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By R. O. Leach, O. W. Wagner

Because of unfavorable wetting conditions much residual oil is left when a porous material is Pushed by water. Methods suggested to change reservoir wetting to improve oil displncernrnt efficiency are generally expensitlr. The present 1aborator.y study was undertaken to gain an under.standinx of the factors which determine reservoir wettability, arid to find out if oil displacement efficiency might be improved by a wettahility change accomplished at low cost in on oil reservoir. Contact angle measurements were made on mineral surfaces using sevc.r~zl sets of reservoir oil and water samp1es. Results of the contact angle studies suggest that reservoir wetta-hility may he primarily determined by natural surface-active substances present in the reservoir fluids. The effect of changing sa1inity and pH of the water phase was studied. The re.suits suggest that gross changes in preferential wettability might be acc~o~npli.shed by injection of water containing simple chernicnls to alter pH or salinity in the reservoir. Such treatment could he much less expensive than injection of commercial surface-active agents. Waterflood tests have also been made using synthetic cores and oil and water having wening characteristics similar to those of reservoir fluids. Cores initially oil-wet were flooded in such a way that they were made prefermtial1y water-wct by the advancing flood water. This reversal in preferential wettability achieved greater oil displacement efficiency than when either oil-wet or water-wet conditions were maintained throughout the flood. For the systems studied, the higher the oil viscosity the greater the percentage improvement obtained over conventional waterflood recovery. This suggests that a flooding process making use of wettability-reversal may extend the oil viscosity range over which water flooding is attractive. Because a precise adjustment of reservoir wettability does not seem to be required, and because altering the pH or salinity in some reservoirs may be inexpensive, it appears that a waterflooding process employing wet-[ability-reversal could find .succesful field application. I NTRODUCTION The efficiency with which water will displace oil from a porous material is related to the nature of the capillary forces present. These in turn are controlled by the preferential wetting of the solid by the two fluids. Because of unfavorable wetting conditions, 30 per cent or more of the original oil in place may remain unrecovered in that portion of a reservoir flushed by water. This paper is concerned with the possibility of improving waterflood oil displacement efficiency by alterations in the wettability of the porous material. A laboratory study was made to gain a better understanding of the factors which control reservoir wettability, and to determine if the oil displacement efficiency could be improved by some inexpensive means of manipulating wettability of the porous medium. Contact angle measurements were made with several natural and synthetic oil, water and solid systems (1) to obtain a better understanding of how to duplicate reservoir wettability in the laboratory, and (2) to discover possible means for changing preferential wettability of natural reservoir systems. Flooding tests were also made in synthetic systems to determine if oil displacement efficiency could be improved by those wettability manipulations suggested by the contact angle measurements. Based on these studies a possible method for improving waterflood oil displacement efficiency is presented. This method involves causing an originally oil-wet porous material to become preferentially water-wet during the course of a water flood. The purpose of this paper is to present results of the laboratory studies. THEORY Rock surfaces in some oil reservoirs are believed to be covered with a firmly attached bituminous or other organic coating. Such surfaces would be preferentially oil-wet in the presence of both oil and water, regardless of composition of reservoir fluids. Other reservoirs are believed to contain rock surfaces not permanently coated with such materials, and which would be preferentially wet by water in the presence of water and oil free from surface-active substances. However, when the reservoir fluids do contain certain natural surface-active materials in sufficient quantity, rock surfaces acquire a degree of preferential oil wettability caused by adsorption of these natural surface-active materials on the solid. The equilibrium amount of these materials adsorbed per unit surface area is believed to depend upon their concentration in the bulk liquid phases.

By W. A. Backofen, D. Lee

The deformation of textured sheet of titanium and several of its all-a (hcp) alloys was investigated with two kinds of experiments: tension testing along different directions in the plane of the sheet, and combined-stress loading along the principal axes of anisotropy (the rolling and transverse directions). Texture and plastic anisotropy were evaluated with pole figures and by measurement, as a function of orientation, of the tensile transverse-strain ratio, or R parameter. The results as a whole can be rationalized qualitatively with the present understanding of deformation mechanisms in titanium. Quantitative agreement between the orientation dependence of tensile yield strength and the Predictions of continuum ANISOTROPY in the properties of engineering materials is more the rule than the exception because anisotropy in structure is so common, and the one generally follows the other. Two broad categories of structural anisotropy are represented by mechanical fibering and crystallographic texture. The former is important in many aspects of fracture.' The latter has more significance for yielding and plastic deformation, theory, using the R measurements, was relatively poor. However, in tension-tension quadrants of the yield-locus diagrams, the difference between theory and experiment was hardly more than 10 pct. The maximum texture-hardening effect was found in a 4Al-1/4O2 alloy to be nearly 50 pct. In the compression-compression quadrant, {1012} deformation twinning prevented the locus from expanding much beyond the Position predicted for isotropic material. With increasing temperature the trend in R was downwards, approaching unity (isotropy) near the a-transus temperature; an accompanying development was large amounts of neck-free extension. which are of special concern in this paper. The tendency has been to view crystallographic texture more as a liability or curio than as an asset. The prominent exception is found in silicon-ferrite sheet for power-transformer cores, which is processed to develop a new optimum texture for high electrical efficiency. Yet it should be possible to find other examples, involving other kinds of properties. More specifically, there is good analytical reason to expect improved combined-stress yielding resistance in suitably textured material,2,3 and it has now been shown by experiment that texture hardening or softening is a potentially useful phenomenon in certain engineering devices and processes.'-I To date, work has included measurements of the transverse (width to thickness) strain ratios in the

Jan 1, 1967

By C. E. Wood, E. P. Barrett, T. L. Joseph

The United States Bureau of Mines has been studying the blastfurnace process for about ten years. An experimental furnace was developed by the Burcau in cooperation with the Minnesota School of Mines Experiment Station, University of Minnesota. Many data have been obtained and published.' Royster, Joseph and Kinney §(48) found that the particle size of ore had an important effect upon the blast-furnace process. Kinne(28) stated: Economy in blast-furnace practice depends largely upon efficient gas-solid contact in the shaft of the furnace. If efficient work is not done in the shaft, the hearth and bosh will not function properly. A condition may be readily imagined where the particles of ore in the shaft are so large that the time entailed in the descent of these materials into the bosh is not sufficient to permit proper reduction and preparation prior to the time the ore enters the bosh of the furnace. Another condition may be pictured where the density of theatock column and the flow of stock is such that the ore will take one course and the gas another. Both of these examples will result in insufficient contact between the gas and the ore. Unreduced ore will reach the hearth, and the gas which has not been efficiently oxidized will reach the stock line. The result is the use of an excess of carbon in the smelting process. It is obvious that fine ore particles occurring in the ore as charged, or formed in the furnace due to heat and mechanical action, place a definite limitation upon the efficiency of the operation. There is also an economic loss of fine material as dust. Effect of Size of Material Kinney reported (p. 83(29)) the reduction of iron oxides between planes at three furnaces as given in Table 1. The Chicago furnace was operated on Lake ores. Distribution of gas was not good and much of the charge passed into the hearth before the iron oxide was reduced. The Holt furnace was operated on coarse ore. Distribution of gas was fairly uni-

Jan 1, 1930

Jan 1, 1910

By M. Sagheer

This paper gives a report of the laboratory work investigating the fundamental flotation characteristics of chromite and its commonly associated mineral, serpentine. Floatability curves, showing floatability of chromite at different concentrations of sodium oleate and pH, were obtained by pick-up method. One of the difficulties encountered in flotation of chromite in presence of serpentine has been attributed to dissolved metal ions. The influence of metal ions, dissolved in pulp filtrate, on floatability of pure chromite and serpentine has been studied and it has been shown that Mg, Ca and Fe ions depress chromite. A considerable amount of work applying bubble pick-up method was carried out to counteract the depressing action of metal ions. Various methods and reagents were applied in this connection. Validity of each method and reagent has been discussed. Probably due to the abundance of high-grade chrome ores, very little has been published concerning the flotation of chromite. As improvements in mineral beneficiation are realized, more attention is being directed to low-grade ores previously considered unusable. Currently, gravity concentration is the principal process applied to upgrade chrome ores, but this cannot be used for finely disseminated ore because of the substantial losses in the fines,1,2,3 To avoid these losses, flotation can be applied to material which is too fine for satisfactory gravity concent ration, and it is probable that a combination

Jan 1, 1967

By D. S. Rowley, F. C. Appl

Assuming that rock behavior, during cutting with a single diamond, may be approximated by that of a rigid, Coulomb, plastic material, a theory of single diamond cutting action has been developed. Using this theory, the stresses on the diamond cutting surface and the components of the cutting force have been determined. Theoretical results agree reasonably well with available experimental data. The theory of cutting of single diamonds may be used as the basis for subsequent study of the perfonnance of surface set diamond drill bits and other surface set diamond cutting tools. INTRODUCTION For more than twenty years, surface set diamond bits have been used successfully in the mining and petroleum industries to drill and core rock formations that range from medium hard to the hardest known formations. Most extremely hard rock formations cannot be economically drilled or cored by any other means. In view of the growing use and importance of surface set diamond drill bits, it is reasonable to study the way in which these tools cut, and the factors that influence wear of the diamonds. Such knowledge will contribute to better bit design and will improve operating procedures. To analyze the cutting performance of these tools it is appropriate to consider the way in which an individual diamond cuts. Once this is established, the over-all performance of the bits can be determined by considering the total effect of the individual diamonds. In recent years there has been a growing interest in rock mechanics and there now exist several publications dealing with the deformation and failure of rocks. Notable experimental work has been reported by Bredthauer,1 Handin and Hager,2, 3 and Gnirk and Cheatham.4 An extensive collection of data pertaining to rock properties at low confining pressures has been given by Wuerker.5 Cheatham and Gnirk have recently presented an excellent review of the state of knowledge regarding analytical and experimental rock deformation and failure.6 Generally rocks are extremely weak in uniaxial tension, and weak or only moderately strong in uniaxial compression. Both tensile failure and compressive failure are generally brittle in nature. This means that there is little or no deformation or "flow" of the material before shear or tensile fracture occurs. Thus, until fracture occurs, rock behaves very nearly like an elastic material in uniaxial stress. Significant changes in behavior of rock occur under conditions of triaxial compressive stress. There is generally a marked increase in compressive strength and in ductility. It has been demonstrated that the failure becomes plastic (in a macroscopic sense) at sufficiently high values of confining pressure. Sharp wedge chisel indentation studies conducted by Gnirk and Cheatham indicate that many rocks behave in a plastic manner at relatively low triaxial compressive stress states.4 If "failure" under triaxial compressive conditions is considered to be either complete rupture or macroscopic plastic flow, then the general failure characteristics of a rock can be reasonably well represented by the commonly known Mohr envelope. This certainly is not a perfect failure criterion (since the effect of the intermediate principal stress is neglected) but it has been found to be adequate for most engineering purposes. Mohr envelopes usually are constructed graphically using experimental triaxial test data. For purposes of analysis it is convenient to represent the envelope in equation form. Among the several approximate forms appearing in the literature, a parabolic form is suggested by Cheatham,7 and an exponential form is suggested by Paone and Tandanand.8 The exponential form has been adopted for this study, and based on published data, appropriate parameters have been established for 19 rock types. A typical plot of the data compared with the approximate envelope, and a summary of the rock properties and

Jan 1, 1969

By W. L. Phillips

Stress-train curves were obtained for single crystals of silver, Ag-5 pct Zn, Ag-10 pct Zn, and Ag-20 pct Zn tested in tension and shear at 78°, 195°, and 297°K. At room temperature the critical resolced shear stress gC increased, the length of' the easy-glide region increased, and the rate of' work hardening dwving easy glide decreased with increasixg zinc concentration. The change in the ratio of uc at room temperature to that at lower temperatures was significantly greater for the alloys than for pure silver. It was found that an increment in stress was necessary to continue slip when the slip direction was rotated 60 deg. The magnitude of this increment increased with strain for all alloys, increased with zinc concentration for a given strain, and for a given strain increased with decreasing -temperature. DESPITE its practical importance in improving the mechanical properties, alloying is not fully understood. Except for copper alloys few sets of systematic data are available. Von Goler and Sachs' studied the deformation of Cu-Zn alloys of increasing zinc content and found that, for dilute alloys, the critical resolved shear stress increases linearly with concentration. The range of easy glide was found to increase with increasing zinc content. Schmid and seliger,2 Sachs and Weerts,3 and Osswald4 have shown that with Mg-A1, Au-Ag, and Cu-Ni crystals, respectively, the critical resolved shear stress also varies linearly with concentration. More recently, Linde and his coworkers have investigated the variation of the critical shear stress of copper alloyed with tin , antimony, indium, germanium, silicon, nickel, and gold. They found that the slope of the critical resolved shear stress is related to the change of lattice parameter with composition, and also to the difference in Goldschmidt's atomic diameter between solvent and solute atoms. Garstone, Honey-combe, and creetham6 have shown that similar relationships can be found for small additions of silver, gold, and germanium to pure copper. They found that, with increasing silver or gold concentration, the critical shear stress for glide is increased by alloying, and so is the range of easy glide, which reaches as much as 60 pct for 0.50 pct Ag alloy and 0.62 pct Au alloy, as compared to 6 pct for pure copper of similar initial orientation. They also found that the alloying additions had little effect on the rate of hardening during easy glide, the slope scarcely changing with increasing alloy content. General secondary slip was detected only when the crystals began to harden rapidly. Although the slip appeared to be very fine in the early stages of deformation, coarser slip bands were formed towards the end of the extensive easy-glide range. The present investigation describes the deformation characteristics of single crystals of Ag-Zn containing different concentrations of zinc. Tension and shear testing were used for this study. EXPERIMENTAL PROCEDURE The method of growing the single crystals, sample preparation, and method of testing have been described in detail previously.' EXPERIMENTAL RESULTS A) Tension-Room Temperature. The initial orientations and stress-strain curves of single crystals of silver, Ag-10.0 pct Zn, and Ag-20.0 pct Zn are shown in Fig. 1. It is evident that there is considerable change in the stress-strain characteristics as a function of zinc concentration. The effects of zinc concentration on the critical resolved shear stress for both CU-zn8 and Ag-Zn alloys are summarized in Fig. 2. At all concentrations the resolved shear stress of the Cu-Zn alloys is higher than that of the Ag-Zn alloys. The resolved shear stress increases parabolically as a function of composition for both alloy systems. The length of easy-glide region increased with increasing zinc concentration, Fig. 3b). As the length increased the slope (do/de) decreased slightly, Fig. 3(b). Metallographic investigations demonstrated two significant effects of increasing zinc concentration. First, the amount of clustering increased, compare Figs. 4(a) and (b). The slip lines changed from uniform in pure silver to clustered in the Ag-20 pct Zn and Ag-30 pct Zn alloys. Second, the amount of cross slip decreased as the amount of clustering decreased.

Jan 1, 1968

By T. A. Wilson, S. L. Hoyt

THE plastic deformation of slender single crystals of zinc has been described in some detail in the paper by Mark, Polanyi and Schmid,1 which has become a classic, and also by one of the present authors in a somewhat shorter account.' The study of single-crystal zinc is termed classical because zinc single crystals offer, perhaps, the best material yet available for the study of atomic behavior during deformation and the effect known as "strengthening" in metals. A considerable amount of additional work has also been done on single-crystal zinc, but as it is not closely related to the present paper it will not be considered. Throughout all the former work, the mechanism of plastic deformation first described by Mark, Polanyi and Schmid has been assumed to hold. This may be said to offer the strongest confirmation of its correctness. Even so, the picture of the process has never been as completely portrayed as is desirable. The first object of the present paper is to describe work that has been done in this field, and which is even yet being carried on, in the hope that a more complete picture may be obtained. Mathewson and Phillips' have recently described a new mechanism of the deformation of zinc based on their study of large rectangular crystals. One of their conclusions was that deformation produced twinning with a rotation of some of the basal planes into positions 94° removed from their original position; a position almost the same as that of the prismatic planes before twinning. A second conclusion was that fracture occurred along these basal planes in their new position, and, therefore that fractures previously regarded as prismatic were in reality basal. Such findings are of great significance and they raise a question as to the generality of such behavior. Professor Mathewson's opinion is that even the slender cylindrical single crystals behave in the same manner as his large rectangular crystals when strained by simple tension.

Jan 1, 1928

By T. B. Counselman

PRobably the earliest concentration of iron ore in this country was carried on in the northeastern magnetite areas. Magnetic concentration was relatively simple and gave a concentrate that, after agglomeration, and in spite of beillg high in phosphorus hecause of the dry concentrating methods then in use, was satisfactory blast-furnace feed. Production from the northeastern magnetitc area languished after the discovery and development of the Lake Superior ores, where there was seemingly an unlimited tonnage of high-grade ore, first the Michigan ores, and subsequently the still larger deposits of Minnesota. For years only the higher grade, direct shipping ores of the Lake superior district were mined. Those of Michigan, and of the Vermilion Range in Minnesota, were hard ores and came principally from underground mines. The softer ores of the Mesabi came partly from underground mincs, but mostly from the enormous deposits that could be worked by open-pit methods. The costs of ore from these open-pit deposits, even with the high initial cost of stripping, were so low that the underground mines of the Mesabi could hardly compete. The so-called Old Range ores, of Michigan and of the Vermilion Range of Minnesota, were hard and lumpy, and opened UP the burden in the blast furnace, therefore making possible harder driving with greater output. Also, some of these Ores were of such grade and physical characteristics that they were suitable for charge ore in the open hearth. These ores, therefore, commanded a price premium. and could compete with the softer, finer, but cheaper, Mesabi ores. The big tonnage reserves, however, are on the Mesabi. and it is these big open-pit deposits that contitue- our stock pile of iron ore, from which we are drawing so heavily during this war period. On the western end of the Mesabi the ore was found to be high in silica, and not suitable as furnace feed. As early as 1902, attempts were made to concentrate this so-called wash ore and by 1910 the first washing plant was put into operation. The Process was very simple, consisting essentially of a sizing and washing operation, with scalping screens, logwashers and tables, which later were replaced by classificrs. Ore particles finer than I00 mesh were deliberately wasted, because these fines were undesirable in the furnace. Fortunately, these tailings were impounded, and already are being reworked. Before long some of the low-grade ores began to require more elaborate treatment than the simple washing operation and, tables having been discarded because of their low capacity, in favor of classifiers, jigs were next introduced. These were able to discard coarser pieces of tailing than classifiers. Jigs are in active use today, various improvements having been made in their design and application. Various other machines and methods of concentration have been tried from time to time, and have in turn been discarded for more improved processes., The latest and most important process that has been 38

Jan 1, 1944

By T. B. Counselman

PRobably the earliest concentration of iron ore in this country was carried on in the northeastern magnetite areas. Magnetic concentration was relatively simple and gave a concentrate that, after agglomeration, and in spite of beillg high in phosphorus hecause of the dry concentrating methods then in use, was satisfactory blast-furnace feed. Production from the northeastern magnetitc area languished after the discovery and development of the Lake Superior ores, where there was seemingly an unlimited tonnage of high-grade ore, first the Michigan ores, and subsequently the still larger deposits of Minnesota. For years only the higher grade, direct shipping ores of the Lake superior district were mined. Those of Michigan, and of the Vermilion Range in Minnesota, were hard ores and came principally from underground mines. The softer ores of the Mesabi came partly from underground mincs, but mostly from the enormous deposits that could be worked by open-pit methods. The costs of ore from these open-pit deposits, even with the high initial cost of stripping, were so low that the underground mines of the Mesabi could hardly compete. The so-called Old Range ores, of Michigan and of the Vermilion Range of Minnesota, were hard and lumpy, and opened UP the burden in the blast furnace, therefore making possible harder driving with greater output. Also, some of these Ores were of such grade and physical characteristics that they were suitable for charge ore in the open hearth. These ores, therefore, commanded a price premium. and could compete with the softer, finer, but cheaper, Mesabi ores. The big tonnage reserves, however, are on the Mesabi. and it is these big open-pit deposits that contitue- our stock pile of iron ore, from which we are drawing so heavily during this war period. On the western end of the Mesabi the ore was found to be high in silica, and not suitable as furnace feed. As early as 1902, attempts were made to concentrate this so-called wash ore and by 1910 the first washing plant was put into operation. The Process was very simple, consisting essentially of a sizing and washing operation, with scalping screens, logwashers and tables, which later were replaced by classificrs. Ore particles finer than I00 mesh were deliberately wasted, because these fines were undesirable in the furnace. Fortunately, these tailings were impounded, and already are being reworked. Before long some of the low-grade ores began to require more elaborate treatment than the simple washing operation and, tables having been discarded because of their low capacity, in favor of classifiers, jigs were next introduced. These were able to discard coarser pieces of tailing than classifiers. Jigs are in active use today, various improvements having been made in their design and application. Various other machines and methods of concentration have been tried from time to time, and have in turn been discarded for more improved processes., The latest and most important process that has been 38

Jan 1, 1944

By Warnie Flint

PERSONAL INJURY ACCIDENTS According to statistics compiled by the National Safety Council, US Bureau of Mines, American Medical Association, and other agencies, accidental injuries cause more deaths than all the leading diseases. NO one is immune to an accident. Probably the best way to describe an accident is to say that it is an unexpected happening. The automobile driver is not expecting a terrifying crash, the electrician does not expect to be electrocuted, nor is the coal miner expecting the roof to fall on him. All personal injuries will not result in death. There is a multitude of victims who are living proof of what accidents can mean to an individual-victims who are blind, paralytic, missing arms, legs, etc. In most instances the earning power of these individuals is gone, and they are utterly dependent upon family or welfare. For many years there seemed to be an attitude that prevailed in industrial America that accidents were inevitable, and that so many fatalities and injuries should be expected. This, of course, was utter nonsense. Since the birth of such organizations as The National Safety Council, American Society of Safety Engineers, and the US Bureau of Mines, much progress has been made in reducing accidents. The enactment of compensation laws greatly contributed to the progress that has been made. Does this mean that all accidents can be prevented? Unfortunately, it does not. Human psychology indicates that men will work unsafely or perform unsafe acts for the following reasons : 1) Lack of knowledge or skill. 2) Conflicting motivations, such as: (a) to be more comfortable, (b) to save time or effort, (c) to be accepted by a group. 3) Physical or mental condition. Nearly everyone desires his own safety, but not all individuals are willing to do what they know to do to insure their own safety.

Jan 1, 1981

By H. A. Wilhelm, P. Chiotti, G. A. Tracy

A summary of analytical, X-ray, thermal, and metallographic data obtained in the study of the Mg-U system is presented. No intermetallic compounds are formed by these two elements, and their mutual solubility is limited at temperatures up to 1255°C. The compositions of the liquids which coexist at 1135°C under a pressure of 3 atm are 0.14*0.05 wt pet U in magnesium, and 0.004 wt pet Mg in uranium. The solubility of uranium in magnesium decreases to 0.0510.03 wt pet at 675OC, and to about 0.0005 wt pet at 650°C. Due to the reactivity of both uranium and magnesium toward crucible materials, the choice of a suitable crucible presented a problem. Crucibles made from high purity magnesia to which 10 wt pet MgF2 was added to reduce porosity proved to be satisfactory. Some observations made with the use of other crucibles are given. THIS investigation was made to establish the phase diagram for the Mg-U system. Ahmann,' formerly of the Ames Laboratory, did some work on the system. He used several methods in an attempt to prepare Mg-U alloys. One of the methods involved the reduction of UF, with a large excess of magnesium. In these experiments, the magnesium wet the surface of the uranium, but there was no evidence for compound formation. The maximum solubility of magnesium in uranium was indicated to be 0.01 wt pet. In another set of experiments, uranium chips as well as uranium powder were heated in contact with molten magnesium in a graphite crucible for periods of time up to 48 hr. A reaction layer was found at the Mg-U interface in several instances. X-ray analysis of the layer material showed the presence of UC and some additional unidentified lines which were interpreted as indicating the possibility of an intermetallic compound of uranium and magnesium. These studies indicated the maximum content of magnesium in uranium to be 0.043 wt pet. One sample of magnesium which had been heated at 1025°C in contact with excess uranium was found by chemical analysis to contain 0.275 wt pet U. Rules, based on empirical or semi theoretical considerations, which attempt to predict the alloying behavior of metals have been presented in the literature. Although these rules are not infallible, they nevertheless serve as useful guides. Using them, several generalizations can be made concerning the Mg-U system. According to Hume-Rothery's' atomic

Jan 1, 1957

By Frederick M. Becket, Russell Franks

In a recent article,l which described the softening effect of columbium in plain high-chromium steels, the authors stated that their investigations had shown columbium to be also a particularly valuable inhibitor of intergranular corrosion in steels of the 18 per cent chromium, 8 per cent nickel type. It is the purpose of the present paper to record some of the results obtained through the introduction of columbium to the austenitic chromium-nickel steels. The damaging effects of this type of corrosion have become so widely known as to restrict considerably the applications of the steels under consideration, and therefore there is little question of the importance of the goal to be attained. Numerous contributions concerning the susceptibility of the austenitic chromium-nickel steels to intergranular corrosion have appeared during the past few years, and among others who have dealt constructively with the subject are such well-known authors as Strauss and Houdremont of Germany, Hatfield of England, and Bain in the United States. Different theories have been propounded as to the cause of intergranular corrosion, and various remedial measures have been proposed, the majority of which involve the use of addition agents. Titanium is the addition agent at present most generally employed, as suggested by Houdremont and modified as described by Bain, Aborn and Rutherford. Little has been published on the effects of holding these steels for long periods at the relatively lower temperatures in the presence of corroding media, and the effects have mot been fully realized by producer and consumer.

Jan 1, 1934

By L. G. Huntley

I. HISTORY OF OIL DEVELOPMENT IN MEXICO THE occurrence of oil or "tar" in Mexico was mentioned as early as the seventeenth century by Friar Sagahun, who gives the Indian name "chapopote," by which these asphalt seepages are still called. This asphalt was apparently used, as it has been used by primitive people in many parts of the world, in religious ceremonies and for medicinal purposes. Travellers also report that the ruins in Yucatan and the pyramids in southern Mexico show traces of the use of "chapopote" as a building cement.1 DeGolyer says that the first attempt to exploit oil or gas in Mexico in a commercial way is shown by the records of the Memoria de Fomento of 1865, when permission was granted to a Senor Ildefonso Lopez to exploit the deposits of petroliferous substances in the San Jose de Ias Rusias area in the State of Tamaulipas. Other concessions follow, and probably refer to surface seepages which occur in that district. This was several years after the discovery of oil in Pennsylvania. In 1868, a well 125 ft. deep was drilled by a company organized in Mexico City, in what is now known as the Furbero district, and a little oil was refined there. In 1873, residents of Tampico denounced seepages along the Tamesi River, and asphalt was mined near Tempoal in the Canton of Tantoyuca. No drilling was attempted. But between 1880 and 1883 several shallow wells were drilled for oil in Mexico, two of them being near the present Potrero de Llano field west of Tuxpam. The wells were drilled by a Boston company with Canadian rigs, and are said too have reached a depth of about 400 ft., while one is reported to have flowed. Several other abortive attempts were made to drill for oil between 1885 and the beginning of the present century, about which time the Mexican, Petroleum & Liquid Fuel Co., Ltd., in which Cecil Rhodes was interested drilled 24 wells unsuccessfully, several of them as deep as 1,500 ft., in the State -

Jan 9, 1915

[NORTH AMERICA UNITED STATES ALABAMA America.-Dyar, 0. C. Anniston.-Klugh, B. 0. Ashland.-Pallister, H. D. Auburn.-*Poor, R. S. Bessemer.-Creveling, J. 0. Lindstrom, W. A. McKenzie, W. 0. Mitchell, F. R. Birmingham.-Abbott, C. E. Aldrich, T. H., Jr. Armstrong, 0. R. Beard, A. H. Benjamin, F. S. Blackburn, E. 0. Blair, A. J. Blair, 0. S. Blair. H. W.]

Jan 1, 1946

By Edgar Bain

THE results are presented of an investigation to discover the fundamental atomic conditions existing in Corson's high-copper alloys hardenable by means of silicide solution and reprecipitation. The study attracted the writer because it offered a very convenient example of the general type of hardenable alloys exemplified by duralumin, Sykes' iron-tungsten and iron-molybdenum alloys and the hardenable lead antimony. SUMMARY OF RESULTS AND CONCLUSIONS In brief, the investigation shows that very perfect crystallinity exists in the solid solutions prepared at high temperature to contain as much dissolved silicide as possible. The lattice parameter of copper is altered very little by the amount of cobalt, nickel or chromium, and silicon dissolved. The hardening by drawing at a temperature to initiate precipitation of excess silicon and metal produces a remarkable change in the atomistics of the solid solution. The old perfection of crystallinity in the solid solution is destroyed and the new atomic spacings are of variable magnitude even in one grain, and a condition in a measure resembling that found in martensite is observed. Were no particles whatever precipitated by the drawing action, still ample causes for hardness would be in evidence in the solid solution alone. The lack of plane continuity in the crystal grains would oppose slip in a very effective manner. Complete annealing restores the crystalline perfection in large measure. In these alloys even the most sensitive methods failed to reveal the characteristic pattern of the silicide precipitated by the anneal, but this was largely to be expected as the amount is relatively small.

Jan 1, 1927

By C. F. Jr. Nagel

THIS paper is written primarily for those who are familiar with the processes mentioned but who desire a further insight into some of the fundamental principles. It does not give a complete description of the various practices employed in the working of aluminum and its alloys, but presents a few illustrations of the essential respects in which aluminum differs from other common metals, and emphasizes the controlling factors of the processes under consideration. HEAT TREATING Certain aluminum alloys are capable of having their mechanical properties greatly altered by a heat-treatment process. The degree of this improvement may be illustrated by the typical properties of duralumin (Table 1). It is essential that the material be in the wrought condition in order to obtain maximum heat-treatment effects.

Jan 1, 1927

By R. E. Steiner, A. F. Weinberg, R. J. Van Thyne

Uranium solubility in molten bismuth was determined in the temperature range 350" to 600°C, varying from 0.09 wt pct to near 2 wl pct, respectively. Zirconium and magnesium, simulated fission products, and sodium were found to increase or decrease uranium solubility in bismuth in the temperature range 370° to 420°C, depending upon the addition or temperature. Data were obtained by both chemical analysis of samples obtained by filtration from saturated melts and by measurement of the variation of electrical resistance with temperature. IN a study for the United States Atomic Energy Commission, a Liquid Metal Fuel Reactor Experiment (LMFRE) was proposed in which a solution of uranium dissolved in molten bismuth served as both the fuel solution and the primary coolant. It was proven necessary to add other elements to this solution for certain desirable properties: 1) zirconium acts to prevent reaction of the fuel solution with the graphite core (which would result in the formation of uranium carbide) and also to inhibit mass transfer of iron and chromium from the walls of the reactor tubing to cold spots resulting in blockage; and 2) magnesium acts as a deoxidant and prevents loss of uranium. In addition to these intentional additives, other elements entering the solution are: 1) fission products which are a by-productof reactor operation, 2) sodium (the secondary coolant) through possible small leaks in the heat exchange system, and 3) iron and chromium from the container walls. Each of these elements may affect the solubility of uranium in the fuel solution. Since the concept of this reactor is based upon a liquid solution, the relatively low solubility of uranium in bismuth will dictate the minimum temperature at which the reactor heat exchanger can be operated. The solubility of uranium in liquid bismuth and the effect of some additives on this solubility have pre- viously been investigated1-' (more recent results6" became avaliable after initiation of this investigation). However, some discrepancies between the various results have been noted, and also the cumulative effect of the several additions or impurities was not known. This investigation was commenced to obtain definitive results. MATERIALS Analyses of the materials used are presented in Table I. Although ostensibly of extreme purity (99.999 wt pct), the bismuth was found to contain a significant amount of impurities, probably oxides. Except for determination of the binary system, Bi-U, prior to use all bismuth was hydrogen-refined and

Jan 1, 1962

INCREASING realization that pouring and ingot-mold practices involve many factors of fundamental importance to ingot quality and general steel-mill operations has caused these phases of steelmaking to become major concerns of operators and metallurgists engaged in control of quality and costs. Methods of pouring steel from the ladle into the ingot molds have some direct effects on ingot quality. The mold itself governs solidification and dimensions of the ingot and in so doing exerts some very tangible influences not only on ingot quality but also on product yields and general steel-mill processing. In addition, practices are employed' in the handling of molds during daily open-hearth operations that are important to quality and production costs. Therefore, pouring and mold practices must be considered highly specialized and important steps in steel-mill operations. MOLD DESIGN Mold design is difficult to discuss in a precise manner because it varies greatly throughout the industry, both in theoretical concepts and practical application, and few well developed data are available. Most ingot molds are designed to meet conditions peculiar to a given plant wherein quality standards are dictated by end-use requirements, which may differ considerably, even for the same grade of steel. The mold designer must also consider the equipment available to process ingots and the product obtained from them. Such equipment, used for stripping, heating, blooming and finishing operations, is seldom, if ever, exactly the same in any two steel plants. Thus, pronounced contrasts in mold designs can be expected to continue, even among plants making strictly comparable types of product, particularly because some producers are just beginning to realize the benefits possible from specialized designs. Certain fundamentals are used in mold design but even these

Jan 1, 1951

By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963