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By P. K. Kaiser, C. Mackay

A circular shaft with a diameter of 6m was excavated by the conventional drilling and blasting method to a depth of 235m through 60m of glacial till, 1 Om of water bearing basal sand, 1 1 Om of clay shale (Bearpaw Formation) and finally a strata of coal, mudstone, siltstone and sandstone (Oldman Formation). The lined shaft was instrumented at three levels by multipoint extensometers to determine the displacement field near the shaft bottom, embedment strain gauges to measure the strains in the liner and IRAD-stress change gauges to observe the radial and tangential stress changes in the rock mass. The data from these gauges were used to determine the in situ stress field. An attempt to measure in situ stresses by overcoring was also made at a higher elevation. The performance of the shaft and its support was then evaluated by use of the "Convergence-Confinement Method". For this purpose the measurements of stress changes and displacements were combined to determine by extrapolation the displacements ahead of the shaft and after the liner installation. The convergence curves calculated in this fashion were then used to evaluate the performance of the cast-in-place concrete liner and of an alternate shotcrete shaft support system.

Jan 1, 1983

By David H. Browne

Nickel has always been a fruitful mother of problems. Previous to the year 1906 nickel was regarded as an element replacing iron in copper-mattes, and it was believed that the same laws which governed the elimination of iron could be applied to nickel. This conception has lately undergone a complete change, and nickel in all its stages is now regarded as an element replacing copper; in other words, copper-nickel is considered not as two elements, but as one metal. When we commenced our investigations on Monel metal we made a great many experiment* on the conversion of mattes, both high copper and high nickel. We studied closely the composition of the mattes and the changes produced by the blow. We found in all cases certain agreements which me believe are due to some law. Briefly stated, our conclusions are as follows : 1. Nickel is not an element replacing iron in matte. 2. Nickel-copper alloys act in the matte-blow like one metal. 3. Nickel-copper alloys follow, during the matte-blow, exactly the same laws that govern the behavior of copper alone. This brings up the question: What are the laws governing the production of metallic copper, and what are the relations of copper to sulphur and iron during the Bessemer blow?

Jan 1, 1911

By Bryon W. Cheever

The greatest objection to be brought against the present methods for estimating phosphorus in iron and steel, is the time consumed in the operation. The following method, originated and perfected by Mr. E. D. Campbell, assistant in the chemical laboratory of the University of Michigan, will, 1 think, if carefully followed out, give results that are sufficiently accurate for technical purposes, and will give them in less time than they can be obtained by any other process. The process consists in comparing the color obtained by the action of stannous chloride upon a solution of the phospho-molybdate precipitate obtained from the solution of iron or steel, with that obtained from a standard solution of molybdie acid which represents a given amount of phosphorus. The operation is as follows : Take of ordinary steel 1 grm. and treat as in any of the wellknown processes until the phosphorus is precipitated as ammoniumphospho-molybdate. When precipitated, the phospho-molybdate precipitate is filtered out, thoroughly washed with an acid solution of ammonium nitrate, and, finally, twice with water, to remove most of the ammonium nitrate. The precipitate is then dissolved in about 1 c. c. of 10 per cent. potassium hydrate, which is let fall drop by drop on the filter till the precipitate is dissolved ; the filter is now washed with about 25 or 30 c. c. of water, and the potassium hydrate solution, which now consists of 25-32 c. c. of solution, is boiled until the peculiar frothy appearance, which first appears on boiling, is entirely gone. The solution is then cooled until perfectly cold, and about 10 or 15 c. c. of strong hydrochloric acid added ; if the solution is kept cold this will form no precipitate, but a light yellow or colorless solution. The solution is now ready for the addition of stannous chloride, and the subsequent comparison of color produced with that obtained from the standard molybdie acid. The comparison is made in tubes that are calibrated like carbon-tubes, but which are larger, about 5/8-inch bore, and graduated to 100 c. c.; this makes them about 18 inches long. To make the comparison of color, first transfer the now acid solu

Jan 1, 1886

By Norman P. Goss

It is generally agreed that cold-working mechanically refines the grains into smaller fragments and with continued working these are oriented with certain crystallographic directions bearing a relation to the direction in which the metal is worked. Some of the energy expended on the metal during plastic deformation appears in the form of heat, but a very small portion remains in the metal as stored energy. The entropy, specific heat capacity, temperature at which recrystallization will just begin, density, ductility, elasticity, tensile strength, and resistance to corrosion are affected. These properties have been studied extensively and some of the changes in the physical properties due to cold-working were attributed to lattice distortion.l-8 The broadening of the Ka lines on the X-ray diffraction diagrams of plastically deformed metals is believed to indicate lattice distortion, and consequently the existence of internal stresses. The evidence supporting this theory rests solely upon the observed experimental fact that the diffraction lines are broadened and the Ka doublets are completely diffused. Elam9 has reviewed the matter of lattice distortion in relationship to the hardening of metals by plastic deformation. The X-ray diagrams of plastically deformed metals differ in general from annealed metals. The hardening of a metal was believed due to lattice distortion.9 The resolution of the doublet is lost when a metal is cold-worked and the Laue spots are elongated. At one time this elongation was thought to indicate the elastic bending of the crystal planes. However, more careful work showed that the asterism was due to new orientations developed within the fragmented grains during plastic deformation. Some theories attributed the hardening to fragmentation of the grains into smaller units. Jeffries and Archer,ll after carefully considering the problem of work-hardening from many angles, came to the conclusion that cold-working mechanically refines the grains into smaller crystal fragments, some of which at least differ in orientation from the parent grain. The increase in

Jan 1, 1940

By Norman P. Goss

It is generally agreed that cold-working mechanically refines the grains into smaller fragments and with continued working these are oriented with certain crystallographic directions bearing a relation to the direction in which the metal is worked. Some of the energy expended on the metal during plastic deformation appears in the form of heat, but a very small portion remains in the metal as stored energy. The entropy, specific heat capacity, temperature at which recrystallization will just begin, density, ductility, elasticity, tensile strength, and resistance to corrosion are affected. These properties have been studied extensively and some of the changes in the physical properties due to cold-working were attributed to lattice distortion.l-8 The broadening of the Ka lines on the X-ray diffraction diagrams of plastically deformed metals is believed to indicate lattice distortion, and consequently the existence of internal stresses. The evidence supporting this theory rests solely upon the observed experimental fact that the diffraction lines are broadened and the Ka doublets are completely diffused. Elam9 has reviewed the matter of lattice distortion in relationship to the hardening of metals by plastic deformation. The X-ray diagrams of plastically deformed metals differ in general from annealed metals. The hardening of a metal was believed due to lattice distortion.9 The resolution of the doublet is lost when a metal is cold-worked and the Laue spots are elongated. At one time this elongation was thought to indicate the elastic bending of the crystal planes. However, more careful work showed that the asterism was due to new orientations developed within the fragmented grains during plastic deformation. Some theories attributed the hardening to fragmentation of the grains into smaller units. Jeffries and Archer,ll after carefully considering the problem of work-hardening from many angles, came to the conclusion that cold-working mechanically refines the grains into smaller crystal fragments, some of which at least differ in orientation from the parent grain. The increase in

Jan 1, 1940

By R. Maddi, I. R. Kramer

The delay time for the initiation of slip was studied in single crystals of a brass, aluminum, and ß brass. A delay time for slip was found in ß brass when the specimens were tested below room temperature; however, one was not found for a brass or aluminum. A general theory for the existence of the brittle transition temperature is proposed. A LTHOUGH a considerable amount of effort has A been devoted to the study of the deformation and fracture of single crystals, the vast majority of the work was concerned with static tests or with tests carried out at relatively slow strain rates. The necessity for the study of a possible incubation time for slip becomes apparent when the various theories which have been postulated for the elucidation of the mechanism of slip are considered. The existence of an incubation period would strongly indicate that slip occurs by a process of nucleation and growth; whereas the absence of an incubation would present rather convincing evidence that slip occurs by a cataclysmic process. In addition to shedding light on the process of plastic deformation, an understanding of the early stages of plastic deformation may be helpful in finding an explanation for the brittle behavior of the body-centered metals under certain conditions. It is well known that these metals, such as iron, molybdenum, tungsten, ß brass, etc., will become brittle as the test temperature is lowered or the strain rate is increased. In spite of the fact that this subject has received considerable attention since the turn of the century, no adequate theory exists today which explains the phenomenon. In the ductile temperature range the metal breaks with a "fibrous" fracture after considerable slip has taken place. In the brittle temperature range the metal fails essentially by cleavage on the {loo) planes: however, some plastic flow is always present even in the most brittle fractures. It is possible, as will be explained later, to ascribe this brittle behavior to the length of the incubation time for slip. Clark and Wood,' using polycrystalline metals, showed that a delay time existed for the yield point in mild steels and that the delay time depended upon the applied stress. These authors stated that the delay time was observed only with those materials for which the stress-strain curve showed a definite yield point. In their work only the mild steel specimens exhibited a delay time at the yield point, while the other materials studied-type 302 stainless steel, SAE 4130 normalized steel, SAE 4130 quenched and tempered steel, 24s-T aluminum—did not show a delay time. These authors' in an extension of their work, found that as the temperature was lowered the delay time was increased. It is, then, the purpose of this investigation to measure or to set an upper limit on the delay time for plastic flow in single crystals of a brass, aluminum, and ß brass. The delay time will also be studied as a function of temperature. The incubation time may be measured by determining the length of time the specimen will support a stress without slip occurring when the stress is greater than the static critical resolved shear stress. In order to accomplish these measurements use was made of a pendulum which was so designed that a single crystal specimen could be placed at various positions along its length. When a pendulum is struck by another pendulum of the same length, an elastic wave is transmitted down the bar with the velocity of sound in the material and is reflected from the far end of the bar. The reflected wave then travels back and unloads the stress until it reaches the impacted end of the bar and the two pendulums separate. The length of time that the specimen is subjected to the stress is equal to the time it takes for the stress wave to travel twice the distance from the specimen to the end of the bar. The stress applied to the specimen is governed by the velocity of impact of the two pendulums. The stress at which the specimen first suffers plastic: deformation was determined in these experiments by examining the specimen under the microscope for the first appearance of slip lines and by measuring the residual strain after each impact. In these experiments the critical resolved shear stress was approached from the low stress side and no attempt was made to determine it exactly. To determine it exactly, it would have been necessary to find that stress at which slip would have just started. However, since the stresses were increased in rather small increments the critical stress is believed to be approached rather closely, as will be seen from the experimental results. The critical stress will be taken as the highest stress obtained before the onset of plastic deformation. The stresses

Jan 1, 1953

By H. E. Cline, J. L. Walter

Grain boundary sliding and migration were studied in pure aluminum bicrystal and polycrystal samples with two-dimensional grain structure. Scratches, 50 P apart, were used for measurement of sliding and migration distanceso. Samples were deformed at constant rate at 315C and events recorded continuously on wrotion picture film. Electron micrograPhs of boundary-scratch intersections were obtained. Yield and flow stress values were measured. The sequence of sliding and migration events for a three-grain junction is described in detail. Sliding depended only on the resolved shear stress imparted to the boundary. Sliding was accowmodated by formation of shear zones in grains opposite triple points and adjacent to curved boundaries. These shear zones provided the driving force for grain boundary migration. Migration caused rumpling of the boundaries, decreasing the sliding rate. Sliding and migration generally began at the same time, occurred simultaneously and ended at the same time. In the bicrystal, sliding and migration rates were proportional. Initial sliding rules of 5 X joe cm per sec. were measured for the polycrystal and bicrystal samples. These sliding rates agree wilh the internal friction experirnents of K;. The observations seem consistent with a viscous boundary sliding nzechanism. GRAIN boundary sliding is the translation of one grain relative to its neighbor by a shear motion along their common boundary. Sliding is thought to be an important mode of deformation at elevated temperatures and at low strain rates such as prevail in creep,' and perhaps in the area of superplastic behavior.2"4 Although much work has been done to investigate grain boundary sliding, the effort has not led to the identification of a mehanism. KG showed that grain boundaries in aluminum exhibit a viscous nature under very small displacements of internal friction measrements. Various dislocation mechanisms have been proposed but are without conclusive experimental support. Attempts to relate sliding to 6's viscous boundaries have been unsuccessful in that measured rates of sliding are always several orders of magnitude lower than KG'S results would predict.= In bi crystals7and polycrystalsR of aluminum tested under constant load, the grain boundary sliding was found to be proportional to the total creep elongation which indicated that sliding might be controlled by deformation of the grains. Shear zones were observed to extend beyond grain boundaries at triple points to accommodate the sliding.8 Surface observations brought forth the opinion that sliding and migration occurred alternately, in sequence.' Measurements of sliding at the surface have been criticized because they might not be representative of the interior of the sample. Generally speaking, it seemed that much of the previous work and knowledge was based on observations made at relatively low magnification and examination of samples after deformation had been accomplished. Thus, it was the purpose of the present study to continuously record, at high magnification, the events occurring during the deformation of pure aluminum. Samples with two-dimensional grain structures were used to simplify interpretation of the results. The sliding and migration of small areas of many samples were continuously recorded by time-lapse motion pictures. Replicas of the surface were used to provide high-resolution electron micrographs. These observations, coupled with tmsile strength data, provide sufficient information to arrive at an understanding of the phenomenon. EXPERIMENTAL PROCEDURE An ingot of 99.999 pct A1 was rolled to sheet, 0.127-cm thick. Tensile specimens, with a gage length of 0.85 cm, were machined from the sheet. Bicrystal tensile specimens, of the same dimensions, were spark cut from a large bicrystal ingot. The grain boundary was oriented at 45 deg to the tensile axis. The surfaces of the tensile samples were ground flat on fine metallographic paper and were then electropolished in a solution of 75 parts absolute alcohol and 25 parts of perchloric acid. The solution was cooled in an ice-water bath. Using a weighted sewing needle suspended from a small pivot on a precision milling machine, a grid of fine scratches, 50 p apart, was scribed on one surface of the sample. The polycrystalline samples were then annealed in hydrogen for 15 min at 350" to 400°C to produce a two-dimensional grain structure of about 0.2-cm average grain diameter which would not undergo further growth at the test temperature, 315OC. Examination of both surfaces of the samples showed that the grain boundaries were perpendicular to the surface of the polycrystal and bicrystal samples. A hot-stage tensile machine was constructed for use with an optical microscope as shown in Fig. 1. The specimen is shown mounted in the grips. The grips ride in V-ways so that the sample can be mounted without damage. The rear grip is free to slide so that when the sample expands during heating it is not put under a compressive stress. When the grips and samples are at temperature, the rear grip is locked in place by two set-screws. The other grip is connected to a synchronous drive motor which, through a worm gear and a fine-threaded rod, deforms the

Jan 1, 1969

By James B. Cathcart

The potash mine of the International Minerals and Chemical Corp. is about 18 miles east of Carlsbad, New Mexico, in sec 1 and 12, T 22 S, R 29 E, N.M.P.M. Potash is produced from two zones in the Salado formation of late Permian age. The lower zone, consisting of a mixture of sylvite (KCl) and halite (NaCl), lies at a depth of about 900 ft, and the upper zone, in which the principal potassium mineral is langbeinite (K2S04.2MgS0d), lies at a depth of about 800 ft. Because of the plastic nature of the material, fractures in the Salado formation are extremely rare and have been noted only on the 800 ft level of the International mine. The open fracture described below is almost unique. Only one other open fracture has been noted, and it was on a working face in the same general area as the one described, but was destroyed before the writer had a chance to examine it. According to J. E. Tong, foreman on the 800 level, this fracture was similar to, but smaller than, the one herein described.

Jan 1, 1949

By Robert Maes, Robert de Strycker

The Cu-Sn-As systeM was studied in the region near the Cu-42 and (214-As binary diagrams, where reactions in the solid state appear, resulting from the decomposition of the y(Cu-Sn) phase and from the formation of the 7 phase (Cu,As). The techniques used were microscopic observation, thermal analysis by dilatometry, and X-vay diffraction. The formation of the 7 phase gives rise to a ternavy pevitectoid veaction; the decomposition of the y phase gives rise to five transitional reactions. The temperatures of almost all these reactions could be determined; in the most favorable cases , the accuracy of this determination was of 11.5-C. The 7 phase is stabilized by tin additions, the arsenic atoms being replaced by tin atoms up to 35 pct; this has allowed the preparation of pure j) phase and the confirmation, by extrapolation, of the conrposition of this compound in the Cu-As diagram. In the first part of this work, the solidification reactions in the Cu-Sn-As phase diagram were studied. In the copper corner, the structure of the alloys presented the evidence of reactions in the solid state: on the one hand, all the alloys containing the y phase of the Cu-Sn diagram showed, under the microscope, that this phase had formed different decomposition products after complete solidification; on the other hand, the appearance of the 7 phase of the Cu-As diagram necessitated the introduction of a peritectoid formation reaction. The study of the decomposition of the y phase has been done by preparing about forty alloys that were homogeneous y at high temperature. The formation of the 7 phase has been studied by means of a few alloys with a composition near the homogeneity field of this phase at room temperature. The part of the Cu-Sn phase diagram of interest for this study is represented by Fig. 1, with the phase designation which will be used in the remainder of this paper; it is drawn after Hansen and Anderko.' The Cu-As diagram has already been presented in Part I of this work; the significant features of this study are the existence of the arsenides CusAs and Cu5Asz, and the formation of a compound CUEAS, designated as the 7 phase, by a peritectoid reaction at about 325°C. EXPERIMENTAL METHODS The fundamental technique for the investigation of this part of the Cu-Sn-As constitution diagram was microscopic observation; the greatest part of the observed alloys has also been subjected to thermal analysis by dilatometry; a few selected alloys have then undergone an X-ray analysis by powder diffraction. Alloy Preparation. The alloys were prepared from the same products as in Part I of this study: cathode copper, arsenic with a purity better than 99.5, and tin with a purity of 99.98. The fusion of the ternary alloys was realized from

Jan 1, 1967

By C. A. Eligwe, F. W. DeVries, A. E. Torma

This study is an investigation on using hydrogen peroxide for tank-leaching of uranium with sulfuric acid. The optimum sulfuric acid concentration was found to be 0.03 mole 11 -'for a 25% pulp density suspension. The order of reaction with respect to sulfuric acid concentration was found to be ns0.75. The best results vith hydrogen peroxide were obtained at a 4.64 molar ratio of 6202 to U in the ore. The order of reaction was found to be zero with respect to hydrogen peroxide concentration. The theoretical maximum rate effect of Hz02 on uranium extraction was derived as Vm = 8.15 x mole &-'min-'. The highest rate experimentally attained was 8.09 x mole kL'min-'. It was found that the uranium extrac- tion was not affected by the pulp density up to the 50% used in this study. However, the final yieldswere significantly higher (over 90%) for leaches carried out in the presence of Hz02 than (less than 90%) for leaches carried out in the absence of H202. The reaction was found to follow a first order course with respect to substrate concentration (pulp density) regardless of the presence of H202. The effect of temperature was more explicit at moderate tempetatures (30 to 55 C) than at lower (10 C) or at higher (70 C) temperatures. At this latter temperature an almost complete extraction was realized even without H202. The apparent activation energies were found to be AEa = 2.68 kJ mole-' in the absence of H202, 0.5 kJ mole-'with Hz02 at 40 C to 70 C. and 4.72 kJ mole-' with Hz02 at 10 C to 40 C. All these activation energy values suggested that the uranium extraction process is diffusion controlled regardless of the presence of H202. Further, the change in activation energy in the presence of Hz02 indicates the possibility of change in the reaction mechanisms at lower and higher temperatures.

Jan 1, 1980

By D. D. Dunkin

Sandstone has been prepared for glassmaking purposes, and marketed from the White River Valley in Arkansas at Guion, Izard County, since about 1910—soon after the completion of the White River Branch of the Missouri Pacific R. R. Co. Until 1921, operations were somewhat spasmodic and ended in many failures. In that year a plant was built by the Silica Products Co., Inc., and since that time the operation has been continuous and steady. The land is held under leases, covering about 30 square miles of the best sandstone adjacent to the railroad. Most of the product is shipped to glassmakers. Geology The St. Peter sandstone is rather widely distributed in north central Arkansas and is exposed most prominently in outcrops along the slopes of the White River Valley and its tributarirs that form the division between the Boston Mountains to the south and the Salem Plateau of the Ozarks to the north. It is of Ordovician age and is generally underlaid by Cotter dolomite and capped by Plattin limestone, except in the vicinity of Bellefonte and Everton. At those places, it is a massive cross-bedded, laminated, saccharoidal sandstone; underlying it is the Everton limestone and overlying it, the Joachim magnesium limestone The sandstone at Everton contains numerous phosphatic pebbles and inclusions of sandy limestone. The irregularity of cross-section, the evidence of sorting action and the phosphatic pebbles appear to be indications of secondary deposition The St. Peter sandstone occurs as a massive formation in the picturesque bluffs along the White River Valley from near the eastern escarprnent of the uplift northwestmard into the Ozarks. The exposure shows a series of gentle anticlinal and synclinal folds. The greatest thickness is at the southeastern end, where it is over 100 ft. in many places. It thins out to the north and west and then to isolated and scattered deposits which cap the ridges and mountains of the Ozarks.

Jan 1, 1928

By Henry Rogatz

During the year 1937, there were 663 oil wells drilled in the Texas Panhandle, making a daily initial production of 322,332 bb1.—that is, 191 more oil wells drilled than in the previous year, with an increase in the total daily initial production of 66,283 bbl. The total daily potential of the field as determined by the Texas Railroad Commission in its Schedule of Dec. 17, 1937, was 1,039,982 bbl., or an increase of 205,094 bbl. over the previous year. On Dec. 17, 1937, the daily allowable of 68,578 bbl. was assigned to the entire field. The total amount

Jan 1, 1938

By B. Alexander, G. Derge W. Peifer

This is part of a research project in the Metals Research Laboratory of Carnegie Institute of Technology, sponsored by the Carnegie-Illinois Steel Corporation. In organizing our program it became apparent that the problem of analyzing molten steel for hydrogen must be divided into two parts: (I) the correct analysis of a given sample, and (2) the correct sampling of the bath. Emphasis has been placed upon these divisions in the order named because methods of sampling cannot be evaluated until a satisfactory method of analysis is available. Vacuum fusion was selected from the list of possible analytical methods because it seemed to us to offer the best possibilities for giving rapid, accurate results on solid steel samples. A number of objections have been raised against this method as usually practiced. We have sought to meet some of these by proper design of the apparatus. Experiments will be described which show that others are not valid. In the conventional apparatus the sample is held under high vacuum for a period of several hours before it is actually analyzed and one might expect considerable hydrogen to escape during this period. We have provided a means of introducing the sample to the vacuum just before analysis. Another difficulty has been that the entire apparatus has been designed primarily for the purpose of analyzing for oxygen, which constitutes upward of go per cent of the total gases evolved from the sample The volume and pressure measurements have therefore been insensitive to the relatively small amounts of hydrogen present. This difficulty obviously can be taken into account in any apparatus designed especially for the amounts of hydrogen expected. Analysis in Vacuum-fusion Apparatus A number of experiments were carried out to determine the importance of several factors that have been stated as possible sources of error or uncertainty in vacuum-fusion analysis for hydrogen; namely, that hot graphite will absorb some of the gases, that metal vapor will cause discrepancies, and that low results may be obtained as a result of the water vapor (produced by the oxidation of the hydrogen) dissolving in the butyl phthalate of the manometer, or that the blanks obtained from the apparatus are so great as to make the method inaccurate. The experiments also checked on the accuracy and feasibility of using differential freezing as a method of gas analysis in a vacuum-fusion apparatus.

Jan 1, 1945

By E. W. Davis

If the tonnage of merchantable iron ore remaining in the Lake Superior district is divided by the average of the annual shipments for the past 20 years, it will be found that this ore supply will be exhausted in approximately 35 years. This computed exhaustion period would be an indication of the future activities of the iron-mining industry if it were not for the fact that merchantable ore is being manufactured from low-grade ore, of which there is an almost inexhaustible supply in the Lake Superior district. It is true that at present only the simplest of these low-grade ores are being concentrated to any considerable extent, but progress is being made with the treatment of the more complex ores, and now, in addition to 20 washing plants on the Mesabi Range, three plants are equipped with jigs for the treatment of ore that cannot be concentrated simply by washing. The latest addition to the ore-treating plants of the Mesabi Range is a magnetic roasting and concentration plant at Cooley, Minn., in which ore that cannot be concentrated either by washing or by jigging is roasted to the magnetic state and concentrated on magnetic separators. This plant is beginning its third season of operation, and while it is too soon to make definite predictions, there are strong indications that this new process may make commercially possible the manufacture of high-grade, merchantable iron ore from large quantities of low-grade ore now considered worthless. After the iron oxide contained in an ore has been converted to magnetite, almost any desired grade of concentrate can be produced, using magnetic-concentration equipment of the types now in general use for the concentration of the natural magnetites of New York, New Jersey and Pennsylvania. The conversion of hematite (Fe203) to magnetite (Fe3O4) is easily accomplished by heating the ore to a dull red temperature in a reducing atmosphere. The reaction is slightly endothermic, and while it requires 200 B.t.u. to heat to 900' F. one pound of hematite ore containing 45 per cent Fe, it requires only 100 B.t.u. to convert the oxide into magnetite. In the laboratory, using small quantities of ore, this conversion is very simple, but large furnaces suitable for commercial

Jan 1, 1939

By E. W. Davis

If the tonnage of merchantable iron ore remaining in the Lake Superior district is divided by the average of the annual shipments for the past 20 years, it will be found that this ore supply will be exhausted in approximately 35 years. This computed exhaustion period would be an indication of the future activities of the iron-mining industry if it were not for the fact that merchantable ore is being manufactured from low-grade ore, of which there is an almost inexhaustible supply in the Lake Superior district. It is true that at present only the simplest of these low-grade ores are being concentrated to any considerable extent, but progress is being made with the treatment of the more complex ores, and now, in addition to 20 washing plants on the Mesabi Range, three plants are equipped with jigs for the treatment of ore that cannot be concentrated simply by washing. The latest addition to the ore-treating plants of the Mesabi Range is a magnetic roasting and concentration plant at Cooley, Minn., in which ore that cannot be concentrated either by washing or by jigging is roasted to the magnetic state and concentrated on magnetic separators. This plant is beginning its third season of operation, and while it is too soon to make definite predictions, there are strong indications that this new process may make commercially possible the manufacture of high-grade, merchantable iron ore from large quantities of low-grade ore now considered worthless. After the iron oxide contained in an ore has been converted to magnetite, almost any desired grade of concentrate can be produced, using magnetic-concentration equipment of the types now in general use for the concentration of the natural magnetites of New York, New Jersey and Pennsylvania. The conversion of hematite (Fe203) to magnetite (Fe3O4) is easily accomplished by heating the ore to a dull red temperature in a reducing atmosphere. The reaction is slightly endothermic, and while it requires 200 B.t.u. to heat to 900' F. one pound of hematite ore containing 45 per cent Fe, it requires only 100 B.t.u. to convert the oxide into magnetite. In the laboratory, using small quantities of ore, this conversion is very simple, but large furnaces suitable for commercial

Jan 1, 1939

By D. I. Bardos, F. X. Spiegel, R. K. Malik, Paul A. Beck

Study of the occurrence of elongated ß-Mn phase fields and of their direction of extension in fifteen ternary systems indicates that the ß-,mn phases formed by manganese with other transition elements and with either silicon, germanium, or tin may be considered as electron phases. In these phases the alloying behavior of silicon on the one hand and of germanium and tin on the other shows a significant difference . Formally all observations can be satisfactorily described by attributing to germanium and tin an apparent electron concentration of nine electrons per atom. This behavior may be interpreted by assuming that germanium and tin exclude itinerant electvons because of a strong repulsive potential arising fromthe requirement that their wave junctions be orthogonal to those of- the closed d shells of these atoms. The absence of a d shell in silicon allows this atom to admit itinerant d electrons. The following new ternary phases of unknown structure were identified by means of their X-vay difjraction patterns: (Mn,Co,Si)I , (Mn,Co ,Si)Y, (Mn.Co,Si)Q , (Mn ,Ni ,Si)W , and (Mn, Ti ,Si)A. The X-ray data suggest that these phases have large unit cells and that to some extent they may he related structurally to the 0 phase. The a phase and certain other phases formed by transition elements are characterized by their preferred occurrence at a constant electron concentration. AS a result, these "electron phases" have relation to electron concentration. The tendency of the B phase to form elongated phase fields in ternary systems along the directions of constant electron concentration has been previously demonstrated. The occurrence of an elongated 0-Mn phase field in the ternary system Mn-Co-Si was schematically indicated by Cherkashin et al.l0 The present study includes fifteen ternary systems, each containing in addition to manganese a second transition element from the group Ti, V, Cr, Fe, Co, Ni and one of the nontransition elements silicon, germanium, or tin. In each system the boundaries of the B-Mn phase were determined in the 900°, 950°, or 1000°C isothermal section, the temperature being dictated on the one hand by the requirement of sufficient rates of diffusion to approach equilibrium conditions in reasonably short annealing periods and on the other hand by the need to avoid as much as possible the partial melting of alloys during annealing.

Jan 1, 1967

By Oscar Weiss

STILFONTEIN and surrounding areas gave nega-tive results in all prospecting attempts since about 1904 when Goerz and Co., a forerunner of Union Corporation Ltd., first drilled in the region and on the farm Stilfontein. Subsequent efforts by African and European Investments Co. and Anglo American Corp. from 1934-37 were completely unsuccessful. Holes drilled by these companies on the farms Riet-fontein, Hessie, and Palmietfontein were stopped in the Lower Witwatersrand system without finding payable reefs. The results of gravimeter, ground magnetometer, and aerial magnetometer surveys are presented in the area, in and around the new Stilfontein Gold Mine, in the Klerksdorp District of the Transvaal in the Union of South Africa. The gravimeter and ground magnetic surveys were completed in 1947—48. The gravity anomalies suggested a block of Upper Witwatersrand quartzites faulted-up between denser rocks of dolomite and Ventersdorp lava. Boreholes S.T. 1, 2, and 3 were drilled in 1948 and, after penetrating the dolomite and Ventersdorp lava, entered Upper Witwatersrand quartzites and intersected the Gold Estates Reef and Vaal Reef. Subsequent drilling delineated the suboutcrop of the Vaal Reef and determined the main structure of this horizon. The gold content of the Vaal Reef was highly payable and shaft sinking is now in progress. The Stilfontein Gold Mining Co. has been formed and, up to date, f5,000,000 capital has been raised for plant, shaft sinking, and development. The payable Vaal Reef horizon extends further south from Stilfontein, the reef occurring at increasing depths. It is possible that at least another mine may be established on these deeper horizons. The farm Stilfontein 39 is situated in the Klerksdorp District of the Transvaal. This farm and the surrounding areas have been subjected to repeated programs of prospecting dating back to about 1904, when Goerz and Co., the forerunner of Union Corporation, Ltd., first drilled on the farm and in the surrounding areas. From 1934-37, numerous boreholes were drilled on the neighboring farms, Riet-fontein. Hessie. and Palmietfontein, by African and European Investment Co. and Anglo American Corp. All these efforts were completely unsuccessful, and nobody suspected any possible gold-bearing area on Stilfontein until about 1947, when a gravity traverse run by B. D. Maree on the main road, showed a negative gravity anomaly. During 1947-48, the writer's organization completed gravimeter and magnetic surveys on Stilfontein and Rieffontein. An area of negative gravity anomalies was mapped, and it was suggested that this could be caused by blocks of Upper Witwatersrand quartzites, of the average density of 2.65, faulted up between dolomites and Ventersdorp lavas, the density of both of these rocks being 2.8. Fig. 1 shows the geology of the area as mapped by L. T. Nel of the Geological Survey of South Africa. The boreholes on Stilfontein, with the exception of a single hole of Goerz and Co., were drilled after the completion of the geophysical survey. The grouping of the first boreholes S.T. 1, 2, 3, 4, 5, and 6, clearly shows that these were located in the zone of negative gravity anomalies. Fig. 2 shows the gravity anomaly contours. Fig. 3 shows two sections across the gravity anomaly, together with the corresponding geological sections as obtained from boreholes. The close relation between gravity values and thickness of dolomite plus Ventersdorp lavas is striking. The two latter formations having the same density (2.8), act as one mass as far as gravity effects are concerned. Fig. 4 shows the magnetic anomalies observed on the ground by vertical magnetometers and at 500 ft abbve mean ground level by aerial magnetometer. The latter are anomalies of the total magnetic intensity. The magnetic results show that, on the farm Rietfontein and on the northern half of Stilfontein. Lower Witwatersrand magnetic shales were to be expected at relatively shallow depths. As the strongly

Jan 1, 1952

By W. M. Rutherford

A knowledge of the limits of miscibility between reservoir oil and possible injection fluids is required for selection of the optimum miscible-injection fluid. Limits of miscibility can be estimated from the results of equilibrium phase-behavior experiments. They can also be determined by means of displacement experiments conducted in a high-pressure sandpack. This paper describes the equipment and procedure which have been developed for determining miscibility conditions by stable displacement. A systematic series of displacements of a West Texas reservoir oil was carried out. The results indicate that, at constant pressure, miscibility is a function only of the pseudocritical temperature of the injection gas. This fact, together with improved experimental methods, makes the displacement technique a rapid, reliable means for determining miscibility conditions. In conjunction with the displacement experiments, phase diagrams were constructed for the oil with dry gas and propane and with dry gas and ethane. Phase behavior of the methane-ethane-propane system was determined at 110°F. The experimental work demonstrates the feasibility of using ethane-rich gases to reduce cost and pressure requirements for miscible displacement. INTRODUCTION In recent years, interest in the miscible displacement of oil by light hydrocarbon mixtures has been high. Many pilot and a few field scale projects have been started.1 These projects have made use of various methods for achieving miscibility: (1) the LPG-slug process, (2) the enriched-gas-drive process and (3) the high-pressure gas-drive process. Some field projects have been successful; the results of others are debatable. In general, projects which have performed best have involved the injection of an appreciable fraction of a pore volume of miscible material. Economical application of miscible displacement depends strongly on the cost of the miscible-injection fluid. If an appreciable fraction of a pore volume of material is required for successful application of these methods, a precise knowledge of the minimum requirements for miscibility in terms of composition of injection fluid is essential. Therefore, reliable experimental methods for determining miscibility conditions are important, and a procedure for estimating these conditions from the composition of the reservoir fluid is highly desirable. The subject of this paper is the problem of determining conditions which result in miscible displacement of oil by light hydrocarbon mixtures. Miscibility conditions can be estimated by means of equilibrium experiments conducted in a PVT cell, or they can be determined by means of high-pressure displacement experiments. This paper describes the equipment and procedure which have been developed for the determination of miscibility by high-pressure displacement experiments. These methods have been applied to the displacement of a West Texas reservoir oil with mixtures of dry gas, ethane and propane. In conjunction with the displacement experiments, triangular phase diagrams have been constructed for mixtures of the oil with dry gas and propane and with dry gas and ethane. The effect of injection-gas composition on conditions for miscible displacement in high-pressure sandpacks and cores has been the subject of several published papers.2-5 The experimental methods used in these investigations were such that displacements were unstable, and the effects of fingering and/or gravity layover are clearly evident in the results. Miscibility conditions were probably correct in spite of the instability phenomena, but the experiments evidently were time-consuming, and limited data were reported. Systematic high-pressure flow studies which would support a correlation of miscibility conditions have not been reported; however, Wilson5 has proposed the use of pseudocritical temperature of the injection gas as a parameter and Benham, et al,6 have based a miscibility correlation on observed and calculated equilibrium data.

By John C. Sawyer

A brief review is given to show that catastrophic oxidation of stainless steel in the presence of lead oxide is similar in many respects to catastrophic oxidation as caused by MoO3 and V2O5, Experimental data are presented to show that lead oxide accelerates the normal oxidation process of stainless steel by chemically altering the normally protective oxide film formed on the base metal. Data are given to show that similar reactions occur during oxidation of stainless steel in the presence of MOO3,and V2O5. THE mechanism by which pure metals oxidize at high temperatures has been the subject of intensive research for many years and much has been accomplished towards understanding the processes involved. The mechanisms by which alloys oxidize have also been investigated, but due partly to the fewer number of investigations and partly to the complexity of the oxide systems present, available knowledge is not as extensive as with pure metals. When oxidation processes are further complicated by atmospheres contaminated with sulfide, halide, or oxide vapors, the knowledge of fundamentals becomes meager or altogether lacking. Thus, it is not surprising to find that the catastrophic oxidation of stainless steels in metal oxide vapors of MOO, and V2O5 is not a well understood phenomenon despite the fact that a number of investigations have been undertaken. The literature in dealing with the subject of catastrophic oxidation is primarily concerned with the effects of MOO3 and V2O5, but does mention that other metal oxide vapors, one of which is lead oxide, appear to promote a similar type of accelerated oxidation. While this latter effect is virtually unknown, the deleterious effect of lead oxide is of considerable commercial importance, as it is believed to be one of the fundamental reasons for exhaust-valve failure in gasoline engines. For this reason studies have been in progress for many years attempting to better understand the mechanism involved. Modern exhaust-valve alloys"2containing 20 to 25 pct Cr plus nickel and/or manganese are in effect high-grade austenitic stainless steels exhibiting ex- cellent oxidation resistance in air at exhaust valve operating temperatures of 1100° to 1700°F; yet these same alloys are prone to corrode during engine service because of the conditions attending their operation. These conditions are such that the valves become coated with deposits of complex lead compounds mainly derived from gasoline additives of tetraethyllead, ethylene dibromide, and ethylene dichloride. Literature searches3-7 and discussions with various investigators show that considerable difference of opinion exists as to the nature of the lead-bearing deposits found on the surface of exhaust valves and the atmospheres to which they are subjected; yet, all seem to generally agree that corrosion, a gradual transformation of alloy to nonmetallic products of corrosion, is a consequence of the presence of lead compounds. This majority opinion seems to be substantiated by laboratory engine tests which show that corrosion does not occur to any appreciable extent when lead-free fuels are used. The first observations of catastrophic oxidation reported in the literature were probably made by pfeil,8 but it was Leslie and Fontana9 who undertook the first detailed study of the phenomenon. Their work was chiefly centered on the acceleration of oxidation which took place when stainless steels containing more than 3 pct Mo were heated in air with restricted circulation. These investigators reported that the presence of other oxides near the surface would further accelerate the rapid oxidation which occurred. While they recognized that the effect was attributable to the presence of molybdenum, it was Rathenau and Meijering" who emphasized the fact that the presence of molybdenum in the alloy was incidental to the presence of MOO3 vapor in the atmosphere surrounding the specimens. Evans,11 as well as Cunningham and Brasunas 12 studied similar

Jan 1, 1962

By R. Kerby, T. R. lngraham

The rates of cadmiuln cementation from buffered solutions were studied on both the cylindrical and circular faces of a rotating zinc disk. The activation energies are equivalent on both surfaces, but the rate is more rapid on the cylindrical face. At higher temperatures and at pH values above 6.4, the rate of deposition increases because of an increase in the cathodic area of the deposit. The rate may also be increased by decreasing the thickness of the diffusion layer by rapid stirring. The presence of small amounts of copper, cadmium, lead, iron, or aluminum in the zinc does not affect the cementation rate, but when srnall amounts of copper, cobalt, and arsenic were present in the solution cadmium deposition ceased shortly after it started. Small amounts of copper in solution become cemented with the cadmium to form a coarse deposit of Cd3Cu. When zinc ores containing cadmium are processed for electrolysis, the cadmium appears with the zinc in the leach liquors. Because of the discharge potential of the cadmium ion and the hydrogen overvoltage on metallic cadmium, the cadmium ion must be removed prior to zinc electrolysis to prevent its codeposition. Cadmium is usually removed from acidic zinc sulfate solutions by cementation on zinc. When zinc sheets are used with the appropriate conditions of pH and temperature, a finely divided, high-purity cadmium powder is obtained; it floats to the surface with attached hydrogen bubbles and, after careful washing, may be processed directly to a marketable product.' The reaction on zinc sheets is relatively slow because of the limited amount of exposed cathodic area on the sheets. A much more rapid reaction is obtained when zinc powders are stirred into the solution, but this procedure does have a potential disadvantage: some unreacted zinc may be trapped in the cemented cadmium and thus lower its grade.1 The equilibrium constant at 25°C for the displacement of cadmium by zinc is of the order of lo", which indicates that at equilibrium the displacement would be essentially quantitative and no back reaction need be considered. This indication is not entirely true, however, because in the presence of oxygen any loose cadmium which is out of contact with metallic zinc tends to redissolve after cementation.' The overall effect is much the same as that to be expected if the equilibrium constant were much smaller. Previous experimental work on cementation reac- tions3 is in general agreement that the rates of cementation usually follow first-order kinetics. The metal on which cementation occurs is considered to consist of anodic areas from which metal dissolves and cathodic areas onto which the reactive metal is cemented. For the reaction to continue, the cemented deposit must remain open and porous for the removal of ions. Usually, the deposited metal influences the rate of cementation; when it blocks the pores in the deposit, the rate of cementation will be decreased. Alternatively, when the cemented metal grows as den-drites or as coarse powder the cathodic area is correspondingly increased and the rate of cementation increases,3 Thus, it is only during the initial stages of cementation, prior to the development of deposit effects, that the kinetic behavior of the reaction may be studied without ambiguity. In this paper, experiments will be described for cementation of cadmium from dilute solutions onto the surface of a rapidly spinning zinc cylinder. The effects of ionic concentration, disk rotation speed, temperature, and impurities will be described. APPARATUS AND PROCEDURE The apparatus used for the experiments was described in a previous paper.4 It consisted of a 2-liter vessel in which the contents were protected, against oxidation, by a stream of prepurified nitrogen. The vessel was immersed in a water bath which controlled

Jan 1, 1970