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By Nicholas J. Grant, H. C. Chang

EMPHASIS on the importance of grain boundary sliding as a mode of deformation at elevated temperatures has been presented elsewhere.' The extent to which boundary sliding occurs under certain creep conditions has been determined for high purity aluminum2,3 and aluminum alloys.' In general, boundary deformation extends quite far into the adjoining grains, resulting in a rather wide band of deformation along the grain boundaries. This has led some investigators to doubt that grain boundary sliding consists of shearing along the boundary surface; it has been contended instead that boundary sliding is a result of concentrated slip in the neighborhood of the deformed grain boundaries."' The purpose of this note is to present evidence that grain boundary sliding takes place by a bulk shear process. gh purity polycrystalline aluminum, wherever and whenever there is grain boundary sliding, boundary migration and concentrated deformation along both sides of the deformed boundary are associated with it. Therefore, it has been rather difficult to obtain unambiguous evidence of boundary sliding. On the other hand, it would be expected in certain alloys of aluminum, when tested under particular conditions. that the severity of the interfering effects of boundary migration and concentrated deformation along the deformed boundary might be reduced. Current research in this laboratory' shows that a 20 pct Zn-A1 solid solution alloy fractures in an intercrystalline manner during creep at 500°F with a small total elongation of not more than about 14 pct, and that it does so with extremely limited grain boundary migration. Accordingly, this alloy was chosen for the present study. The experimental procedure was similar to that used in previous work and has been presented elsewhere.' Two parallel flat surfaces were milled from a round specimen. The gage portion of the specimen was 1 in. x .09 in. x .17 in. The specimens, which were annealed at 1030°F for 24 hr, showed two to four grains across the width of the test bar. The specimens were subjected to creep at 500°F at stresses of 2000 to 5000 psi. The rupture times were from 10 sec to 3 hr. Appreciable boundary sliding occurred in all the tests. A typical example of boundary sliding is shown in Fig. 1. (The tension axis is vertical in the micrographs.) Sliding has taken place along the boundary between grains A and B unaccompanied by important boundary migration. The sharpness of the offset at the triple point can be clearly seen in grain C. As a result of sliding along the boundary between grains A and B, a new boundary surface between grains A and C was created. The offset at the triple point is about 0.07 mm. This boundary sliding is accompanied by the formation of rather sharp kinking bands and, of course, slip on several slip systems in grain C. This type of deformation has been referred to as fold formation' in previous work with high purity aluminum.

Jan 1, 1957

John P Hammond '59, President T C Frick '58, Past President Basil Kantzer '60. President-elect George R Gray '58, Vice-President Earl M Kipp '58, Vice-President G M Stearns, Treasurer Joe B Alford, Executive Secretary 800 Fidelity Union Bldg Dallas, Texas

Jan 1, 1957

By Frank C. Morris

It is generally recognized that the productivity and ultimate recovery of an oil well may be reduced as a result of reduction in permeability of the sand at the well bore by invasion of filtrates and clay particles from drilling fluids. As a means of determining whether a sand has been "damaged" from these sources, several investigators2 3 4 5/ have developed methods of analysis based on the rate of increase in bottom-hole pressure while a well is shut in. Because of growing recognition of the importance of completion practices as related to the quantity of oil that may be recovered from wells, the Bureau of Mines has studied completion practices in California and the Midcontinent area. Well-interference and pressure-buildup tests were completed Ear seven wells in the Scurry Reef field to determine the effective permeability in the reservoir.6/ Also, a study was made of the pressure-decline curves obtained from 35 water-input wells in 5 different production areas of northeastern Oklahoma and eastern Kansas.7/

Jan 1, 1957

By F. E. Jaumot, R. L. Smith

Self-diffusion in zinc at temperatures below 200°C has been studied using both single crystal and polycrystal samples. Anomalous results were obtained for single crystal samples, the data indicating that in some cases grain boundary diffusion predominated. These anomalous results are presumed to be due to low angle lineage boundaries in the single crystals. When volume diffusion occurred in either single or polycrystal samples, the values for the diffusion coefficient were as much as several orders of magnitude larger than would be expected from high temperature data. ONSIDERABLE work has been done on self-^-*diffusion at temperatures in the neighborhood of two thirds of the melting temperature (in OK) and higher, but very little has been done at lower temperatures. This is particularly true of self-diffusion in single crystals. This paper reports work on self-diffusion in zinc at temperatures below 200 °C where both polycrystalline and single crystal samples have been used. The measurements were made using both the sectioning and absorption techniques. The experiments on diffusion at low temperatures were initiated primarily for three reasons: to obtain data from single crystal diffusion covering a wide range of temperatures, to obtain values of the activation energy for grain boundary diffusion, and to obtain, if possible, a lower limit to the temperatures at which the absorption technique may be used. It is possible to determine whether volume or grain boundary diffusion predominates at low temperatures by analyzing the manner in which the concentration of the diffusing atoms varies with the depth of penetration. The analysis is possible only for the sectioning technique. For volume diffusion and for the boundary conditions of the present experiment, the curve of the logarithm of the concentration, C, vs the square of the penetration depth, x, is a straight line with the slope proportional to — 1/D. If grain boundary diffusion predominates, Fisher' has shown that a curve of In C vs the first power of the penetration depth should be a straight line. This linear dependence of concentration on depth has been observed experimentally by several investigators. (See, for example, refs. 3 and 4.) Following Fisher's analysis, the grain boundary diffusion coefficient can be written as where 8 is the grain boundary width, D, is the volume diffusion coefficient at the temperature involved, t is the time of diffusion, C is the concentration of diffusing material, and x is the depth of penetration. A more general analysis employing the same model as Fisher's but with fewer assumptions has been given by Whipple.' In contrast to Fisher's analysis the more general analysis of Whipple does not always yield a straight line relation between In C and x. Recently Turnbull and Hoffman have discussed both analyses and have applied the Fisher-Whipple model to a more refined dislocation model of the grain boundary. They have also discussed the possibility of a large effect of grain boundary direction on diffusion. In the case of the absorption technique, for which results are also given, one simply gets a value for the diffusion coefficient with no indication of the predominating mechanism. Experimental Techniques Single crystals of 99.99+ pct Zn were grown using a modified Bridgman method. Polycrystal samples were prepared in three grain sizes (small, about 4 mm2; medium, about 9 mm'; and large, about 25 mmz) by quenching, air cooling, and furnace cooling. The grains of the polycrystalline samples tended to be columnar, with some preferred texture such that the c-axis was inclined at about 20" to 25" from the normal to the diffusion face, particularly in the medium and large grain size samples. The samples were cut from the rod, polished, and heavily etched, and faces cut accurately parallel using a jeweler's lathe. They were again etched to remove the lathe smear and annealed for 3 hr at 250" to 300°C. After annealing, they were etched, examined, and the orientation determined by Laue back reflection photographs. They were then electroplated with Zn. The plated surfaces were examined for uniformity; nonuniform coatings were removed by etching and the samples replated without additional preparation. For the diffusion anneals, the samples were placed in pairs, with active faces together, in evacuated Pyrex tubes. Constant temperature baths were used, and the variation in temperature did not exceed ±l°C, Diffusion runs were made at l00°,

Jan 1, 1957

By Milton E. Wadsworth, Edward M. Eyring

BETTER understanding of solid surfaces and their associated adsorption products is of both academic and practical value. The study of detergents and their behavior in cleaning surfaces is fundamentally related to the nature of the products adsorbed and their ability to compete for certain surfaces. Similarly in flotation, the nature of the adsorbate before and after adsorption is basic to clear understanding of the process. The recently developed pellet technique1,2 employing infrared spectroscopy provides a powerful tool for the study of solid surfaces. Absorption bands, which are infrared-active, may be observed for adsorbed products. Also any changes in the surface substrate that occur as a result of adsorption may be detected by means of differential spectra. In applying the pellet technique to solids of large surface area, French and his coworkers3 have surveyed the adsorption of organic flocculants on clay minerals, oleic acid on fluorite, and ammonia on cracking catalysts. Recent work on application of differential infrared spectroscopy to the study of solid surfaces' has demonstrated that the difference between a sample and a reference can be obtained with double-beam instrumentation. In this way displacement of surface products, adsorption of new products, and differences in the substrate, if any, may be detected. Experimental Procedure: Potassium iodide pellets were used in this study, prepared from recrystallized analytical reagent grade KI. Grinding was carried out in a Fisher mechanical agate mortar. Two-gram plates containing the solid under study were pressed in a special evacuated die constructed in the laboratory at the University of Utah." Concentration depended on the solid in question. Zinc sulfide and willemite are sufficiently transpar- ent in the infrared region for concentrations as high as 20 mg of mineral in 2g of KI to be used. Zinc oxide is even more transparent, permitting concentrations as high as 60 mg in a 2-g plate. For non-differential operation, however, much lower concentrations (2 to 10mg/2g KI) had to be used. Spectra were obtained on a Per kin-Elmer 21 double-beam recording infrared spectrophotometer. A sodium chloride prism was used giving a spectral range of approximately 2 to 15 v wave length. For differential runs a resolution of 1000 was used and the scanning speed was controlled commensurate with instrument response. The response was checked continuously and each spectrum was repeated several times. For nondifferential runs a resolution of 927 was used. Zinc oxide used was analytical grade oxide fume. The zinc sulfide was precipitated from solution with analytical grade zinc sulfate and sodium sulfide. The precipitate was washed and centrifuged several times and dried. Before use the precipitate was washed in dilute HCl and then treated with saturated NH4Cl to remove any bulk oxides and sulfates. X-ray patterns of the precipitate were comparable to that of the natural mineral sphalerite. The precipitate was much more satisfactory than finely ground natural ZnS because of its very large surface

Jan 1, 1957

By D. L. Martin

THAT small amounts of impurities have a harm-J- ful effect on the malleability of metals and alloys is well-known. One common type of em-brittlement involves the formation of a small quantity of eutectic at the grain boundaries, and is typified by sulfur embrittlement of nickel. Another example of eutectic embrittlement—sulfur embrittlement of cobalt—is described in this report. In the preparation of specimens for a study of Co-Pt alloys, it was observed that the hot swagabil-ity of the alloys appeared to be influenced by the grade of cobalt used as melting stock. The cause of the hot-shortness was not traced to any particular impurity, although sulfur was suspected.' The damaging action of sulfur on the malleability of cobalt has not been generally recognized,'; in spite of the fact that the Co-S phase diagram8 eveals the same basic conditions—low solubility and eutectic formation—responsible for sulfur embrittlement of iron and nickel.7, 8 Apparently sulfur embrittlement has not been a serious problem in the fabrication of cobalt alloys. One related factor is likely the limited commercial experience with high cobalt alloys, since the predominant use of cobalt has been in alloys containing less than 75 pet Co. A series of Co-S alloys was prepared and studied to establish the effect of sulfur on the hot working characteristics of cobalt. Specimens, 5/8 in. diam by 4 in. long, were prepared by vacuum melting in magnesium oxide crucibles and casting in a copper mold. Two grades of low sulfur electrolytic cobalt were used as the basic material for the study, one from Johnson, Matthey and Co. and the other from the International Nickel Co. Each contained about 99.5 pet Co and had a nominal sulfur content under 0.005 pet. The sulfur was added initially as cobalt sulfide powder. Later, some low sulfur alloys were prepared by diluting the high sulfur alloys with cobalt. Trouble was experienced in controlling the sulfur content. Apparently much of the cobalt sulfide powder was lost during melting, as most of the samples contained a lower sulfur content than was added. The alloys were evaluated for hot brittleness by heating to 1000°C in a hydrogen furnace and swaging in air. The results of these tests are summarized in Table I. All the alloys containing less than 0.008 pet S were successfully hot swaged to 1/4 in. diam. The bars containing more than 0.015 pet S could not be swaged because of the formation of intercrystal-line cracks similar to those illustrated in Fig. 1. Examination of the microstructure of the cast bars revealed cobalt sulfide eutectic at the grain boundaries, Fig. 2. The sulfide was not always continuous at grain boundaries in bars that were hot embrittled but, in general, the particles did form a network that could account for the brittleness above the eutectic temperature, 880°C. There is no question about the brittle nature of a specimen exhibiting a continuous sulfide network such as is shown in Fig. 2b, though a sulfide distribution similar to that in Fig. 2a is marginal. This particular bar cracked when hot-swaged. However, other bars with lower sulfur content but with some sulfide phase at grain boundaries were successfully worked. The reduction of area of a hot tensile test specimen was also found to be a sensitive indicator of sulfur embrittlement. The variation of reduction of area with sulfur content is shown in Fig. 3 for specimens fractured at 900°C in an evacuated capsule. The ductility of cobalt is greatly reduced when the sulfur content exceeds 0.005 pet. Similar results were obtained for alloys tested at 800°C, below the eutectic temperature. The upper sulfur embrittlement limit of 0.015 pet, Table I, agrees with the observation of Kalmus8 hat

Jan 1, 1957

By H. R. Shell

Of three known compounds in the ternary system K20 - PbO - SiO2, one having the composition K2Pb4Si8021 crystallizes into a structure with asbestiform properties. This compound, whose silicon-oxygen ratio is between that of the layer silicates (for example, mica) and the double-chain amphiboles, crystallizes in the tetragonal system. It malts, apparently congruently, at 779° C. The fiberized product prepared from crystals is fluffy and closely resembles natural asbestos in appearance, but is more brittle and has less strength. However, potassium-lead silicate may be separated into fibers with a uniform diameter of 200-300 A.U., and the fibers show with the electron microscope the s criteria that have been interpreted as indicating a hollow tube structure in chrysotile asbestos. Since very few inorganic crystalline compounds have such a structure, the material has unusual scientific interest. Microcrystalline potassium-lead silicate was rapidly and completely formed when powdered glass of the same composition was heated to 650° - 700° C, but macrocrystals grew only slowly from the viscous massive glass. Maximum growth rate was 0.12mm. per hour at 700° C.

Jan 1, 1957

By J. P. Powell

Systematic waterflooding was first tried in Washington County, Okla., in 1937, when a 40-acre project was begun in secs. 24, 29, 32, and 33, T. 27 N., R. 13 E., jointly by the Keener Oil Co. and the Phillips Petroleum Co. The property later was sold to Lee Morrison. A second project was begun in 1941 in sec. 14, T. 6 N., R. 12 E., by the Oklahoma Oil Corp. Both projects were abandoned by the end of 1942. A third project was begun in 1945 and the fourth in 1948, but 1949 actually was the beginning of intensive waterflooding development in Washington County. The results of previous waterflooding projects are described in Bureau of Mines Reports of Investigations.2 3 4/ Oil production in the county followed a similar trend, dropping to a low of 990,000 barrels in 1945, then steadily increasing until 1956, when more than 4 mil-lion barrels of oil was produced. Most of the increase in oil production is directly attributable to water injection.

Jan 1, 1957

By W. A. Selvig

[THE BUREAU OF MINES receives many requests for information regarding the low-temperature carbonization properties of American coals. This report presents in collected form the results of Fischer-Schrader bench-scale, low-temperature carbonization assays at 500° C. made by the Chemistry and Physics Section at the Pittsburgh station of the Bureau of Mines. Most of the assays were made of coals tested in connection with a survey of gas and coke-making properties of American coals,4 which was started in 1928 by the Bureau in cooperation with the American Gas Association. Other coals were assayed in connection with miscellaneous investigations. Since 1930 about 400 samples of coal were assayed from nearly every coal-producing State, Alaska, and British Columbia, Canada. The results of the tests on about two-thirds of the coals are scattered through more than 50 separate publications. This paper summarizes the data in the published reports as well as all unpublished data obtained to January 1, 1956. The report also includes a detailed description of the procedure used in making the assay.]

Jan 1, 1957

By L. J. Kane

While analyzing synthesis gas produced from coal, the Bureau of Mines found that conventional procedures for naphthalene determination were difficult and time consuming. The Bureau developed a rapid and sensitive turbidimetric procedure, which requires only simple instruments and hence can be used in plant-control laboratories. The gas is passed through a saturated aqueous solution of picric acid at 3° to 4° C. whose turbidity is then measured at room temperature. A dispersing agent is added to prevent coagulation of the suspension on warming. Only about 1 mg. (0.015 grain) of naphthalene need be absorbed, and precision and sensitivity are a few ten-thousandths of a grain, or a few hundredths of a grain per 100 cubic feet. The determination can be completed less than 10 minutes after absorption. INTRODUCTION One of the functions of the Branch of Coal Gasification, Bureau of Mines, Morgantown, W. Va., is to develop economical methods for manufacturing, from coal, a mixture of hydrogen and carbon monoxide for producing hydrogen, methane, and other gaseous fuels. This raw gas may contain many impurities, including naphthalene. This impurity is usually determined by first forming naphthalene picrate in a water solution of picric acid, separating the picrate, and titrating the unreacted picric acid or the picrate itself.

Jan 1, 1957

By R. R. Hartman, W. B. Agocs

IN the course of a return flight from Olympia, Wash., to Laramie, Wyo., an airborne magnetometer profile was recorded continuously. The level of flight was controlled at barometric levels along segments of the flight. Barometric altitude was changed from 3000 ft to a maximum of 12,000 ft above mean sea level to take care of topographic variations. Terrain clearance varied from 800 to 7300 ft. Horizontal positions were obtained by recording and tying to cities, towns, airports, river crossings, and other landmarks in the course of the flight. Figs. 1-6 show the course of the flight and the general geologic and tectonic features traversed. The flight line begins south of Olympia, Wash., and proceeds south across the Puget-Willemette depression to the Columbia River. Thence it proceeds eastward along the Washington-Oregon border across the Cascade Mts. and lava flows and the Umatilla basin to Pendleton, Ore. From Pendleton it traverses the Blue Mts. uplift of Oregon in a southeasterly direction, and then to the Boise basin of southwestern Idaho. The flight line swings in an easterly direction as it passes over the Snake River downwarp to the south of the Idaho batholith. It then passes over the northern portion of the Great Basin and the heavily overthrust area at the intersection of the Utah, Idaho, and Wyoming borders. The flight then assumes an easterly course to cross the series of basins and uplifts of southern Wyoming and terminates near the western flank of the Laramie uplift. It should be clearly understood that all statements in this article pertaining to the magnetics were interpreted on the assumption of elongate anomalies transverse to a single profile. Hence any theories or ideas advanced here are in line with future paths of research rather than trying to prove or disprove existing data. Magnetic Interpretation: Depth determinations were made by the slope method of Peters: which is stated as follows: "Draw a line in the maximum slope (at the point of inflection); draw a line whose slope is one-half this maximum slope; draw two lines parallel to this line tangent to the anomaly curve. The horizontal distance between the points of tangency is approximately equal to 1.6 times the depth [or the distance times 0.6251." Certain assumptions must be made for determinations of the causes of the magnetic anomalies:' 1) The anomaly is caused by a susceptibility change rather than basement relief. 2) Polarization of the basement rocks is in the same direction as the earth's inducing field. 3) The disturbing magnetic mass has a great horizontal length in comparison to its width and its sides are vertical and of great vertical extent. 4) The anomaly is unique and not affected by the anomalies from nearby sources.

Jan 1, 1957

By A. D. K. Laird, C. A. Johnson

Drag coefficients for a cylinder being towed through water at constant velocity and also at constant linear acceleration were measured. Drag coefficients for constant velocity towing showed reasonable agreement with previous results. The drag coefficients found for constant acceleration showed little correlation with either the magnitude of the acceleration or the value of the modulus AD/V2 and tended to be slightly lower than those for constant velocity. INTRODUCTION For the design of offshore structures, wave forces acting on immersed cylinders are of importance. Several investigations have been made of these forces and of how they can be predicted from wave theories. A paper by Crooke' summarizes much of the work already done. More recent research by the Wave Research Laboratory at the University of California, Berkeley, has added much to the body of data collected under ocean wave conditions, but has not found a reliable method of force prediction from basic theories of wave motion. The present investigation is part of a long-range program to collect data with which to test current and future theories and correlations. The immediate objective was to measure drag forces on a circular cylinder subjected to linear accelerations over the range of Reynolds numbers between l04 and 105 where the drag coefficient was a constant for constant velocities. In particular, the effect of constant acceleration from rest and from uniform motion was to be investigated. The effect of acceleration may be evaluated in terms of drag coefficients. A useful resistance coefficient, C, is defined by the equation for total drag force, D, exerted by the fluid on the cylinder. DT =CSp V2/2.........(1) The coefficient C may be plotted as a function of the parameter AD/V2. Here D is the diameter and S is the projected area of the cylinder. The acceleration and velocity are A and V. The mass density of the fluid is p. An alternate drag coefficient, C, corresponds to the total force of the fluid opposing the motion minus the virtual mass force. This drag coefficient, arising from the velocity of the fluid, may be compared with that for the same cylinder in uniform motion. The similarities and differences between this coefficient as calculated for accelerated and for steady motion are of interest in the inverse process of predicting drag forces on cylinders under arbitrary conditions. One serious difficulty in this method is the specification of the virtual mass which depends also on the flow picture about the cylinder.1 EXPERIMENTAL EQUIPMENT The experiment was performed in the combination wave and towing tank at the Engineering Field Station of the University of California. The tank is 200 ft long, 8 ft wide, and 6 ft deep. The tow carriage is externally propelled by a cable, and the velocity of the carriage is maintained essentially constant by means of an am-plidyne. For the purpose of the present investigation, the speed control of the amplidyne was modified by inserting a linear speed control rheostat, which was rotated at a constant speed by a small d-c motor equipped with a slip-clutch. Accelerations which were constant over a reasonable length of time were thus produced. The magnitude of the acceleration depended upon the speed of the d-c motor and the limiting speed of the carriage. Data were obtained for a range of accelerations of 2 to 10 ft/sec,2 and a range of velocities of 2 to 15 ft/sec. An accelerometer (Statham Type C-2-350) with a range of ±2g was attached to the carriage and connected to a Brush analyzer and penmotor. A continuous coil of wire with 10 turns/ft wound around a fixed wooden form extending for a distance of 40 ft along the length of the tank was connected by an electrical contact mounted on the carriage to a Brush analyzer and penmotor, to give the time-position history for each run. The test cylinder was machined from solid aluminum alloy, 17-ST. to a diameter of 1.250 in., and could be

Jan 1, 1957

By Lawrence H. Van Vlack, Alfred S. Keh

The distribution of sulfur in iron was found to be dependent upon the time and temperature of the treatment as well as the chemical composition of the sulfide. With higher temperatures, the sulfide phase spreads more extensively between the iron grains. A complete network, however, does not form until approximately 1300°C (2372°F), ot which temperature the dihedral angle approaches zero. Silicon has little effect on this change. Aluminum, oxygen, and manganese all modify the temperature of sulfide network formation to a higher value. The microstructures which result and have significance in relation to hot-shortness are discussed. SULFIDE inclusions in steel were recognized by metallurgists before the turn of the century. Considerable attention has been paid to them, and numerous studies have been made on the working properties of steel as affected by them. It has been suggested that ho t-shortness of steel is due to the presence of an enveloping liquid sulfide film at the grain boundaries of the steel in the range of the hot-working temperatures. However, several facts have been observed in commercial steels which do not seem to be completely consistent with this explanation: 1) the frequent absence of continuous films of sulfide as observed under the microscope, 2) the absence of hot-shortness in some high sulfur and resulfurized steels, and 3) the limitation of hot-shortness to a definite temperature range. The role that manganese plays in steel to eliminate hot-shortness is well known, but the theory behind it is still under question. Moreover, the effect of de-oxidizers such as aluminum and silicon, and the effect of oxygen are still not clearly known. In this study, the effect of heat treatments and of additions of manganese, aluminum, silicon, and oxygen upon the distribution of sulfide inclusions in iron was investigated. Both the as-cast and the heat treated structures were studied, using microscopic and autoradiographic techniques. Part of the results were interpreted in terms of Smith's' concept of microstructure. Review of Literature Metallurgists used to consider sulfide inclusions as suspended particles. It was Wohrman' who first pointed out that sulfide inclusions are soluble in liquid iron. Many observed facts may be understood on the basis of this concept of solubility. Wohrman found that small castings contain small inclusions. and larger castings contain larger ones. Also, inclusion sizes are smaller near the chilled surface. For the same size ingot, the average inclusion size in a given heat of steel depends upon the rate of solidification. That is, with slow solidification, enough time for precipitation and agglomeration of these

Jan 1, 1957

By Herty, C. H.

Three distinct processes take place during the conversion of iron ore to steel. First: the raw ore is reduced to metallic iron in the blast furnace and during this reduction certain constituents are dissolved in the iron, either through the solution of a solid into a liquid phase, as in the case of carbon, or by reduction of an oxide existing in the slag to the metallic element of that oxide, with subsequent solution of the metallic element in the iron. Thus by the process of solution and reduction, a pig iron results which contains about 4 per cent carbon, 1 per cent silicon, 1 to 2 per cent manganese, 0.1 to 0.4 per cent phosphorus, and 0.03 to 0.10 per cent sulfur. To obtain a sufficient yield of iron from the ore it is necessary that the reducing process be carried as far as possible, with the result that the impurities mentioned accompany the reduced iron. Second: to convert this iron into steel it is necessary to oxidize a part of the iron in eliminating the impurities to the extent desired for the particular product being made. In eliminating these impurities by oxidation a certain amount of iron oxide (FeO) dissolves in the steel. This dissolved FeO reacts with the metalloids, except sulfur, and to eliminate them to the desired extent it is necessary to leave a considerable amount of FeO in the metal. The reaction of iron oxide with silicon, manganese, and phosphorus results in the formation of the oxides of these elements. The oxides enter the slag and the extent of elimination of the elements depends on certain equilibria between the slag and the metal. The reaction of FeO with carbon results in the formation of the gases CO and CO, which, after saturating the metal, pass into the furnace gases. Third: after the iron has been purified to the desired extent as far as the elements listed are concerned, it is necessary to deoxidize the bath to remove the FeO, which is the vital factor in gas formation as the steel solidifies.

Jan 1, 1957

By O. Mellgren, A. M. Gaudin, P. L. De Bruyn

In the January 1956 issue: TP 4137B. Adsorption of Ethyl Xanthate on Pyrite. By A. M. Gaudin, P. L. de Bruyn, and Olav Mellgren. P. 65. Since P. L. de Bruyn is now a member of the AIME, the word "associate" should be removed in describing his status. The address of the third author, Olav Mellgren, should read: 74-2 Chingola, N. Rhodesia. P. 68, second paragraph, last line: the word "300-fold" should be replaced by "3000-fold." Also in the January 1956 issue: TP 4158B. Energy Transfer by Impact. By R. J. Charles and P. L. de Bruyn. The authors wish to express their disapproval of the omission of the abstract from the article, since they believe that an abstract fulfills a very important function in every paper.

Jan 1, 1957

ON FEBRUARY 4, 1952, the Phelps Dodge Corporation signed Contract GS-00P(D)-12068 with the United States Government. This interesting document dealt with the "Bisbee East" project as part of the Government's program to increase the supply of needed copper by encouraging private enterprise to expand production. The ore deposit involved was a relatively small body of low-grade ore lying east of the remnants of the old Sacramento Hill deposit that was exploited with indifferent success from 1923 to 1931, as related in THE PORPHYRY COPPERS. Planning for the entire enterprise had been directed from the start by Harrison M. Lavender, who in 1945, succeeded Percy G. Beckett as vice-president and general manager for all of Phelps Dodge's Western mines and smelters. The untimely death of Mr. Lavender in 1952 prevented him from seeing his plans brought to fruition; but in his honor the mine was fit- tingly named "The Lavender Pit" and was so dedicated on August 7, 1954. The Copper Queen Branch operates under- ground mines at Bisbee (production in 1955 was 28,000 tons) ; but, as this volume is concerned only with Porphyry operations, this chapter deals only with the Lavender Pit project, or as the Government knows it, Bisbee East. My reason for going into some detail regarding the floor-price contract is that it is fairly typical of contracts made by the Government in connection with a half-dozen other copper-expansion projects; and, incidentally, with various projects involving other strategic metals. Phelps Dodge did not seek a loan or other financial aid. The only encouragement asked consisted of (a) the privilege of a five-year write-off (commonly called rapid tax amortization)

Jan 1, 1957

By D. Perry, G. W. Binkley, G. K. Dumbauld, F. A. Brooks

A new cementing technique has been developed which is particularly applicable to permanent-type well completion operations. The technique makes use of the accelerating effect of calcium chloride on setting time and strength development of cement cake deposited in squeeze cementing. An unique feature is that the accelerator is applied after the unaccelera-ted cement slurry has been squeezed and the excess has been reversed from the well. Laboratory data on the accelerating effect of calcium chloride applied to the fi1ter cakes of three low-water-loss cementing compositions demorzstrate that the procedure results in relatively rapid development of strength and impermeability of the cement cake. Simulated squeeze-ceinenting tests made in the laboratory likewise corroborated the practicality of the procedure. The laboratory tests showed that a newly developed oil-emulsion cemerzting composition is more susceptible to acceleration of set than are modified cements containing high percentages of bentonite. The acceleration procedure has been used successfully in field operations. INTRODUCTION Nature of Problem In squeeze-cementing operations, a substantial amount of time is consumed in waiting on the cement to develop strength after it has been squeezed into the well. Frequently, an interval of 18 to 24 hours or longer is required for the development of strength sufficient to prevent failure of the cement during subsequent operations in the well. Reduction of this waiting-on-cement time offers appreciable savings both in time and in money. A particular type of squeeze-cementing operation to which an increasing amount of attention has been given is encountered in permanent-type well completion operations wherein perforations are to be squeezed off1. In this procedure, it is customary to pump the cement slurry down the tubing and out into the perforated section through a retractable extension pipe. Squeeze pressure is then applied, which forces the cement slurry into the perforations and causes the build up of a compact filter cake of cement within the perforations. The excess slurry remaining in the hole is then removed by reverse circulation. The extension pipe is then retracted, and, if a new interval is to be perforated, a perforating gun is run through the tubing. The newly perforated interval may then be tested by swabbing. In such operations, it has been customary to allow approximately 20 hours or so for hardening of the cement squeezed into the perforations. This time interval is usually measured from the time that the cement is reversed out of the hole to the time that subsequent swabbing is started. If the cement has not developed strength at the commencement of swabbing, the pressure differential caused by swabbing results in failure of the squeeze job. At the time that the work described in this report was initiated, particular consideration was given to the reduction of waiting-on-cement time in squeeze cementing by the permanent-type completion technique. Consequently, much of the experimental work was directed to this specific objective, though the process which was developed for acceleration of strength development has possible application in other than permanent-type completion operations. Method of Attack Although quick-setting cements

Jan 1, 1957

By F. H. Ellinger

A BRIEF description of the thermal expansion characteristics and of the four known crystal structures among the six allotropes of plutonium has been covered in a summarizing report on plu- tonium by E. R. Jette.' A detailed description of the crystal structure and thermal expansion of y plutonium has been published.' The present paper deals with the crystal structure of d plutonium, and with the thermal expansion of 6, 6' and € plutonium, as determined by X-ray diffraction methods. The X-ray diffraction patterns were taken in Uni-cam high temperature powder cameras using fil-

Jan 1, 1957

By P. L. Allsman

Butte mining district contains extensive manganese vein deposits forming a peripheral zone. Oxidation in the veins studied usually extends to a depth of about 75 ft. Secondary minerals formed by oxidation were found to be ramsdellite—always accompanied by intermixed pyrolusite—and cryptomelane. Enrichment of the gossan is accomplished by reduction of weight upon oxidation; theoretical enrichment is 32.2 pct. Additional enrichment is caused by leaching of soluble minerals, particularly calcium and magnesium carbonates. BUTTE mining district contains extensive manganese vein deposits in the outer zone, surrounding the copper and zinc deposits and corresponding to the well known silver zone. This article describes the mineralogy of the manganese veins, the oxidation and enrichment processes, and the use of this information in prospecting. Information was derived from a study of the Emma, Star West, Tzarena, and Norwich mines, selected as representative of the district. Vein exposures at these mines were mapped, studied, and sampled on the outcrops and throughout the oxidized zone. Specimens were cut and polished for minera-graphic examination, identification, and textural studies. Knowledge of the manganese oxide minerals is scanty, previous information having been rendered obsolete by publication of the first correctly identified list of manganese oxide minerals by Fleischer and Richmond in 1943. Positive identification of the manganese oxides is possible only by X-ray analysis. Identifications for this study were made by the author with a Phillip's Diffractometer at the Montana School of Mines and confirmed by Lester Zeihen of The Anaconda Co., using a Norelco X-ray camera. It was necessiary to re-evaluate some X-ray data, as published patterns of several manganese oxides proved to be of mixtures, mostly showing pyrolusite as a contaminant. Perhaps the most useful information on oxidation and enrichment of manganese is presented in recent books by Goldschmidt1 and Rankama and Sahama.2 While their hypotheses are not conclusively proved, all laboratory and field evidence has served to substantiate them. This information was very useful in this study. Mineralogy: The primary minerals of the manganese veins are chiefly rhodochrosite and quartz. Rhodonite is abundant in the northern part of the district and in places has been found to comprise over a third of the vein matter. A variable but generally small amount of sulfides may be present, principally pyrite and silver minerals. Sphalerite is progressively more abundant near the zinc zone. Rhodochrosite is believed to form complete iso-morphous series with siderite, ankerite, and calcite. Some variation into these compositions is common, and the intermediate forms are termed manganosid-erite, manganankerite, and rnanganocalcite. Much of the rhodochrosite is remarkably pure. Other manganese minerals in the district include huebner-ite, alabandite, and helvite. Ramsdellite (MnO2, orthorhnmbic) is the principal manganese oxide mineral, comprising perhaps two-thirds of the total oxides. It is dull to iron black, and generally massive or platy in structure. A prominent platy cleavage is the only distinguishing megascopic characteristic. Pyrolusite (MnO2, tetragonal) is next most abundant to ramsdellite, with which it is usually intimately mixed. The luster is often brighter or more metallic than in ramsdellite, and needle-like crystals are diagnostic. Pyrolusite is common in small cavities formed by oxidation of pyrite grains. It is relatively abundant in zones of high limonite content. Cryptomelane (KMnO16 tetragonal ?) is rare in the outcrop, but becomes more abundant with depth. At depths of several hundred feet it is the principal oxide. Although its appearance varies, a blue-black flinty luster and blocky to conchoidal fracture are most common. A potassium flame test will identify this mineral. Hardness of all three oxides varies from 2 to 6. The three are quite commonly intermixed, and their textures can vary greatly. The commonest textures are massive or colloform, representative of colloidal deposition, or vuggy and boxwork textures, formed by partial leaching and oxidation in place. A box-work of either ramsdellite or chalcedony is formed after rhodochrosite rhombs and is indicative of ore shoots in this district. Some replacement of both quartz and the granitic wallrock by ramsdellite has been noted, but most of the oxide was deposited as a fissure filling by fine particles. No trace of manganite, hausmannite, braunite, or manganosite was found. No minerals of the psilome-lane group were detected besides cryptomelane. Amorphous MnO, was found at several spots. A specimen of oxide coated with yellow barite crystals was amorphous and not psilomelane (BaMn9O18. 2H2O). Voids formed by the leaching of sphalerite were coated with cryptomelane, not hetaerolite (ZnMn2O4) as might be expected. No manganese sulfate minerals were found in the gossans; however manganese alum (apjohnite ?) has been re-

Jan 1, 1957

By F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.' The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.' It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957