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By E. P. Klier, V. Weiss

IN studies of the X-ray diffraction line geometry of iron with chromium radiation using techniques aimed at minimizing the background intensity, Kp and Ka emission satellites* were resolved with three techniques. These satellite lines are present with sufficient intensity to lead potentially to erroneous structure analysis, if not properly interpreted. The techniques used were: 1) film technique with un-filtered radiation and polycrystalline specimen, 2) film technique with unfiltered radiation and single crystal, and 3) counter technique with unfiltered radiation and single crystal. An example of results obtained with technique 1 is given in Fig. 1.

Jan 1, 1958

By S. Mellgren, W. Opie

AN equilibrium state of importance in the process of electrolytically depositing titanium from fused chloride electrolytes is that which exists between titanium metal, titanium dichloride, and titanium trichloride. This can be expressed by the reaction titanium concentration of the solution, temperature, and the proportion of strontium chloride and sodium chloride in the solution. Procedure The general procedure used consisted of the following steps: 1) Development of an analytical method for determining Ti+2 and total titanium. 2) Preparation of batches of fused salt solutions containing various amounts of total titanium, Ti+2 and Ti+3 3) Blending of the prepared batches and excess titanium metal in Vycor tubes and allowing the solutions to come to equilibrium. By blending, solutions with different total titanium content could be prepared and equilibrium could be approached from the high Ti+2 and low Ti+2 sides. 4) Studying the effect of titanium concentration, temperature, and the mole ratio of the solvent chlorides, SrC1, and NaC1, upon the equilibrium.

Jan 1, 1958

By R. H. Winn

In this paper a heterogeneous carbonate reservoir is considered as a succession of layers of formations of radically different porosities, permeabilities, water saturations, and rock matrix types; i.e., the heterogeneity is vertical rather than radial to the wellbore. Presumably each layer is more or less homogeneous. To determine the "net oil in place" in this reservoir it is desirable to know the porosity and water saturation of each layer. In addition, the section must be subdivided into that which will produce oil, that which will produce water, and that which will produce little or nothing. In numerous wells drilled in these reservoirs radioactivity surveys, guard electrode surveys, and caliper surveys have been made. These logs have been compared with core analysis data, when available, and the analysis of the surveys compared with production data. This study, still in progress, is intended to provide improved analytical techniques if such are possible. This paper is a progress report on the work. DETERMINATION OF POROSITY The neutron-gamma log has long been recognized as a measure of hydrogen concentration.1,2,3 In reservoirs that are free of clay, shale, or other hydrogen containing matrices, it has been accepted as a measure of porosity.4,5 Empirical methods to relate relative neu-tron-gamma intensity to porosity are often employed." To provide a more precise determination of porosity from the neutron-gamma log each instrument is calibrated immediately prior to each survey by a method which refers all tools to a hydrogenous cylinder. To insure stability a calibration check is made after each survey. These calibration records are printed as an integral part of the log that is recorded in standard counts per second. A detailed description of the calibration procedure is available in the literature.' The procedure employed insures that each Survey is numerically reproducible within the limits of statistical variation. To relate the standard neutron counts per second to porosity and hole size, records were made in test wells constructed of blocks of limestone. The porosities of the blocks were accurately measured and the blocks completely saturated with fresh water. Fig. 1 presents some of the results obtained in these test wells.' The lines shown in Fig. 1 were obtained by deriving an empirical equation relating the 11 points shown so that the relationship may be projected to larger and smaller hole sizes. A detailed description of the tool is available in the literature.' Field tests indicate that the tool is adjacent to the wall of the hole most of the time when the surveys are made in uncased holes drilled with saline muds. In this circumstance porosity may be calculated from Fig. 1 if the hole size is known. When fresh muds that form thick mud cakes are employed, the centralizing effect of the mud cake must be considered and the porosity determination is less reliable. In cased holes the combined effect of variations in hole diameter and the unknown eccentricity of the casing in the hole may make porosity determinations extremely unreliable. In any event, an accurate knowledge of hole size is essen-

Jan 1, 1958

By J. J. Becker

BEAN1 has discussed the magnetic behavior of mixtures of small ferromagnetic particles on the order of 20 to l000A in diam. As he points out, there are three size categories with characteristic properties: 1) Particles large enough to contain many ferromagnetic domains magnetize initially by the motion of domain walls. The initial susceptibility of such particles, if domain-wall motion is assumed to be perfectly easy, depends only on their shape. It is equal to the reciprocal of the demagnetizing factor (and is thus 3/4 tt for a sphere) and is independent of temperature. 2) Smaller particles find it energetically undesirable to contain domain boundaries. They are always spontaneously saturated, and reverse their magnetization only by rotation of their entire magnetic moment. As assemblage of such particles has a remanence which is a large fraction of the saturation of the assemblage; its coercive force is on the order of 2K/1,, where K indicates magnetic aniso-tropy from any source, and I, is the saturation magnetization of the substance of which the particles are made. 3) Particles which are still smaller continue to be single-domain, but the direction of their magnetization fluctuates thermally, as first pointed out by Neel.' They have no remanence and no coercive force and possess the temperature-dependent magnetization curve of a paramagnetic substance with a very large moment. Bean calls this superpara-magnetism. All of these kinds of behavior are observable in alloys consisting of a precipitate of ferromagnetic phase in a nonferromagnetic matrix. Fig. 1 shows a typical aging curve for the room temperature coercive force of a sample of 98 pct Cu-2 pct Co alloy

Jan 1, 1958

By P. E. Baker

An improved method of logging formation density has been developed in which the formation is bombarded with a collimuted beam of gamma rays. By means of a scintillation detector and pulse height discriminator, the gamma-ray energy band is accepted and recorded which corresponds to deepest penetration into the formation. Laboratory tests on a field tool revealed no borehole diameter effect for smooth holes and no effect of formation chemistry, except insofar as chemistry affects density. In extensive field tests, the density log has exhibited satisfactory agree-ment with core measurements and has correlated accurately with other logs. INTRODUCTION This paper describes an improved method of logging formation density by means of back-scattered gamma rays to penetrate the formation together with energy discrimination to select only that energy (or frequency) range corresponding to deepest penetration into the forma- tion. This method of density logging was developed at the La Habra laboratory of California Research Corp.* Field instruments have been built and tested by McCullough Tool Co. and commercial service has begun in some areas. All of the data discussed here were obtained for the original field tool. The density log can be a valuable adjunct to existing logs because of its use in determining porosity quantitatively. It is useful also in connection with seismic and gravity surveys where formation density information is of interest. PHYSICAL PRINCIPLES The intensity, I, of a beam of gamma rays after traversing a distance, x, in an absorbing medium is given by I = loe -ax where I, is the intensity of the beam entering the medium and a the attenuation constant or macroscopic cross section of the medium for gamma-ray absorption. The macroscopic cross section depends on the number and types of atoms per unit volume and the gamma-ray energy. In brief, it is the sum of the atomic cross sections of all atoms per cubic centimeter. The density of the material is the sum of the masses of all atoms per cubic centimeter. Thus, the density and the macroscopic cross section for gam-ma-ray absorption vary in propor- tion to the number of atoms per cubic centimeter. The density of the material increases, of course, if the atomic masses increase without a change in the number of atoms per cubic centimeter. When the density increases in this latter way, the macroscopic cross section increases also, but disproportionately. This results from the fact that part of the gamma-ray absorption arises from the photoelectric effect and the pair-production effect**, which are proportional to the sixth and to the second power, respectively, of the atomic number of the absorber. The remainder of the absorption results from the Compton effect, and is directly proportional to the atomic number. The gamma rays that undergo Compton scattering are not immediately absorbed. Since these rays are scattered in all directions, a fraction will emerge from the face of the medium at which they entered. If a gamma-ray shield is placed between the source and detector, most gamma rays reaching the detector will be those scattered out of the medium. The intensity will depend on absorption and scattering in the medium, and so indicates the density of the medium. For gamma rays for which Compton scattering prevails, the intensity

Jan 1, 1958

By R. L. Smith, J. L. Rutherford

ZONE refining, as developed by W. G. Pfann,1 has been used extensively for the purification of semiconductors. This method has made it possible to obtain the extremely high purity material necessary for the transistor industry. It has also been utilized to some extent for the purification of relatively low-melting-point metals. However, very little attention has been given to reactive, high-melting-point materials, with the exception of silicon. For this element, it has been necessary to use the floating zone technique in order to avoid contamination from the crucible containing the melt. The method is one in which a narrow molten zone is formed in a vertical rod by induction heating. The molten zone is supported between the two solid sections of the rod by surface tension. It is then moved longitudinally along the rod in order to effect a redistribution of solute. This technique has an advantage over the horizontal boat method, since crucible contamination is avoided. It has the disadvantage of being a much more difficult technique than zone refining in a crucible. Furthermore, it is necessarily a slow process, since only one zone at a time can be formed. However, the floating zone process offers a means of obtaining high-purity metals that are either not available, or can only be obtained in powder or pellet form as the result of complex chemical or electrochemical methods. It should be emphasized that the process is not effective in removing all impurity elements. Those that cannot be redistributed in an ingot during zone melting must be removed by some other means. Very little is known of the prope~ties of very high purity reactive metals such as iron, titanium, zirconium, beryllium, etc. It is quite likely that trace elements in such metals can affect their properties drastically. Therefore, one of the primary objectives of this work is to study the properties of metals which have been obtained in the purest form available and then zone refined. Trace elements can be introduced in a variety of ways, such as by inserting wafers between solid portions of the ingot to be melted, by placing the

Jan 1, 1958

By R. A. Swalin, B. W. Roberts

ONSIDERABLE controversy has centered about the existence of an order-disorder transformation in alloys in the composition vicinity of 75 atomic pct Ni and 25 atomic pct Cr. All the evidence to date for such a transformation is of a rather indirect nature, since direct X-ray confirmation is difficult to obtain as a result of the small difference in X-ray scattering factors between nickel and chromium. As a result, superlattice lines would be very faint if present. Several investigators1-5 have observed anomalies in the electrical resistivity vs temperature curves of alloys in the vicinity of 25 atomic pct Cr. The observed change is characterized by a rather broad resistivity peak at about 540°C. A discontinuous drop in resistivity is normally associated with ordering. However, Taylor and Hin-ton4 have rationalized that the discrepancy could conceivably be caused by changes in the Brillouin zones upon ordering. The same investigators measured the specific heat as a function of temperature and have also observed anomalies in the vicinity of 540°C. Nordheim and Grant5 have proposed, because of the absence of superlattice lines and the absence of a discontinuity in the resistivity vs temperature curve, that long-range order is improbable and that the results could be better explained by short-range ordering. To date, however, the question has not been resolved satisfactorily. Neutron diffraction techniques provide a method for partially resolving the question since nickel and chromium have considerably different atomic scattering factors in the case of neutrons and, therefore, superlattice peaks, if ordering occurs, should be readily discernable. The results of a neutron diffraction investigation* coupled with a dilatometric in- vestigation are reported here. An alloy containing 28.0 atomic pct Cr was prepared from carbonyl nickel and electrolytic chromium in the form of a 1-in. diam x 10-in. ingot. Melting was done in an alumina crucible and casting in a graphite mold. The ingot was homogenized at 1250°C for seven days, after which a 5-in. long piece was cut into shavings in order to obtain a suitable neutron diffraction sample. Hardness samples and samples suitable for dilatometric analysis (% in. diam x 2 in.) were prepared from the remainlng piece. The neutron diffraction sample, along with a hardness sample, was annealed at 501°C for seven days, at which time the temperature was lowered to 479°C and held at this temperature for twenty-four more days. The hardness was observed to increase from 133 to 147 Vhn during the course of the annealing treatment, in qualitative agreement with Nordheim and Grant." Neutron diffraction traces taken at room temperature and at 42 °K are shown in Fig. 1. The insert shows the trace taken at room temperature with short counting times and thus only fair statistical accuracy. No evidence for superstructure reflections of Cu3Au-type ordering is observed. The statistical accuracy of the 4.2°K trace was improved by using longer counting periods. Several weak intensities are observed at small angles, including an aluminum reflection from the cryostat assembly and a very

Jan 1, 1958

By R. F. Domagala

SOME of the results of a program designed to study the kinetics of transformation and related mechanical properties of prototype Zr-X binary alloys systematically are presented here. The object of this program was to provide a sound basis for a scientific approach to the realization of optimum properties in binary zirconium alloys. Alloys of Zr-Mo (eutectoid), Zr-Sn (peritectoid), and Zr-Ti (a and ß isomorphous) were prepared and studied. The data herein are confined to a presentation of the results of studying the eutectoid prototype alloys. The Zr-Mo phase diagram has been determined.&apos; A definitive metallographic study of isothermaily annealed samples prepared from high purity elements served to position a sluggish eutectoid reaction, ß?a + ZrMo2, at 780°C. The compositions of the phases involved in this reaction are: ß, 7.5 ±1 pct Mo; a, <0.18 pct Mo; and ZrMo2, 67.8 pct Mo. Inasmuch as a lower purity sponge zirconium was used in this work boundary placements were rein-vestigated with the less pure alloys. Materials and Procedures Hafnium-free sponge zirconium was used to prepare all ingots. The arc melted hardness of a small button of this zirconium was found to be Vpn 168. Chemical analyses conducted at Armour Research Foucdation are shown in Table I, High purity molybdenum sheet was used as the alloy addition. A typical analysis is shown in Table I. Several 200-g Zr-50 pct Mo alloys were made by arc melting. Crushed granules of this material were used to ensure inqot homogeneity Ailoy ingots were prepared by double melting techniques. First, three 5-lb ingots of each alloy composition were are melted in 2 nonconsumable electrode arc furnace. After melting. the ingots were ground to remove surface defects. A subse-

Jan 1, 1958

By R. L. Segall

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

Jan 1, 1958

By P. K. Foh, C. G. Dunn

IN an investigation of the rolling and recrystalliz-ing textures obtained from single crystals of Si-Fe, Koh and Dunn included specimens in the (111) [lie] orientation.1,2 This note reports some additional results obtained on samples of this orientation set aside for further study. After, primary recrystallization longer annealing treatments at 980°C produced only normal grain growth; after 16 hr at 980°C the largest grains were approximately 0.010 to 0.020 in. in diam. The orientations of 13 of the larger grains were found by the transmission Laue method. The unidentified (110) poles of these grains have been added to the (110) pole figure obtained after primary recrystallization2 to give the plot shown in Fig. 1. When grain identifications are also included, such a plot reveals the following. Two orientations agree almost exactly with the peak pole ,density positions of component B of the primary recrystallization texture, one with component A, and one with component C. All the remaining orientations except one have (110) poles near weaker and unidentified pole density peaks. In fact, the correlation is good enough for an identification of eight components. Previously only components A, B, and C were certain. The results are perhaps even more informative when combined with the (110) pole figure of the cold-rolled crystal to give the plot shown in Fig. 2. Each of the 13 orientations is identified and uniquely determined by selecting two (110) poles per crystal, which are 90" apart. The plot shows that every grain of the 13, except grain 6, has a (110) pole in common with a (110) pole concentration of the cold-rolled crystal. The orientation relationship with the cold-rolled orientation may be expressed as approximately 25" rotations about <110> axes, which is in agreement with the results found for coarse-grained primary recrystallization.2 If primary recrystallization had occurred according to the <110> rule without preference, there would have been 12 components. Actually our limited data reveals nine of the possible 12. The integrated pole figure also shows preferences among them, since three are considerably stronger than the rest. In addition to the above direct information, the following conclusions may be drawn. Primary recrystallization of the (111) [110] cold-rolled crystal produces a limited number of weak and strong components with the larger than average primary grains from these components related to the cold-rolled crystal by 25° <110> relationships. In arriving at this conclusion of limited orientations the (111) [110] orientation has to be ruled out as a source of large primaries for two reasons. First, growth in this orientation was not observed, despite an expected high grain boundary mobility (due to its 25" <110> relationship with every component of the texture). Secondly, primary recrystallization usually produces grains in new orientations, particularly in a single orientation matrix; but (111) [110] is not new. Other orientations besides those of the <110> type may be considered unlikely, of course, because the <110> relationship holds quite well for primary recrystallization2 and should produce the large primaries. There are exceptions to this rule, but probably not enough to provide large

Jan 1, 1958

By T. A. Read, H. M. Otte

THEORETICAL analysis by Wechsler, Lieberman and Read of the crystallography of martensite formation has shown that the requirement for the existence of a macroscopically undistorted plane between austenite and martensite permits a calculation of the indices of the habit plane of the marten-

Jan 1, 1958

By Wm. C. Phelps, R. E. Grace

b R.c c)nduciivity of slags and glasses is of particular interest when viewed as an activated ionic flow process. The ionic conductivity, for example, has been found to obey the Easch-

Jan 1, 1958

By E. H. Bronson

PROPERTY of Malartic Gold Fields Ltd. is situa-ated in the great clay belt in the northern part of the Province of Quebec. This belt represents the floor of the glacial lake Barlow-Ojibway. The clay blanket has a gently rolling, almost flat surface, with here and there projecting knobs and ridges that outline the large irregularities of the surface on which the clay was deposited. At irregular intervals glacial eskers dominate the landscape. The ore-bearing country rock is covered by strata of clay, sand, and silt to a depth varying to 40 ft. There are serious structural problems when it is necessary to place loads of unequal intensities on this surface to support buildings and machinery for a modern mining plant. Earlier mining companies and their engineers paid little attention to the science of soil mechanics, partly because they believed it unnecessary and partly because they knew little of the subject. The results are evident in some of the tottering structures in older camps. Careful analysis of soil problems is well worth-while, since cost of foundations may vary from 20 to 50 pct of the final cost of a structure. Low operating and maintenance costs can be achieved only in this way. If it is definitely established that a plant will be in operation for only a few months, this limited time factor will probably influence the design of the foundation, and rightly so. If sensitive and complickted equipment is to be mounted on these foundations and the plant is to operate for several years, there should be a thorough study of foundations and a very careful design. A familiar problem is presented by the difficulty of operating a permanent plant originally designed for a few months&apos; work. The engineer must beware of these hazards and disassociate himself from them if he cannot prevail on the promoter to spend the proper amount for a thorough foundation study. Laws of certain provinces and states hold the engineer equally responsible with the contractor for any &apos;damage that may be caused to building through inadequate study-ignordnce of the facts is no excuse in the eyes of the law. Types of Soil: The engineer should be familiar with such terms as silt, clay, peat, and varved clay, as well as perpafrost, especially if he is to work in the far northern reaches of the country. He should also be familiar with soil attributes such as porosity, texture, consistency, permeability, compressibility, consolidation, and shearing resistance. The design of any foundation requires an accurate knowledge of the physical properties and location of the soils involved. Older textbooks on the subject outline various empirical methods to determine the carrying power of soil. Tables are given in reference books. The modern ehgineer should be wary of these modes of thinking. He should analyze his problem carefully, calculate to what depth of soil the loads may be transmitted, and then check the bearing value of all soils to that or greater depths. If the strata are water-carrying, he must determine the possibility of this water being accidentally re-

Jan 1, 1958

By Richard F. Hinds, F. O. Reudelhuber

Application of the conventional depletion drive calculation methods to volatile oil reservoirs results in erroneous estimates of ultimate recovery. In view of the increasing number and importance of volatile oil reservoirs, a special technique has been developed which will result in more realistic predictions using laboratory data obtained from reservoir fluid studies of a specific type. The experimental data are designed to permit continuous material accounting and, therefrom, provide the hy-clrocarbon composition of both the flowing oil and gas phases. The resultant well-stream composition data are then used directly in surface recovery calculations utilizing equilibrium ratios. A step by step procedure, specifically designed for routine use by the practicing reservoir engineer, is presented in an appendix. An actual study performed on a deep Mid-Continent reservoir is used ay an il-lustrathe example. INTRODUCTION It has been a practice for many years to utilize the conventional ma- terial balance methods in conjunction with relative permeability concepts for the prediction of recovery from solution gas drive reservoirs.&apos; Those who have performed such calculations recognize that compromises of several types are necessary in order to reduce the calculations to a reasonable degree of complexity. The most serious assumption involved results from the necessity of treating the produced oil and gas as separate fluids, independent of each other in their behavior. It is further assumed that the gas which is evolved in the reservoir as a result of pressure decline will not yield liquid upon the reduction of pressure and temperature resulting from production through surface equipment. Although these shortcomings have been recognized,&apos; it has been difficult to attempt refinement of calculation procedures since the laboratory data available normally were not of the proper type or extent to permit such calculations. Three general procedures have been available for depletion drive calculations when laboratory fluid data are of the conventional type. Differential Procedure The most simple, and most widely used, method requires use of the formation volume factor and gas sol- ubility data obtained from a differential liberation performed at reservoir temperature. This procedure ignores the differences existing between the fluid behavior in the reservoir and its behavior as it is produced through surface separation equipment. The errors introduced are not serious when dealing with very low volatility fluids and this method may be utilized if the laboratory data indicate only slight differences between the differential data and the flash data obtained from separator tests. Modified Differential Procedure This method was developed when it became apparent that medium volatility fluids evidenced a wide difference between the flash and differential data. The differential data are adjusted by changing from a residual oil basis to a stock tank oil basis. All that is required is multiplication of the differential data by the ratio of residual oil to stock tank oil relative volumes existing for the original reservoir fluid at the determined saturation pressure. This procedure generally results in increased calculated ul-timate recovery; however, such results should be viewed critically. Upon examination it may become apparent that the results are influenced by errors in reservoir liquid

Jan 1, 1958

By Charles Prasky

ABOUT five years ago the Bureau of Mines began a study, at Minneapolis, of the various methods for beneficiating the low-grade manganese deposits of the Cuyuna range. Several samples of green carbonate slate from the Cuyuna range, containing about 7 pct Mn and about 28 pct Fe, were obtained for this study. The component minerals in the carbonate slate formation were so intimately associated that mineral dressing methods were not suitable for concentrating manganese to a ferrograde product. Although upgrading of manganese and iron minerals has been effected by flotation methods, it appears that manganese cannot be separated from iron except by chemical means. Because the flotation studies at Minneapolis were carried out simultaneously with the hydrometallurgical studies, only crude slate was available for process testing. An important economic consideration in selecting any one of the several chemical methods proposed for recovering ferrograde manganese is the availability of the chemical reagent. Fortunately, large tonnages of sulfur are available on the Cuyuna range in low-grade pyrite and pyrrhotite deposits that are readily concentrated by flotation to a suitable feed for a sulfide roasting furnace as indicated by a Bureau of Mines investigation in 195 0-1951.1 The roasted residue from the sulfide concentrates is a potential source of marketable iron oxide. Therefore, if these sulfide deposits were employed in recovering manganese, utilization of two heretofore unused mineral deposits would be accomplished. Laboratory investigations of several proposed leaching processes were made as a preliminary step in the investigation of hydrometallurgical methods for the treatment of Cuyuna carbonate slate using sulfur as a chemical reagent. From results obtained in the laboratory tests, these leaching processes did not appear entirely suitable for treating Cuyuna carbonate slate. The method developed at the North Central Experiment Station and selected for a more intensive pilot-plant investigation has been termed the differential high-temperature sulfatizing process. Essentially, this sulfatizing process consists of the following steps, described in the order in which the small-scale pilot-plant investigations were made. The first and perhaps most significant step in the process consists of a sulfate roast. Carbonate slate is roasted in an atmosphere of sulfur dioxide gas and air. The overall chemical reaction for converting manganese carbonate to a sulfate at a high temperature in a sulfur dioxide atmosphere follows MnCO8 + SO2 + 1/2 0, = MnSO4 + CO2 (H077°O = —64,180 cal per g mol) .&apos; The need for concentrated sulfuric acid is avoided. Fine grinding is not essential. Removal of carbon dioxide from the slate during roasting produces a more porous structure and permits easier permeation by the sulfatizing gas mixture. The temperature limits for this conversion of manganese have been established as 600" and 850°C. Iron sulfate is unstable and is not formed at these temperatures; phosphorus is not converted to a water-soluble form; and polythionates are not formed. The second step in the process consists simply of a water leach of the sulfatized product. Manganese sulfate in the sulfatized product is dissolved in water. Iron, phosphorus, and calcium remain in the leach residue as water-insoluble products. The third and final step consists of the recovery of ferrograde manganese oxide from manganese sulfate leach solution. Water is evaporated from the leach solution, and impure monohydrate crystals of manganese sulfate are recovered. The moist crystals are formed into pellets or extrusions and thermally decomposed to produce a ferrograde manganese

Jan 1, 1958

By S. A. Braley

DRAINAGE water from coal mines is probably the most serious water pollution problem today, varying in importance according to location of the mines and geological structure. Drainage may be either acid or alkaline in character. Acid discharge, the most severely detrimental to a stream, is caused by natural oxidation of the sulfuritic material (FeS2) in the strata associated with the coal seam. Since the acid is the result of a natural reaction the acid water differs because it does not cease with abandonment of the mining operations. There is no known economical method of neutralizing acid mine water or any practical method to prevent oxidation of exposed pyrite. Since production of acid from a mine does not stop when mining stops, the total quantity produced depends entirely upon the excavated areas. The increasing volume of acid water in manv mines has greatly increased operating costs. Pumping is expensive and acid mine waters are destructive of all equipment, especially metals in pumps and piping, and necessitate the use of corrosion-resistant materials. Discharge of the acid mine drainage into streams neutralizes their normal alkalinity, causes them to become acid, and produces an environment unfavorable for aquatic life and unsuited for industrial or domestic use without costly treatment. Mine drainages vary in percentage composition over wide limits, although the usual dissolved substances are ferrous and ferric iron, aluminum, calcium and magnesium sulfates, and lesser amounts of sodium, potassium and manganese sulfates and chlorides. Some alkaline discharges may contain heavy concentrations of iron as iron bicarbonate. These waters may produce iron hydroxide deposits in the receiving stream but do not cause it to become acid. In the extensive literature on acid mine water there appears to be a great deal of confusion about the importance of various components and the methods for their determination. In many instances faulty conclusions have been drawn from use of unsuitable methods of analysis. It is desirable that the factors and terms used in evaluation of analyses of mine waters should be so clearly defined that any interested person could properly appraise any analytical report. Some analysts report complete chemical analyses of mine waters and neglect to record drainage volumes. Others report only a minimum of analytical data after taking no precautions to preserve the original composition of the water during the time elapsing between collection and analysis. Some use methods of analysis intended for so-called pure waters of the potable and boiler water classes. These methods are not applicable to highly buffered waters such as mine water. Probably the most common criteria for evaluation are pH, free acidity, or acidity or alkalinity to methyl orange or methyl red, total acidity or acidity to hot phenol-phthalein, and the sulfate content. If these determinations are made on carelessly collected samples after a few days to weeks standing in warm rooms, they do not in any way represent the character of the water flowing from the mines. It is hoped that a brief discussion of the fundamental value of some of these factors may lead to a bettqr understanding of the need for more careful evaluation of mine water discharges. The term pH is one used by chemists to express relative acidity or alkalinity in terms of concentration of effective hydrogen ion in a solution. It is defined as the negative logarithm of the hydrogen ion concentration or activity in equivalents per liter. pH = logarithm A neutral solution, which is one containing the same number of hydrogen and hydroxyl ions, has a pH of 7. As the hydrogen ions increase and the solution becomes more acid, the pH decreases toward zero; and as the hydroxyl ions increase and the solution becomes more alkaline, the pH approaches 14. When dissolved in water to a dilute solution acids like sulfuric and hydrochloric, commonly known as strong acids, ionize completely, and the pH or hydrogen ion concentration varies with molar concentration of the dissolved acid. However, in high concentrations of such acids, the pH or hydrogen ion concentration is less than the acid concentration because the acid does not completely ionize. In only very dilute solutions does the pH represent the total amount of acid that can be neutralized by an alkali. All ionization reactions are equilibrium reactions. If other chemicals are added to the solution of an acid and the added chemical produces an ion that is the same as one of the ions of the acid, the degree of ionization of the acid is altered and the pH changes to some value that represents the active hydrogen ion of the new solution. Thus if iron sulfate is added to a solution of sulfuric acid the pH increases, since the common sulfate ion suppresses the degree of ionization of the sulfuric acid and decreases the effective hydrogen ion. However, the total acidity of the solution is increased. There are two salts composed of iron and sulfate— ferrous and ferric sulfate. In these salts there is no hydrogen ion that can ionize to give an acid solution, but when they are dissolved in water, the pH is less than 7 and the solution becomes acid. This is caused by a reaction known as hydrolysis and is represented by the equations FeSO4 + 2H2O ? Fe(OH)2 + 2H + SO,: or Fe,(SO,)3 + 6H2O ? 2Fe(OH)3 + 6H+ + 3504 A solution with a total acidity of 5000 ppm according to the first equation will have a pH of 4.40 but one with an acidity of 75 ppm, according to the sec-

Jan 1, 1958

By J. H. Wernick

IN temperature-gradient zone-melting1 a molten zone is moved through a solid or across a solid surface by the establishment of a temperature gradient. This technique has both practical and fundamental aspects. One practical application is to make p-n junctions for semiconductive devices, particularly for devices in which the junctions are desired within the semiconductor. From a fundamental point of view, the technique is being investigated as a method for determining diffusivities in liquid alloys, and preliminary diffusivity results have been reported by the writer." In this paper, the effects of crystal orientation, temperature, and molten zone thickness in temperature-gradient zone-melting, and the bearing of these effects on diffusivity measurements and n-p-n junction formation are discussed. Experimental Procedure An effect of crystal orientation was noted in early experiments. To facilitate its study, movements of wire zones across a surface, rather than through the body of a single crystal, were observed for various surface planes and travel directions. The experirr-entai setup is illustrated in Fig. 1. The graphite end-section for the high temperature heater has an apron about 1/16 in. above the upper surface of the crystal. This apron insures that the surface temperature of the block is equal to or greater than the temperature within the block at every point, Thus, the zone does not penetrate the block and convection in the liquid is minimized. The experi-through a block is shown in Fig. 2,

Jan 1, 1958

By S. Weinig, E. S. Machlin

IN a previous study of the grain boundary stress relaxation phenomenon,&apos; the authors had arrived at the conclusion that two successive steps were involved in the complete relaxation of stress at a grain boundary. These two steps were grain boundary migration and grain boundary slip. It was further suggested that the slower of these two processes is rate controlling. In an attempt to ascertain the validity of the above, a study of grain growth kinetics on the same alloys used for the previous study was undertaken. Separate wire specimens, 0.030 in. diam, in the same as-deformed state (99 pct reduction in area) as in the previous investigation were heated to the various temperatures for a sequence of times. The compositions used and the temperatures of testing are summarized in Table I. A statistical determination of grain size was then made on each specimen, using the average length of traverse between boundaries as a measure of the grain size. Examples of typical results obtained are shown in Figs. &apos;1 and 2. The grain growth law D = ktn was found to fit most of the data. Using this relation, values of the grain growth exponent n were calculated and the inter -esting dependence of n on solute content shown in Figs. 3 and 4 was then obtained. Also, it was found that the constant K which was obtained from extrapolation is roughly independent of solute content. (K is uncertain to within ±25 pct.) An estimate of the activation energy for grain growth was made using the technique of Burke? This method utilizes the plot of the reciprocal of time necessary for the grain size to increase from a definite starting size Do, to a final size D, for each isothermal heat treatment. The slope of this curve corresponds to the heat of activation for the process. In Fig. 5 the rate of grain growth is plotted against the reciprocal of absolute temperature. The activation energies were obtained from these curves and are summarized in Fig. 6. Discussion It is interesting to note that the same saturation in the variability with concentration has been found for the grain growth exponent n in this research as was found in the previous researches on both grain boundary stress relaxationa and internal friction of dislocation origin." The significant feature is that saturation in the variation of these properties has been found to occur at about the same level of solute concentration, namely, between 0.1 and 0.5 atomic pct. The only characteristic common to these different quantities is that solute adsorption at grain boundaries and dislocation can take place and affect these values in a similar fashion. Thus, it is concluded that the grain growth exponent n depends upon solute adsorption at the grain boundaries. It appears, therefore, that theoretical considerations leading to the contrary conclusions5,6 have not treated the real process by which solute atoms exert their effect on grain growth. Prior to the analysis of the observed activation energies, certain of the aspects of the aforementioned grain boundary stress relaxation investigation will be briefly reviewed. It was found that with the addition of solute atoms the grain boundary stress relaxation peak (internal friction vs temperature) decreased in intensity. Simultaneously a second peak was observed which increased with increasing solute atoms. Both of these peaks were shown to be the result of grain boundary stress relaxation. They have been termed, respectively, poire peak and solute peak. It was suggested that the solute peak was dependent upon grain boundary migration, whereas the pure peak was a manifestation of grain boundry slip. Activation energies for both peaks were obtained as a function of Solute content. The value of the activation energy in the temperature range corresponding to the solute peak was

Jan 1, 1958

By R. H. Jacoby, V. J. Berry

Future depletion performance and ultimate oil recovery from reservoirs producing under volumetric control are often predicted with the aid of a material balance equation. When the reservoir fluid is very volatile, however, certain assumptions implicit in the use of the conventional methods are no longer valid. This is became laboratory differential vaporization test procedures do not adequately represent the reservoir depletion process and the performance of surface separation facilities. In such cases recovery of stock tank oil per unit of pressure decline can be predicted only from a detailed knowledge of the separator conditions and the over-all composition of the fluid entering the wellbore at each stage of depletion. Surface recovery is not simply related to the total quantity of liquid flowing into the well under reservoir conditions. In order to improve predictions for reservoirs which produce volatile oils, a step wise method of calculation has been developed. This method uses relative permeability data and multicomponent flash calculations to predict oil and gas production as a function of reservoir pressure. Calculations are presented for a reservoir containing a volatile crude oil, and predicted tank oil recovery by primary depletion is more than twice that predicted by conventional methods which are known to be adequate for ordinary black crude oils. Calculated maximum produced gas-oil ratio is less than one-fourth of the conventional prediction. Wellstream compositions have also been used to determine variation in stock tank oil composition and liquid content of the separator gas. This information is of particular importance for crude stabilization calculations and for design of gasoline plant facilities to recover LPG and natural gasoline. INTRODUCTION The estimation of oil reserves and the prediction of future recovery performance of petroleum reservoirs is a frequent task of the petroleum engineer. If the reservoir produces under volumetric control, performance calculations for primary depletion are made by combining oil and gas material balances with the gas-oil flow characteristics of the reservoir rock. For black oil reservoirs, the Schilthuis1 type material balance is commonly employed. For gas or gas-condensate reservoirs, where only one phase is flowing under bottom-hole conditions, a more simplified material balance is used. In the period in which these material balance methods were conceived and put into practice, it was common to classify reservoirs according to the type of fluid produced as (1) black oil reservoirs, or (2) gas or gas-condensate reservoirs. Recently, however, deeper drilling and more extensive studies of reservoir fluid properties have led to the recognition of reservoir fluids with phase characteristics between those of ordinary black oils, and gases or gas-condensate fluids. These intermediate fluids contain relatively large amounts of the hydrocarbons ethane through decane and are found in deep, high temperature (250°F) reservoirs. Such fluids are often referred to as high shrinkage crudes or "volatile oils." They are usually characterized by tank oil gravities above 45° API. high solution gas/oil ratios,

Jan 1, 1958

By I. L. Barker

ALTHOUGH valuable information has been pub-lished on the important problems of slag losses with which every copper metallurgist has to contend, a great deal of money is still being wasted in copper smelters all over the world, through metal being irretrievably lost in reverberatory slags. When smelting a relatively low-grade pyritic concentrate together with a proportion of direct-smelting oxi- dized ore, as is done in Oroya, slag volumes are of necessity high, and even a relatively clean slag, say of 0.5 pct Cu, means a loss of almost 4 pct of all the copper charged, or over $1,000,000 annually at present output and prices. While it is known that such losses can often be reduced by allowing the slag time to settle, with or without addition of a reducing agent such as coal or pyrite, the facilities for such treatment are not always available in a plant of old design working to capacity under severe space limitations. Nor is it easy under such conditions to run large scale tests which may endanger the smooth flow of production for considerable periods without yielding

Jan 1, 1958