting the amount of the higher grade ores easily available. As the best and most accessible ores are depleted, it becomes necessary to work harder and with greater ingenuity to produce more from less accessible and lower grade resources. The quantity of mineral raw materials we can have in the future will be determined largely by what we can afford to pay for them in terms of human effort, capital outlay and production energies. We will always have the problem of cost with us and our only real means of keeping ahead of rising costs is by continually improving our technical abilities. We, in this country at least, no longer have open to us large and unexplored virgin wildernesses in which a pick-and-shovel prospector might uncover an untouched mineral bonanza. The rest of the world also has few conventional frontiers left in which the explorer-prospector is free to roam. We do, however, have enormous land areas unexplored, and untouched po-

Jan 1, 1969

By F. Keller, A. H. Geisler

Some of the important changes that take lace in the structure of aluminum alloys are largely submicroscopic in character. This is especially true of the changes that accompany age-hardening and recrys-tallization. Although improved metal-lographic practices have been helpful in indicating some of these changes indirectly, results are limited by the resolving power of optical microscope lenses. The electron microscope, however, provides a new and important means for investigating the fine structure of metals in a range not possible heretofore. It is anticipated that this microscope will yield new and useful information to metallurgists when suitable techniques are developed to utilize its very high resolving power. Several unique methods have been devised to permit the examination of the structure of opaque samples by the electron microscope. These are all based 011 the principle of producing a very thin film that represents the prepared surface of the opaque metal sample, which can be examined in the transmission microscope; however, the available methods fall into three categories, depending on the manner in which the film is obtained. With the oxide-film method developed by Mah13-l7 a very thin surface layer of the metallographic sample is converted into oxide by a thermal, chcmical or anodic treatment. .After removal from the metal sample by one of the special techniques described by Evans,l9 this oxide film is examined in the electron microscope, and is found to portray the structure of the original metal surface. Films formed on aluminum,8,l7 nicke1,7 iron3,8,9 and a nickel-beryllium alloyl1 by heating; films formed on iron8,9 by chemical action; and films formed on aluminum3-'" by anodic oxidation, have been examined. The other two are more recent methods developed principally in this country; they consist in making the thin film in the form of a mold or replica of the surface contour of an etched sample. With the negative replica method the thin film is made directly on the sample; with the positive replica method it is made on a negative reproduction of the sample. With both methods, variations in the contour of the metal sample, caused mainly by etching, produce variations in the thickness of the surface replica. Because of the direct dependence of the amount of scattering of the illuminating electrons upon the thickness of the film penetrated, only the variations in thickness of the replica are responsible for tones in the electron image. Negative replicas are made by forming a thin film of some suitable material directly on the polished and etched metal sample, and derive their name from the fact that after removal from the sample they have the high and low points in the sample reversed, as shown in Fig. I. Nega-

Jan 1, 1944

By H. A. Bright, H. C. Vacher, J. G. Thompson

The methods employed for the determination of oxides and oxygen in ferrous materials may be roughly classed in two groups, "wet" methods and "hot" methods, the first group including the iodine, electrolytic, mercuric chloride, hydrochloric acid, nitric acid, and chlorine methods; the second group including the vacuum-fusion and hydrogen-reduction methods. The wet methods depend upon preferential solubility in a selected medium to separate the metallic portion of the sample from the oxygen-containing constituents. Subsequent analysis of the insoluble residue permits the isolation and separate determination of individual oxides and compounds. The hot methods depend upon the reduction of the oxide constituents of the sample by means of carbon or hydrogen at elevated temperatures. With the exception of the recently developed fractional vacuum-fusion method, the hot methods do not identify individual oxides and compounds but yield only a single value representing the sum of the oxygen contents of several or all of the oxide constituents present. With such diversity in the principles and aims of the different groups, it is not surprising that concordance of results by different methods has usually been difficult to obtain. The present cooperative attempt to define more rigorously than has been possible heretofore the accuracy and limits of usefulness of the various methods, originated in correspondence between Dr. John Johnston, Director of Research of the United States Steel Corporation, and other interested metallurgists. The plan was, briefly, to submit identical samples to a number of laboratories for analysis by different methods and to collate the results of these analyses. The project was endorsed by the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers at the annual meeting in February, 1933, and has been conducted under the joint sponsorship of the Iron and Steel Division and the National Bureau of Standards. The latter organization undertook

Jan 1, 1937

By R. J. Burgess, A. R. Ramey, A. R. Adams

During interpretation of pressure buildup tests on gas wells in a tight dolomite gas reservoir, peculiar behavior was noticed. Two straight lines were apparent. Effective permeability to gas taken from either straight line was about the same, and the Miller-Dyes-Hutchinson dimensionless time check for the straight line was proper for both straight lines. Geological data indicated the likelihood of scattered trending fractures in the reservoirs. Since the first straight Iine yielded permeability values close to the geometric mean permeability from core analyses, it was postulated that the reservoir model was that of an acidized well completed in the tight dolomite, but that widely scattered hairline fractures caused the mean permeability of the reservoir distant from the well to be higher than the matrix permeability. Because all other studies of fractured reservoirs to the authors' knowledge assumed that the fracture matrix was dense enough to communicate directly with the well, no interpretative methods were available. The Hurst line-source solution for a radial change in permeability for interference between oil reservoirs was adapted to pressure buildup testing. The result indicated that the first straight line should yield the proper matrix permeability and wellbore skin effect. The second straight line may be extrapolated to obtain static pressure. The time of bend between the straight lines was used to estimate distance to a fracture. Application to field test data is shown. It is believed that the methods developed and the case history presented will add to present tools available for pressure buildup interpretation. Introduction Since the pioneer studies by Miller, Dyes, and Hutchin-son1 and Horner' in 1950 and 1951, well test analysis has become recognized as one of the most powerful tools available to both production and reservoir engineers. Well test analysis serves as a logical basis for well stimulation and completion analysis, and for long-term reservoir engineering. Since the early 19501s, much effort has been placed on the development of well-test analytical methods. Reservoir and well conditions of increasing complexity have been considered systematically to provide the analyst with a catalog of causes and effects. Matthews and Russella state that some 200 papers dealing with this subject have been published in the last 35 years. Developments in well test analysis appear to have originated in one of two ways. Either a physically realistic field condition was anticipated and analytical solutions for the condition achieved, or anomalous field test behavior was recognized and interpretative methods sought for the anomaly. In recent years, it has appeared that the latter has inspired an increasing number of studies. The analyst today finds an increasing number of known cause and effect studies available for well test analysis, the classic of which is that of finding the specific flow problem that generated the answer — the well behavior. Although it may be impossible to achieve this goal uniquely, the analyst often is able to select a useful interpretation that combines all known performance and geologic data — or to show that various logical alternatives would not significantly affect the interpretation. During a recent reservoir study, we observed gas well test behavior that did not appear to fit behavior described previously. Although it cannot be said that we have found a unique interpretation, we shall present in this paper the peculiar behavior observed, and describe the reservoir and interpretative methods developed. Reservoir Description The subject gas reservoir is a 9-mile-long, narrow dolomite reservoir lying within a limestone of Ordovician age. (See Fig. 1.) The dolomitized rock in the field consists of dark brown to buff, dense to coarsely crystalline, vugular dolomite containing numerous hairline fractures, many of which may have been closed in the reservoir and parted when cores were brought to the surface. Larger fractures are also apparent in core, but usually are filled and sealed with euhedral dolomite crystals. Portions of the north flank of the reservoir are known to be cut by a sealing fault downthrown to the north. Gas wells located near the fault have higher open flow potentials than those more distant from the fault. This is believed to be a result of higher permeability near the fault due to more extensive and open fractures. Detailed coring and core analysis have been performed on several of the wells in this reservoir. Fig. 2 presents permeability variation' plots for both horizontal and vertical

Jan 1, 1969

By Henry Fay

The erosion of guns is a complex problem which can be solved only by a detailed study of all the factors involved. In the present paper it is proposed to submit the results of observations and experiments which have extended over several years. Certain facts have been established and preliminary reports have been published.' Conclusions have been reached since then which, it is believed, are worth presenting for the purpose of promoting discussion, and with the hope that ultimately the whole truth will be known. The particular phase of the problem which will be presented here is the hardening of the inner surface of the gun tube. It has been known for a long time that after firing a large caliber gun for some time, the surface of the metal becomes hard and brittle, cracks, and wears away.2 The character of this phenomenon may be learned by an examination of some results which are typical, obtained from a detailed study of a 12-in. gun. The gun was trepanned and rings representing various sections of the gun were cut out for examination. The first ring represented the metal at the muzzle end, and the other rings were removed at approximately 120, 240, 325 and 337 in., respectively, toward the breech end. The appearance of the surface of the metal in the different sections is shown in Fig. 1. The greatest amount of wear and maximum amount of hard surface layer was found in section marked E, which is nearest the powder chamber and at the beginning of the rifing; the maximum amount of cracking in D; the maximum amount of copper deposition in C. Section B showed heat cracks on both lands and grooves, and section A showed heat cracks on the driving edge of the lands only. There was much flow of metal in both sections E and D, and there was progressively less effect noticeable toward the muzzle end. The polished cross-section of these same pieces is shown in Fig. 2. The extent of the erosion is greatest nearest the powder chamber, and diminishes toward the muzzle end.

Jan 1, 1917

By Peter Tegart

The discovery of gold in the Toodoggone River area is credited to Charles McClair who mined placer deposits in 1925, reportedly valued at $17,500. After he and his partner went missing in 1927, efforts to relocate their workings resulted in the formation of Two Brothers Valley Gold Mines Ltd. in 1933, in which the legendary Grant McConachie (first president of CP Air) played an active role. This was the age when the prospector first utilized the airplane to reconnoitre remote areas. What greeted the observer from the air was an area rich in orange and yellow colours characteristic of gossans formed by the oxidation of sulphides. However, Samuel Black, a Hudson Bay Company fur trader, had also noted in his diary as early as 1824, the unusual and many gossanous colours in the headwaters of the Finlay River. These gossans, coupled with white limestone bluffs and the presence of placer gold, attracted the first reconnaissance of the area by Cominco in 1929. Cominco was ever active in remote areas at this time. They staked and worked several base-metal showings hosted by limestone at the margins of intrusive stocks. These early workers also obtained erratic high gold assays from chalcedony float samples found in creeks draining into the Toodoggone River. However, because the samples gave inconsistent assays, no concerted effort was made to locate their source. Except for the occasional horse-supported prospecting party of the late 1940s and early 1950s, the area did not receive much attention until 1968. Work until this time focused on the base metal lead-zinc showings which contained attractive silver credits. Gold was not an attraction because of the set price established by the US government. The late 1960s saw the northward expansion of porphyry copper exploration into the Toodoggone. A program of gossan soil sampling (gossans which had attracted the early workers) was carried out by Kennco Explorations (Western) Ltd. in 1966-1967. They analysed for base metals in the field, using a cold extraction method. The Kemess copper- gold prospect was staked as a result of anomalous copper values from this early geochemical program. In 1968, Kennco continued the program of silt traversing and field geochemical testing. The samples were further subjected to multielement analysis consisting of copper, molybdenum, lead, zinc, cobalt, nickel, and silver at Kennco's North Vancouver laboratory. Several anomalous creeks, high in combinations of copper, molybdenum, and silver, were outlined. Some initial soil grids were also established. The fall of 1969 saw the return of Kennco prospector Gordon Davies and geologist Bob Stevenson to check out a well-defined molybdenum, scattered copper and silver anomaly in soils from a grid on the Chappelle claims. The subsequent analysis of several selected quartz felsenmeer floats yielded one assay which ran in the order of 0.25 kg/t (8 oz per st) gold and 2.2 kg/t (70 oz per st) silver. Subsequent trenching on the Chappelle claims exposed the source of float in a 4- m (134) wide vein of high grade gold-silver mineralization. These results led quickly to the realization that the district had precious metal potential. Subsequent exploration in the period 1969-1974 by Kennco resulted in the discovery of most of the gold and silver occurrences on the Chappelle and Lawyers properties. Several other gold and silver occurrences were found in this district by Cordilleran, Cominco, and Sumitomo, working the district during this period. Conwest optioned the Chappelle in 1973 and explored underground by adit entry as part of a one-year program. In 1974, Du Pont of Canada Exploration Ltd. optioned the Chappelle claims and in March 1980, using reserves developed on the A vein, placed the Baker mine into production at a rate of 90.7 Vd (100 stpd). The Amethyst zone on the Lawyers property, 8 km (5 miles) north of Chappelle, was found in 1973 by Kennco using continued, persistent followup prospecting of silver silt geochemical anomalies. A silt anomaly in the order of 3.4 ppm silver occurred in a stream flowing 300 m (984 ft)

Jan 1, 1985

By H. I. Kaplan, C. Laird

Pulsating contpresslon experiments have been carried out on coppev single crystals in order to test the adequacy of mechanisms which have been suggested for stage I cvack grouth when tension-compression loading is the mode of- applying stress. Although dejorrrzation continues slowly for many millions 01 cycles under Pulsating compression stresses both within slip bands formed in the first cycle and by the creation of new bands, the morphology of these bands is not typical of fatigue slip bands in general and neither initiation of cracks nor propagation of artificially induced cracks was observed. It is therefore concluded that 1) initiation and growth of cvacks in fatigue is a consequence of repeatedly reviersed, microplastic deformation rather than intermittent, unidirectional deforma-tion, 2) gvowth of- cracks in polycrystalline specimens FAILURE of a plain specimen subjected to cyclic tension-compression stresses is known to take place by two stages of cracking.1,2 The first stage is characterized by propagation along slip planes roughly at 45 deg to the stress axis, in the outermost layers of the specimen, and at a rate of the order of angstroms per cycle. The average macro orientation of a stage I crack is normally at right angles to the stress axis,3 however, except in a few cases, e.g., single crystals in suitable orientation, when both the micro and macro directions of propagation are at 45 deg to the axis. After a stage I crack has penetrated to such a depth that the stress on the remaining section of metal is significantly increased, stage II crack propagation succeeds stage I, at right angles to the stress axis both micro and macroscopically. Direct evidence of the processes occurring during a subjected to pulsating compression stresses is caused by the setting-up of local tensile stresses due to interactions between grains, and 3) both unslipping mechanisms and operation of the "plastic blunting process " within a single slip band are adequate descriptions 01- stage I growth, being fundamentally similar. The slip mode of a material, however, is considered to control whether unslipping or the plastic blunting process takes place. Thus materials of planar slip mode fauor unslipping while those hacing a wavy mode, and capable of cross slip, can fail in stage I by the plastic blunting process. Similarly, and perhaps more importantly, reversed torsion and tension-compression modes of applying stress may be expected to cause the unslipping mechanism and the plastic blunting process, respectively. single stress cycle4,5 shows that stage II crack propagation takes place by a repetitive plastic rounding and closing of the crack tip. This mechanism has come to be called the "plastic blunting process".6 On the other hand, the extreme smallness of the phenomena occurring in stage I growth prevents elucidation of its mechanism by direct observation. Many suggestions have been proposed for this mechanism,'"-" most of them involving some kind of random or systematic unslipping process. It is possible, however, that the mechanism of stage I growth is essentially the same as that of stage 11, but occurring on a much smaller scale.6 In this situation, it has been observed that cracks propagate along slip bands comprising dislocation cell structures and bounded on either side by regions of different dislocation density and distribution." Since there is evidence that such bands are softer than their matrix, * it may be expected that the plastic blunting process occurs within a single slip band during stage I growth, rather than on two gross bands as in stage 11, when the acting stress is greater.= The blunting of the crack tip allowed by coordinated

Jan 1, 1968

By M. S. Rashid, C. J. Altstetter

Allotropic transformations in cerium have been studied by dilatometric, resistometric, X-ray diffraction, and metallographic techniques. The dilatometric study indicated that, on cooling below O°C, the high-temperature fcc phase, y, transforms partly to the hexagonal phase, ß, and, on further cooling, to the collapsed fcc phase, a. The amount of $ phase present at room temperature is increased by repeated cycling through the a-y transformation. It has been shown metallograPhically that the y-ß transformation has many characteristics of a martensitic transformation. In contrast to the y-ß transformation the ?-a transformation does not give the manifestation of a shear transformation. Small cellular ? domains of random shape and size collapse to a in a short time with no apparent coordination with neighboring domains. The considerable confusion in the literature over the existence of more than one high-temperature fcc phase is discussed. Two such phases have been reported in the literature and an attempt is made in this study to clarify the situation. Twelve fcc and two hcp structures have been shown to be easily reproduced or eliminated. It is proposed that the two "additional" allotropes reported in the literature and fourteen of the phases detected here are not allotropes of cerium but are due to contamination. CERIUM exists in several allotropic forms, but there is some disagreement over what the forms are. Furthermore, the conditions favoring the presence of a particular allotrope and the nature of the transformations from one form to another are uncertain. The objectives of this research were 1) to ascertain the allotropic forms of cerium, 2) to establish the conditions under which the allotropes exist, 3) to study the effects of annealing and thermal cycling on the allotropic transformations, and 4) to study the transformation mechanisms. Dilatometric, resistometric, metallographic, and X-ray diffraction techniques were employed. The form of cerium commonly found at room temperature is fcc and is designated ?. A complex hexagonal phase, 8, forms when y is cooled to slightly below room temperature. At still lower temperatures the y fcc structure transforms to an fcc form with a much smaller lattice parameter, termed a cerium. A bcc form, 6, which exists just below the melting point (800°C), will not be considered further in this work. There is a substantial body of experimental evidence (reviewed by Gschneidnerl) which favors the acceptance of these four allotropes, though some investigators have tried unsuccessfully to observe the ß hexagonal form.'-' There is disagreement, however, over the phase-transformation temperatures, due, in part, to broad hysteresis and overlapping of the transformations between the a, ß, and ? forms. The transformations are also sensitive to prior thermal and mechanical treatment. The differing purity of cerium used by different investigators is undoubtedly a factor. Cerium is difficult to separate from other elements and is quite reactive, igniting spontaneously when it is filed in air. The highest purity of cerium to date is reported to contain several hundred parts per million by weight of impurities, and early investigations were carried out on cerium containing several percent of impurities. There have been reports of more than one fcc allotrope at room temperature. Gschneidner, Elliott, and McDonald5 obtained diffraction patterns of an fcc phase with a lattice parameter about 1 pct less than that of the ? phase, instead of the y phase, on slowly cooling cerium filings from 23° to -198°C and warming them back to room temperature. However, when the sample was heated to 447°C and cooled to room temperature it consisted of only the ? phase. They have designated this new fcc phase "a-? intermediate", and say it is quite sensitive to impurities. After prolonged high-temperature treatment of a powder specimen, Weiner and Raynor2 obtained a diffraction pattern of an fcc phase of lattice parameter about 1 pct less than the ? phase. This they called the y' phase. It could not be reconverted to the y phase and is claimed to be different from the a-? intermediate phase.5,6 Dialer and Rothe3 reported two fcc phases* after cycling their powder specimens between room temperature and -192°C. Gschneidner, Elliott, and McDonald5 suggested that one of the fcc structures obtained by Dialer and Rothe was equivalent to their "a-? intermediate" phase. Table I presents some pertinent data on the proposed allotropes. For the ?(fcc)-ß(hexagonal) transformation

Jan 1, 1967

By F. G. Miller

Earlier studies of the mechanism of flotation showed that coal flotation products are contaminated by composite coal and mineral particles. The mineral matter of these particles has the dual effect of increasing the specific gravity and decreasing the coal surface of the particle available for bubble attachment. The present study showed that these particles are more loosely held in the froth column than the high grade coal particles, especially in the coarser sizes. Consequently, it is possible in the laboratory to produce a secondary concentration of the product by sprinkling the froth product with water to wash these loosely held particles from the froth during formation and recovery. To improve coal flotation, Bethlehem Steel Corp.'s research department has been working on a number of related problems based on both physical and chemical factors. The ideal is of course full understanding of the interrelated effects of both sets of factors. However, detailed studies1 of each physical factor have produced immediately usable results in commercial coal flotation and are providing the basis for our current work on the effect of chemical factors. Since these detailed studies provided the basis for the present investigation of froth sprinkling, their key results are highlighted here. For example, for a highly floatable bituminous coal, particle floatability was shown to be directly related to the percentage of coal surface available for bubble attachment and inversely related to particle mass. The data also underscored that in a given size range the addition of mineral matter to a particle makes flotation more difficult both by adding to the mass of the particle and by decreasing the amount of coal surface available for bubble attachment. Size also affects particle floatability in that as the size of particles of a given specific gravity increases, mass increases and the ratio between coal surface area and mass of the particle decreases. Flotation tests showed that any recovery of the coarsest particles in a coal feed is accompanied by progressively higher recovery of finer and finer particles. Consequently, fine high-specific-gravity particles are recovered with the coarse good coal. As a result, when the entire 14 mesh x 0 size range is processed by froth flotation, the good coarse coal is contaminated with high-specific-gravity fines. It is the small quantities of these fines that must be rejected from the froth product if flotation efficiency is to be increased above its present level. These principles and findings, together with work by Professor V. I. Klassen,' led to the froth sprinkling investigation reported in this paper. Working with Russian coals, Klassen had shown that froth sprinkling washes loosely held refuse particles from the froth and compensates for the water lost in the upper froth layers and increases its stability. As a result, the coal particles are retained in the froth and the loss of coarse coal from the froth is prevented. Decreases in ash of 0.1% to 1.5% were reported by Klassen. Working with a 28 mesh x 0 American coal, the author of the present paper found that single-stage flotation coupled with froth sprinkling produced a product comparable to that obtained by the more expensive method of roughing and cleaning.3 The investigation reported in the present paper expanded study of the effect of froth sprinkling to include each of the standard size fractions of a bituminous coal. The main findings are as follows: (1) For those size fractions between 48 mesh and 150 mesh, froth sprinkling produces a marked reduction in both sulfur and ash. In the case of those sizes coarser than 48 mesh, while this reduction is not as significant, the additional benefit of shorter retention time is still a plus for froth sprinkling. Furthermore, when froth sprinkling is coupled with normal fast flotation, the product purity approaches that obtained by starvation reagent feeding, i.e., gradual feeding of flotation reagent to float the recoverable coal from the pulp slowly in several increments. The specific results for these two size groups are: (a) 14 x 48 Mesh. By using froth sprinkling with fast flotation, product sulfur can be reduced to a level

Jan 1, 1970

By P. Gobin, J. Perez, P. Peguin

The strain-amplitude- dependent part of the internal friction of alluminum after several ther momechanical treatments has been measured in the I-cycle range and at the ambient temperature. The internal friction in the outer layer of the torsional specimen us stress is computed from the experimental data. The curues obtained are analyzed in tevnzs of u coirzbinntion of AH and p, which aye, respectively, due to the vecersible unpinning from weak pills and to the plastic strain. Considerirlg the notion of thermally activated unpinning and repinning, it is shown that in our experimental conditions tlze dislocation lines acl as in the H model of Granato and Liiclze. It is also seen that the internal friction p which appears at higher- strains call be described by a simple expression which is in good agreement with our results. A qualitative interpretatiorz is proposed by combining these new types of intelpnal fviction. We define the internal friction 6 as half the ratio of the dissipated energy aW during one cycle to the maximum supplied strain energy W of a material submitted to a periodic stress. Experiment and theory show that internal friction varies with stress above a critical value.' Below this value the internal friction is strain-amplitude-independent and is often masked by an experimental background; so we shall call it AB. ~bove this critical value, the internal friction is strain-amplitude-dependent. This quantity is usually called aH:' and it can be explained as a thermal unpinning of dislocations.3-6 Furthermore, at higher stresses, a rapid increase of internal friction appears. This phenomenon could be caused by the plastic strain,' so we shall call it Ap. It seems interesting to us to study the influence of several t her momechanical treatments on the curve internal friction 6 vs strain E, in order to study the variation of AH and p with the concentration and the repartition of linear and point defects. In order to try to explain the results obtained, we shall propose and discuss models for H and hp and shall show that we obtain a combination of these two types of internal friction. 1) EXPERIMENTAL PROCEDURE 1) Preparation and Treatment of Specimens. We

Jan 1, 1968

By M. Yoshinuga, S. Watanabe

Some iron ores, sinters and pellets occasionally show abnormal behavior during reduction which makes them undesirable as blast furnace burden. These may be divided into the following three types: (1) decrepitation of iron ore, (2) swelling of iron ore and pellet, (3) size degradation of sinter. In this paper reduction experiments and microscopic examinations were made to clarify the mechanisms and causes of these abnormal phenomena. Decrepitation occurs mainly when compact hematite ores containing small amounts of limonite are heated to about 500°C. Abnormal swelling of ores and pellets is caused by the rapid growth of fibrous metallic iron from the surface of wustite grains during rapid reduction and is fundamentally related to their original microstructure. Size degradation of sinter occurs through the development of cracks in the reduction stage from hematite to magnetite. About 80% of the iron ore used in Japan's blast furnaces comes from abroad, and the iron and steel industry must import this raw material from distant overseas places at high freight rates. The blast furnace operators, therefore, have made strong efforts to cut costs under these restrictive raw materials conditions by increasing productivity and simultaneously decreasing coke consumption. If, however, a high proportion of the ore burden consists of unsuitable materials furnace irregularities often result, establishing the need for detailed investigations of the basic natures of the ore constituents and their reactions during the reduction process. Recent investigations '-' of various ore burdens suggest that some iron ores, sinters and pellets are occasionally abnormal in appearance and behavior during reduction studies and may prove to be undesirable for use in the blast furnace. In the present study reduction experiments and microscopic observations were made to clarify the causes and the mechanisms of the abnormal behavior observed in some constituents of the burden and their effect on blast furnace performance. REDUCING APPARATUS The four kinds of reducing apparatus used in this investigation were the following: 1. The JIS* (Modified Gakushin') apparatus shown in Fig. la is most commonly used in Japan to evaluate the reducibility of ores under static conditions. It consists of a stainless steel tube of 60 mm inside diam suspended from a balance. 2. Linder's Reduction Test apparatus (Fig. lc) has a reducing barrel 130 mm diam and 200 mm long which rotates at 30 rpm. Some modifications were made in test procedures. 3. Gakushin Standard Test apparatus for determining the reducibility of granular ores (Fig. Id) consists of a horizontal silica tube 32 mm diam, 370 mm long and a movable electric furnace which enables rapid heating and cooling of the specimens. 4. The test apparatus for reduction under load (Fig. lb) gives a comprehensive evaluation of the behavior of ores under conditions simulating the static loading and the chemical reduction conditions encountered in. a blast furnace stack. A stainless steel tube of 50 mm diam and a carbon rod of 35 mm diam were used as the sample container and the support for the weight, respectively. In each investigation care was taken to select the most suitable method and apparatus to distinguish the abnormal nature of the ore in question. SIZE DEGRADATION OF SINTER DURING REDUCTION Sinter makes up the major portion of the blast furnace burden and its behavior during reduction should bear a close relationship to the iron productivity. Recently, some of the sinter was found to show serious size degradation during reduction at a relatively low temperature range. Because this phenomenon was thought to be a possible source of furnace irregularities, tests were made to clarify the phenom-

Jan 1, 1969

By J. R. Long, R. S. Dean, F. S. Wartman, E. T. Hayes

The production of titanium in I5-lb. lots and with a purity sufficient to be consolidated into ductile metal, as described in a previous paper,' has provided adequate material for a study of the physical properties of titanium and a more thorough examination of its working qualities. Data on the physical properties reported in that paper were obtained on metal fabricated by a fixed procedure, standardized for the purpose of control of the reduction, and are representative only of material fabricated under those conditions. There are many possible variables in the working schedule, which will have significant effects on the properties of the finished material; and since the previous working methods were not necessarily the best, an investigation of the fabrication of titanium by other methods was undertaken. In this work the consolidation of the powder by pressing and sintering was conducted essentially as outlined in the report cited' and all efforts were centered on fabrication methods for those powders and the proper- ties produced by them. Hardness, density, microstructure, and tensile properties were determined at various stages in the working and annealing; and resistivity measurements were made on a few bars and drawn wire. Consolidation of the PowdeR The screen analysis of the available titanium powder is given in Table I. No attempt was made to alter the size distribution from that noted because this powder, although coarse by normal powder-metallurgy standards, produced acceptable compacts suitable for the present work. Because of their large specific surface, finer powders are more contaminated by oxygen and produce harder compacts, which are difficult to work. The powder as produced is soft, compresses in a normal fashion, and exhibits very little tendency to adhere to the die surfaces. Unlike aluminum and magnesium powders, it can be readily pressed without the use of die lubricants. When compacted at 50 tons per

Jan 1, 1946

By G. W. P. Rengstorff

In an effort to find an oxidation-resistant alloy of molybdenum, binary and ternary alloys containing aluminum, chromium, cobalt, iron, nickel, silicon, titanium, tungsten, vanadium, and zirconium were screened. Fourteen other alloying additions were also tested. Many of the alloys were more oxidation-resistant than molybdenum, but none were entirely satisfactory. MOLYBDENUM oxidizes extremely rapidly above 1450°F in air. At 1800°F, a loss of metal at the rate of 0.1 in. in 4 hr is typical. The high speed of this oxidation may be judged by comparison with the oxidation rate of 0.1 in. per year (0.00005 in. in 4 hr), sometimes taken as the maximum permissible oxidation rate at 1800°F for a satisfactory Fe-Cr-Ni alloy. Great strides have been made in the development of coatings and cladding to protect molybdenum from oxidizing atmospheres. These developments in surface protection will undoubtedly make it possible to take advantage of the excellent hot strength of molybdellum and its alloys in many new applications. Still, even the best coating can protect molybdenum only as long as the surface layer is unbroken. Research was undertaken to determine whether an alloy of molybdenum could be found which would resist oxidation. Such an alloy would not deteriorate suddenly when the protective surface layer was destroyed in a small area. In seeking an alloy of molybdenum to resist oxidation, the physical properties of molybdenum could not be sacrificed entirely. The development of an alloy with the desired resistance to oxidation was not achieved. The information obtained on the effect of a large number of elements on the oxidation of molybdenum is, however, of value in the development of coatings. Indeed, many of the alloys tested for oxidation resistance were already known to have poor mechanical properties but were tested to aid in the development of coatings. Oxidation of Molybdenum The rapid oxidation of molybdenum is usually attributed to the volatility of Moo,,. Gulbransen and Wysong have shown that molybdenum oxidizes very slowly up to 850°F, the temperature at which the oxide film begins to evaporate. Melting as well as evaporation of molybdenum oxides promotes the oxidation of molybdenum. MoO melts at 1465°F. MOO, the oxide which is believed to form at the metal-oxide interface, combines with MoO, to form a eutectic having a melting point of 1432°F.' The liquid oxide, even if nonvolatile, could cause poor resistance to oxidation by allowing easy transport of molybdenum and oxygen ions through the oxide. Actually, a sudden increase in the rate of oxidation of molybdenum at 1460°F has been observed to coincide with the appearance of a liquid phase. The formation of a volatile oxide is not unique with molybdenum. The problem is also encountered with vanadium, tungsten, and some of the Pt-Pd group of metals. Vanadium not only forms the volatile V2O3 but, like molybdenum, forms a liquid oxide coating. Few attempts have been made, however, to prevent the rapid oxidation of these metals by alloying. Oxidation of Molybdenum Alloys At the beginning of this work, very little was known of the oxidation resistance of molybdenum alloys. It was known that molybdenum disilicide (with 37 pct Si) has extremely good oxidation resistance,' but this compound is so brittle that it has few uses. It is an effective protective coating for molybdenum when allowance can be made for its brittleness. Chromium was known to retard the oxidation of molybdenum,' but at least 50 pct Cr was necessary to have an appreciable effect. Other, unpublished, reports show that a few other alloys have been given preliminary tests, but the results have not been promising." Choice of Alloys to be Investigated An alloying element might be expected to protect molybdenum in either of two ways: Its oxide might combine with molybdenum oxide to form a stable, nonvolatile complex oxide (a molybdate); or the oxide of the alloying element might form in preference to molybdenum oxide, developing an impervious layer which would prevent the formation of a volatile molybdenum oxide. The knowledge available about the formation of molybdates was meager. Therefore, the initial study was made on alloys of molybdenum with elements having especially stable oxides. On this basis, binary and ternary alloys containing the following six elements were investigated: aluminum, chromium, titanium, zirconium, silicon, and vanadium. Nickel was also added as an alloying element. Although it does not form a more stable oxide than molybdenum, it does impart some oxidation resistance to copper and iron. Its inclusion in the study was fortunate because its alloys proved to be the most promising of those first tested. Apparently nickel formed a stable molybdate. Because nickel was effective in reducing the oxidation rate of molybdenum, the elements iron, cobalt, and tungsten were added to the list. The ten alloying elements mentioned form ten binary and 45 ternary alloying systems with molybdenum. A series of alloys was tested in each of these systems. In addition, at least one test was made on the effect of each of the following alloying elements:

Jan 1, 1957

By Edgar Kidwell

To any one acquainted with the practical conditions surrounding the mining engineer and mine-manager, especially in this country, the presentation to the American Institute of Mining Engineers of a paper on the above subject will need no explanation. The members of this profession are continually called upon to design and erect, both above and underground, structures which involve the use of beams. Not to mention the various buildings connected with large mining operations, I need only refer, in support of this statement, to trestles, derricks, headworks, etc., on the surface, and to timbered stations and other spaces of large span in the mine-workings. Notwithstanding the rapidity with which iron and steel are replacing wood in the construction of large buildings, there will always be cases in which the use of metal will be unadvisable. Especially will this be true in districts remote from large cities. Works of temporary character will continue to use timber. High freight-charges, the liability of delays in delivering iron, and the temporary character of many of the structures, will for many years to come make it advantageous for the mines west of the Mississippi and on Lake Superior to construct their buildings almost exclusively of wood. The timber-resources of the country are decreasing so rapidly that already the engineer finds difficulty at times in obtaining beams of large size. This difficulty will steadily increase, and will force the constructor to resort more frequently to built-up beams, such as have long been used in Europe, owing to the difficulty of obtaining there such large sizes of timber as have

Jan 1, 1898

By A. S. Michaels, R. S. Timmins

A study of the effect upon oil recovery from an un-consolidated porous medium of chromatographic transport of selected reverse-wetting additives during water displacement is described. Flow tests were performed on hydrocarbon oil-saturated sand columns (containing connate water) into which small volumes of short-chain aliphatic amine solutions were introduced during water flooding. Concurrently, meusurements of oil-silica contact angles, oil-water interfacial tensions and oil-water distribution coefficients were measured us a function of additive concentration. Certain treatments were found to cause a slight reduction in oil recovery, while others produced a significant increase (up to 50 per cent of the normtzl irreducible rninimum oil saturation). Recovery eficiency was correlated most satisfactorily with the maximum degree of reverse wetting produced during additive transport; conditions which resulted in only mild oil wettability of the sand reduced recovery, while those favoring strong oil wetting increased recovery. A mechanism of reverse-wetting additive action during chromatographic transport is developed which ascribes the results to transient changes in oil-solid contact angle during flow, with consequent release of oil trapped by capillary forces. Implications of these observations with regard to improved waterflood efficiencies are discussed. INTRODUCTION The need for finding improved methods of oil production is amply illustrated by the large volume of oil considered economically unrecoverable by existing production practice. Water flooding has long been an excellent method of secondary recovery. However, even in those areas of a formation which are well swept by a water flood, 20 per cent or more of the oil remains trapped within the formation and is not recovered. This trapping of oil within the pores of the rock structure results primarily from interfacial forces. If these interfacial forces were altered, it is possible that the trapped oil could be released and recovered. The addition of surface-active agents to a water flood to alter the interfacial properties of the oil-water-solid system has received considerable attention as a method of increasing oil recovery. Studies of surfactant treatment have yielded varied and, in some cases, apparently conflicting results. Increased oil recovery using surface-active agents has been reported by a number of investigators. Others have found that use of surfactants in a water flood either has no effect upon oil recovery or decreases it. Since surface-active agents tend to alter the formation wettability and oil-water interfacial tension simultaneously, several investigators have tried to determine the role these two factors play in oil recovery. Data have been presented which indicate that the most desirable condition for the solid surface is strongly water-wet. Other results indicate that, although breakthrough recovery may be less, the greatest ultimate recovery is obtained when neutral wettability prevails.", " The desirability of low interfacial tension seems to depend upon the wettability of the formation. Reports of higher recoveries, when the interfacial tension is high in a water-wet system and low in an oil-wet system, are at odds with reports of increased recovery in water-wet systems when surfactants which decrease the interfacial tension are added to the water flood. A review of previous work studying the effects of using surface-active agents in a water flood shows that these agents produce widely different effects and that opinions as to the role of the various interfacial properties are diverse. The consensus, however, is that the interfacial properties are quite important in the displacement of oil from a porous medium by water. Even in those investigations where appreciable increases in oil recovery resulted from treatment with a surface-active agent, economic considerations generally made practical application of the treatment unattractive because surfactants tend to be adsorbed within the formation. This adsorption would necessitate using large quantities of surfactant if all of the flood water were treated to contain a given surfactant concentration, even if this concentration were quite low. Preston and Calhoun suggested that the principles of chromatography could be applied to the use of surface-active agents as a means of increasing oil recovery. A small volume of surface-active material is injec-