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By J. Ellzey Hayden

THE Cliffs Shaft mine of the Cleveland Cliffs Iron Co., located in the city of Ishpeming, Mich., is the largest producer of hard hematite ore on the Marquette iron range. The two shafts, A and B, lying 820 ft. (250 m.) apart on the east-west trend of the ore formation, were sunk in the early eighties, and, except for four years, have been steady producers of iron ore. Their location, on a hill overlooking the general offices of the company on the one side and the city of Ishpeming on the other, has made the shaft houses landmarks. In the spring of 1919, as the old wooden shaft houses had become shaky and out of line, and would soon be unsafe, it was necessary to replace them with the least possible delay. Three plans of construction were, therefore, considered: To replace the old shaft houses by somewhat similar structures made of wood; to use steel and radically change the design; or to build reinforced-concrete shaft houses outside of the wooden structures, completely enclosing them. The first plan was disapproved, because it is anticipated that the mine will have a long life and the proximity of other buildings makes the danger from fire rather great. Delay in receiving material, and the necessity for closing the shafts during erection, were other factors in the situation. The second plan was disapproved on account of the high cost of steel, slow delivery, and interference with hoisting during the period of erection. The presence near one of the shafts of a large bed of hard gravel suitable for concrete made, the cost of the third plan considerably less than the second, and little, if any, delay in hoisting was expected. Our expectations in this regard' were fully realized. Furthermore, the work could be done by unskilled labor, which was plentiful, and the erection could be quickly started. When the proposition was submitted to Mr. W. G. Mather, president of the company, he recommended that, on account of the prominence of the buildings due to their location, an effort should be made to combine in the design as far as practicable something of architectural beauty. Following his recommendation, the original plans were submitted to the

Jan 8, 1920

By G. G. Waddell, T. J. Crocker, S. S. M. Chan

A successful engineering structural design often depends upon a thorough understanding of the material properties of the structure. It is no exception when designing a supporting system for stable underground openings. For this reason, studies were made in the deep mines of the Coeur d'Alene mining district to obtain engineering properties of rocks and rock masses immediately surrounding underground openings. In this paper, data concerning laboratory tested physical properties of rocks and in-situ deformation behavior of rock masses from the Galena, Lucky Friday, and Silver Summit mines of the district are presented. Interpretations of the data so obtained and suggestions for the use of the results of the investigations as design criteria are also outlined.

Jan 1, 1973

By M. A. Mallinger

A series of laboratory tests was conducted to determine the limits of practicability in regulating the weights of various cement slurries. It was found that slurry weights of 12 to 19 lb per gallon could be obtained by adding bentonite to decrease the weight and barytes ore to increase the weight. It was also found that barytes ore was not usable in all cements. LIGHTWEIGHT CEMENT SLURRIES INTRODUCTION During the drilling and completion of oil wells the magnitude of the hydraulic pressures exerted on certain formations is critical. In many cases considerable care must be exercised to prevent drilling mud weights from becoming too high, and in those wells where loss of circulation is a problem, the use of normal weight cement slurries will generally result in lost returns during casing cementing operations. While mud weights can easily be controlled, it is necessary to exercise care in the selection of weight reducing additives for cement slurries in order that slurry weights may be reduced sufficiently to prevent the loss of a large portion of the cement to the thief formations without seriously affecting the setting properties of the cement. EXPERIMENTAL RESULTS An extensive search revealed that a large number of materials .that might have been otherwise practicable as a weight reducing additive were not acceptable for use with oil we cements because the imposition of pressure on the slurries caused the additive being tested to be compressed or to absorb water from the slurries, resulting in negligible decrease in the slurry weight. This search for lightweight additives disclosed that bentonite, a material very commonly used for reducing the weight of drilling muds and cements, produced the best results without undue harmful effects on the properties of oil well cements. It was found that there was a limit to the amount of benton-

Jan 1, 1950

By I. G. Grettum, Eugene A. Stephenson

The flooding process was originally the result of accidents to casing and tubing, but it has gradually passed from an accidental condition to a definite engineering procedure. In spite of the general sheetlike char-acter of the major sand body, the position of shale bands, their thickness, the size of the grain and variations in effective porosity all give the sand different characteristics in different layers and in different places in the same layer. This condition has an important influence on the movement of flood oil and water, and on the yield per acre, as well as a bearing on what shall be considered the best method of handling flood wells. . A valuation takes into consideration six factors: (1) Flooding methods, of which four have been in common use, as follows, in order of effective recovery, (a) circular flood, (b) line flood, (c) five-spot and (d) five-spot with delayed drilling; (2) recovery per acre, which is definitely related to the oil content, the porosity, the method of flooding, the spacing program, and the continuity of the water supply; (3) the rate of production per well per day, which is definitely related to the mcthod of flooding, the oil content and the porosity of the sands; (4) the operating cost of the well, including royalty, overhead, taxes, etc. (Operating costs are usually expressed as unit cost per barrel.); (5) the expected price per barrel. It is safer to use the average price over a number of years than to attempt to forecast future price fluctuations. The discount factor (the sixth factor) used in appraisal of Bradford flood properties should be less than that commonly applied to other properties, because the hazards of operations have been reduced almost to those of a manufacturing industry.

Jan 1, 1930

By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of 'oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn'c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

By Walter S. Lutz, J. T. Griffith

The rainfall during the last six months of 1942 in Scranton and vicinity was 24.06 in.—only 4.35 in more than the average for this district in any equivalent period—yet that rain forced The Hudson Coal Co. to handle 38.8 tons of water for every ton of coal mined. It filled to overflowing, or to a higher level, 14 flooded mine areas holding, in total volume, 8.3 billion gallons of water in storage; brought about a pumpage of 11.4 billion gallons in the months of December 1942 and January, February and March 1943 Half of the total energy generated or purchased (44,322,980 kw-hr.) was required to keep the mines sufficiently free of water to permit the mining of coal during a period of much needed output. Fig. I shows the extent to which this flooding of exhausted and idle properties has proceeded, and is known to be proceeding further, at the upper end of the Northern field. This rainfall (24.06 in.) means 80,559,444 tons of water on approximately 46.2 sq. miles of area tributary to the pumping plants. During the high rainfall period, 72,687,661 tons went underground, being pumped at the stations in this territory. This means an inflow of 88per cent, a runoff of 12 per cent compared with 64 per cent during normal conditions in a normal region. During this period no floods, either surface or underground, had to be dealt with, although the streams and rivers were high on several occasions. In general, the rainfall for the first three months of 1943 can be described as heavy but not abnormal.9 These figures not only indicate the large volumes of water to be handled but, by their very size, they also emphasize that the mine-water problem is not to be conquered, at least from an economical standpoint, by merely buying and installing more and more pumps. Into the solving of this water problem must go much planning, adhering to the principle of keeping the highest percentage of water at the highest possible level for the longest period of time; the storage of huge volumes in sumps capable of being reduced after the flood inflow and at rates less than the inflow; plans for prevention of surface inflow; provision of the minimum of pumping capacity arranged to as nearly 100 per cent pumping load factor as is possible; intercompany joint pumping plants; the conducting of water from one plant to another and from one property to another over distances measured in miles; priorities in power to the threatening situations; and. balance of the necessities and dangers existent in one colliery over another, day by day, when quantities of water are running high. Despite these astronomical figures of water volumes, their disposal to the surface is accomplished reasonably cheaply because, although the annual cost of $575,020 is a large sum, the cost per ton is about 0.1168 cents. Credit for this goes

Jan 1, 1947

By J. T. Griffith, Walter S. Lutz

The rainfall during the last six months of 1942 in Scranton and vicinity was 24.06 in.—only 4.35 in more than the average for this district in any equivalent period—yet that rain forced The Hudson Coal Co. to handle 38.8 tons of water for every ton of coal mined. It filled to overflowing, or to a higher level, 14 flooded mine areas holding, in total volume, 8.3 billion gallons of water in storage; brought about a pumpage of 11.4 billion gallons in the months of December 1942 and January, February and March 1943 Half of the total energy generated or purchased (44,322,980 kw-hr.) was required to keep the mines sufficiently free of water to permit the mining of coal during a period of much needed output. Fig. I shows the extent to which this flooding of exhausted and idle properties has proceeded, and is known to be proceeding further, at the upper end of the Northern field. This rainfall (24.06 in.) means 80,559,444 tons of water on approximately 46.2 sq. miles of area tributary to the pumping plants. During the high rainfall period, 72,687,661 tons went underground, being pumped at the stations in this territory. This means an inflow of 88per cent, a runoff of 12 per cent compared with 64 per cent during normal conditions in a normal region. During this period no floods, either surface or underground, had to be dealt with, although the streams and rivers were high on several occasions. In general, the rainfall for the first three months of 1943 can be described as heavy but not abnormal.9 These figures not only indicate the large volumes of water to be handled but, by their very size, they also emphasize that the mine-water problem is not to be conquered, at least from an economical standpoint, by merely buying and installing more and more pumps. Into the solving of this water problem must go much planning, adhering to the principle of keeping the highest percentage of water at the highest possible level for the longest period of time; the storage of huge volumes in sumps capable of being reduced after the flood inflow and at rates less than the inflow; plans for prevention of surface inflow; provision of the minimum of pumping capacity arranged to as nearly 100 per cent pumping load factor as is possible; intercompany joint pumping plants; the conducting of water from one plant to another and from one property to another over distances measured in miles; priorities in power to the threatening situations; and. balance of the necessities and dangers existent in one colliery over another, day by day, when quantities of water are running high. Despite these astronomical figures of water volumes, their disposal to the surface is accomplished reasonably cheaply because, although the annual cost of $575,020 is a large sum, the cost per ton is about 0.1168 cents. Credit for this goes

Jan 1, 1947

By W. F. Holbrock

IN a previous paper1 a method for the measurement of the compara-tive desulphurizing power of slags was described and data, were presented covering the range of likely slags containing up to 10 per cent MgO. In the present work the range is extended to include Tags containing up to 20 per cent MgO, and the effect of temperature on 5 per cent and 15 per cent MgO sings over the range 147.5° to 1525° C. is included. The method used was that described in the previous paper except that some of the temperature measurements were made with a noble-metal thermocouple instead of a tungsten-graphite thermocouple. Twelve-gram charges of 0.S per cent sulphur-metal and 5-gram charges of slag were subjected to heating for 30 min. at a prescribed temperature. The charges were analyzed for sulphur content. For purposes of comparison, desulphuriz-ing power is defined as the ratio of the percentage of sulphur found in the slag to that found in the metal. Six slag and metal charges were made coincidentally in holes in a section of all electrode graphite rod. One slag and metal charge was used as a control by means of which adjustment in the desulphurization value could be made for small varia-tions in temperature and other factors. For convenient presentation of the data, the slags are arranged in groups -in each of which one of the four main slag components is constant. Thus, the 15 per cent MgO slags are presented separately from those containing 20 per cent MgO.

Jan 1, 1938

By W. Joseph Schlitt

The types of copper leaching and recovery operations in the United States are reviewed, along with characteristics and trends in the industry. The contribution of the various leach operations to total mine output is discussed in order to provide a perspective on the relative importance of copper leaching as a method of production.

Jan 1, 1980

By Peter L. Swanson

A microcrack process zone is frequently suggested to accompany macrofractures in rock and play an important role in the resistance to fracture propagation. Attenuation of surface waves propagating through mode I fractures in wedge-loaded double-cantilever beam specimens of Westerly granite has been recorded in an attempt to characterize the structure of the fracture process zone. The ultrasonic measurements do not support the generally accepted model of a macroscopic fracture that incrementally propagates with the accompaniment of a cloud of microcracks. Instead, fractures in Westerly granite appear to form as gradually separating surfaces within a zone having a width of a few millimeters and a length of several tens of millimeters. A fracture process zone of this size would necessitate the use of meter-sized specimens in order for linear elastic fracture mechanics to be applicable.

Jan 1, 1984

By W. R. Hibbard

Evidence is presented which confirms previous findings that models of solution strengthening depending solely on lattice parameter changes are incomplete. Direct evidence for the Suzuki interaction of chemical effects was obtained from alloys with constant lattice parameter, for which solution strengthening was nearly independent of temperature from 300° to 20°K. SOLUTION hardening principles have been reviewed recently by Parker and Hazlett.' In addition, the interactions of dislocations and solute atoms were reviewed by Cottrell.' It is not proposed to review this information again here, but to refer only to those details which are pertinent to the developments which have occurred since these papers were published. Literature Survey To set the stage, it has been known for some time that solid solutions are stronger than the pure parent metals, and that the strength increases with increasing amounts of alloying element. One of the most extensive earlier investigations was that of Lacy and Gensamer,3 who reported that the solid solution strengthening of iron is a power function of the composition, that the relative strengthening is a function of the solubility limit, and that the rate of strain hardening is a function of the amount of solution hardening. Thus, the slope of the plastic portion of the stress-strain curve increases with increasing yield strength. An approach to the development of principles resulted from work by Gulyeav,4 who reported that the strengthening effect of solid solution alloys is periodic in character when plotted as a function of the atomic number of the solute. A more quantitative approach was to relate the amount of solution hardening to the lattice parameter of a solid solution. This was done quite early by Norbury,5 and later by Brick, Martin, and Angier,6 Frye and Hume-Rothery,7 and French and Hibbard. This relationship is only approximate in character. The next development was to relate the amount of solution hardening to lattice stress, as proposed by Frye and co-workers.9 They calculated what they called ionic overlap from the lattice parameter changes represented as a change in volume, using Bridgman's hydrostatic compression equation. The resulting correlation was somewhat improved as compared to the simple correlation with lattice parameter. The next step was carried out by Dorn, Pietrow-sky, and Tietz,10 who suggested an effect of valence differences in addition to the effect of lattice parameter. Their proposed parameter shows flow stress as a single valued function of the concentration and a relationship involving these two atomic variables. In addition, they contributed new data on the temperature dependence of solution hardening which indicated that it was a strong function of temperature for aluminum alloys. Allen, Schofield, and Tate11 carried the valency effect even further by reporting data indicating that with a given solvent element the stress-strain curve is a function of electron density, entirely neglecting the size factor, which varied by a factor of two. This evidence led to a quantum mechanical calculation by Cottrell, Hunter, and Nabarro,12 based on the formation of a dipole around an edge disloca-

Jan 1, 1959

By W. F. Holbrook

IN a previous paper1 a method for the measurement of the comparative desulphurizing power of slags was described and data were presented covering the range of likely slags containing up to 10 per cent MgO In the present work the range is extended to include slags containing up to 20 per cent MgO, and the effect of temperature on 5 per cent and 15 pen cent MgO slags over the range 1475° to 1525° C is included The method used was that described in the previous paper except that some of the temperature measurements were made with a noble-metal thermocouple instead of a tungsten-graphite thermocouple Twelve-gram charges of 0 8 per cent sulphur-metal and 5-gram charge-, of slag were subjected to heating for 30 nun at a prescribed temperature The charges were analyzed for sulphur content For purposes of comparison, desulphurizing power is defined as the ratio of the percentage of sulphur found in the slag to that found in the metal Six slag and metal charges were made coincidentally in 5/8-in holes in a section of an electrode graphite rod One slag and metal charge was used as a control by means of which adjustment in the desulphurization value could be made for small variations in temperature and other factors For convenient presentation of the data, the slags are arranged in groups in each of which one of the four main slag components is constant Thus, the 15 per cent MgO slags are presented separately from those containing 20 per cent MgO SLAGS WITH MAGNESIUM OXIDE CONSTANT 15 Per cent MgO -The data on slags containing 15 per cent MgO cover a composition range of 24 to 50 per cent SI02, 5 to 27 per cent A1203 and 24 to 53 per cent CaO Variation in composition has been in steps of 2 per cent over much of the area Because the change in desulphurization power is generally gradual with gradual change in composition, certain sections have been covered m steps of 4I per cent and even

Jan 1, 1938

By Magnus Troilius

The importance of having methods for the rapid and accurate determination of manganese in modern steel manufacture cannot be overestimated. The method adopted in the laboratory of the Midvale Steel Works is very satisfactory, and I think it will be of interest to some of the members to give a description of it. Before giving the more detailed account of the manipulations, a review of some well-known methods and chemical facts may not be out of place. The " bromine and ammonia" process, as fully described in the tenth volume of the Transactions of this Institute, was certainly an improvement on the methods in which fixed alkaline salts were used, as these gave invariably too high resnlts, as generally carried out. But the separation of all the iron before the manganese was, in both methods, a source of great inconvenience and delay.

Jan 1, 1884

INTRODUCTION TO COMPOSITING Individual drill hole samples may vary greatly in size, length, and weight. The sample interval may represent any convenient unit of hole length, and is usually related to the type of drill being used to obtain the sample. Depending upon the type of mineral deposit, it is desirable to group the individual sample values into composite weighted values representative of some particular zone or volume of the ore body. For example, values of several sequential samples of diamond drill core 3 m (10 ft) in length may be grouped together to represent a 12-m (40-ft) sample value over one bench height. On the other hand, several individual sample values taken across the thickness of a stratiform deposit or a vein zone may be weighted together to represent the value of the total thickness at the point of intersection. The choice of composite intervals is usually dictated by the type of mineral deposit and the mining method selected to produce the mineral. The techniques of weighting values from various lengths of samples into a composite value has already been discussed briefly in Chapter 3. Further examples of determining weighted composite values will be given in the following discussion on compositing for various types of mineral deposits. SAMPLE VALUE COMPOSITES AND TYPES OF MINERAL DEPOSITS There are many kinds of mineral deposits, each of which will require special treatment of sample data to obtain the best composite intervals for evaluating the deposit. It cannot always be known before hand what the optimum composite interval will be. Such composite intervals may properly be determined by geologic factors that are often unknown prior [ ]

Jan 1, 1980

By W. T. Roberts, N. G. Turner

A study of the fatigue properties of several grades of commercially pure titanium has established that the strain-aging process is of minor importance in the development of a fatigue limit and a relatively high fatigue strength ratio. Metallographic observations and damping measurements at room temperature indicate that striations are able to spread from grain to grain only at stress levels above the fatigue limit. This suggests that the fatigue limit represents the stress above which large-scale dislocation unlocking takes place. Fatigue tests on annealed material at - 60" and - 196" c showed that under conditions when a thermally activated diffusion process would be suppressed the fatigue limit is not eliminated. Prestraining at room temperature did not have a detrimental effect on fatigue strength at room temperature but a decrease was recorded at — 60°C. This is further evidence that initial dislocation locking is a important strengthening mechanism. TITANIUM and titanium alloys have S-N curves with a definite fatigue limit, and a high ratio of fatigue limit to UTS can be attained. Other materials which show similar fatigue characteristics are mild steel and some Al-Mg alloys. The fatigue limit of these materials has been associated with their strain-aging capacity. It is well-known that commercial-purity titanium contains interstitial impurities which can give rise to a sharp yield point, and a small strain-aging effect following static strain has been demonstrated.7 This type of aging reaction is differentiated from the dynamic aging process when aging occurs during plastic deformation, and which is generally observed at elevated temperatures. In a titanium at room temperature, dislocation locking is associated with the interaction of interstitial oxygen, nitrogen, and carbon atoms with dislocations. Ehr-lich has shown that the distortion produced by introduction of these atoms into the hcp lattice has no shear stress component and hence there is no interaction between the stress field and the screw component of a dislocation. Thus the dislocations as a whole are only weakly locked. It is clear that strain-aging effects in hcp a titanium will be much less pronounced than those observed in bcc iron and steel. In recent years, the attribution of the fatigue limit solely to strain aging has been questioned. It has been pointed out that a definite fatigue limit is observed at temperatures as low as -196°C in some titanium alloys,' and strain aging is not expected to be effective at this temperature. The role of initial locking of dislocations in determining fatigue behavior has been examined in low-carbon steel by Oates and Wilson. They showed that under conditions in which the aging potential is low the factors which control the buildup of local stresses and hence affect dislocation unlocking, e.g., grain size, are important. There are indications that other metals can have a definite fatigue limit with no established strain-aging capacity, an example being magnesium12 which has the same crystal structure as a titanium. The spread of plasticity from grain to grain in hexagonal metals may be more difficult than in cubic metals because of the limited number of slip systems in the former, and this may account in part for their fatigue behavior. The present work was undertaken to elucidate the relative importance of crystal structure, strain aging, and initial dislocation locking in determining the properties of commercially pure titanium when subjected to cyclic stressing. 1) EXPERIMENTAL METHODS Three grades of commercial-purity titanium were used and a material of lower interstitial content was prepared by melting high-purity Japanese sponge titanium (referred to as H.P. Ti). The compositions and typical mechanical properties of the materials are shown in Table I. Fatigue tests were made in push-pull (zero mean stress) using an Amsler Vibraphore machine at a frequency of about 160 cps. Two types of fatigue specimen were used—one with a waisted gage length for determination of S-N curves and the other with a parallel gage length for metallographic studies and damping measurements. After careful machining and mechanical polishing, all specimens were electropolished prior to fatigue testing. The electrolyte consisted of 10 parts methyl alcohol, 6 parts 2-butoxyethanol, and 1 part perchloric acid (SG 1.54) and it was maintained at a temperature of -10" to -20°C during polishing. Tests at room temperature were normally carried out with the specimen immersed in a silicone oil bath which could be heated for elevated-temperature tests.

Jan 1, 1969

By F. D. Rosenthal, F. J. Dunkerley, G. J. Mills

Activities, free energies, and heats and entropies of mixing of liquid Pb-Zn alloys have been obtained by the electrode-potential method between 400° and 650°C. The large positive deviations observed from Raoult's law are in agreement with the phase diagram, which indicates a wide immiscibility field. A vapor-pressure method was used to extend the activity measurements to 900°C, allowing the maximum of the immiscibility gap to be estimated by thermodynamic calculation. Data on the mono-tectic and eutectic points compare favorably with previously existing work. SEVERAL long-standing methods have been in use for the study of phase diagrams from measurement of the activities of the component metals.' The use of thermodynamic analysis for interpreting equilibria data is comparatively recent, however. Such analysis is usually undertaken by first evaluating the principal thermodynamic functions as, for example, the enthalpy, entropy, and free energy of the alloy constituents. These, in turn, quite often can be correlated with the interatomic potential energies and atomistics of the system, from which a clearer understanding of the causes leading to deviations from ideal behavior is gained. The present study of liquid Pb-Zn alloys is concerned with a determination of these quantities by electrode-potential and vapor-pressure measurements, using these values in calculations involving phase equilibria and to obtain a theoretical insight into an alloy system exhibiting strong positive deviations from ideal metallic solution. A considerable portion of the previously reported work is based on thermal analysis. Supplemented by optical studies of solid alloys, these techniques have revealed the essential nature of the immiscible mixtures that are formed. It is difficult, however, using the phase-

Jan 1, 1959

By H. S. Cannon, F. N. Rhines

The application of a static load to a copper powder compact during sintering at an elevated temperature accelerates the rate of sintering in such a way that a given load induces the same proportional increase in rate for all times of sintering. It is shown that sintering under a load is like creep under a fixed load in that the stress required to accomplish a given degree of densification is proportional to the logarithm of the sintering time. VIRTUALLY all of the theories of sintering that have been put forward within recent years have contained the assumption that the chief driving force of the process is the surface tension resident in the exposed surfaces and internal pores of the compact, or powder mass. An externally applied load might be expected to provide a somewhat equivalent driving force for sintering. It is known that the application of a compressive load, during sintering, hastens densification, but it is by no means clear whether sintering under the influence of surface tension alone and sintering under an applied load are fundamentally similar processes. The present study was undertaken in an effort to obtain an answer to this question and with the hope that the answer may contribute to an understanding of the mechanism of sintering. It has been found that there is a close relationship between sintering and creep processes. Copper powder compacts were sintered in hydrogen at 1000 °C under dead loads of 0 to 165 psi and the progress of sintering was observed by means of density measurements. Using a commercial reduced oxide copper powder, see Table I, cylindrical compacts Yz in. x x in. high were made at a pressure of 12,500 psi. For sintering, these were placed in a cylindrical graphite container into which they fitted snugly. A compressive axial load was applied to the compact through a graphite rod of similar diameter, which rested upon the upper end face of the compact; iron weights, in suitable amount, were placed upon the graphite rod to provide the load. This assembly was encased in a vertical silica tube within a resistance-type furnace capable of maintaining a substantially constant temperature within the working zone. After various predetermined times at temperature, the samples were removed from the furnace and their density was measured by conventional means. The heating-up and cooling-down times have been included in the computed sintering time, using the assumption that the sintering rate doubles for each increase of 10 °C in temperature. The experimental results are presented in Table 11. Upon metallographic examination of the specimens, it was found that there was no apparent change in the shape of the pores as a result of loading, i.e, no flattening, Fig. 1. Substantial contraction away from the container walls was observed in all samples sintered with loads of 10.5 psi and less.

Jan 1, 1952

By W. F. Holbrook

In a previous paper1 a method for the measurement of the comparative desulphurizing power of slags was described and data were presented covering the range of likely slags containing up to 10 per cent MgO. In the present work the range is extended to include slags containing up to 20 per cent MgO, and the effect of temperature on 5 per cent and 15 per cent MgO slags over the range 1475' to 1525' C. is included. The method used was that described in the previous paper except that some of the temperature measurements were made with a noble-metal thermocouple instead of a tungsten-graphite thermocouple. Twelve-gram charges of 0.8 per cent sulphur-metal and 5-gram charges of slag were subjected to heating for 30 min. at a prescribed temperature. The charges were analyzed for sulphur content. For purposes of comparison, desulphurizing power is defined as the ratio of the percentage of sulphur found in the slag to that found in the metal. Six slag and metal charges were made coincidentally in 5/8in. holes in a section of an electrode graphite rod. One slag and metal charge was used as a control by means of which adjustment in the desulphurization value could be made for small variations in temperature and other factors. For convenient presentation of the data, the slags are arranged in groups in each of which one of the four main slag components is constant. Thus, the 15 per cent MgO slags are presented separately from those containing 20 per cent MgO. Slags with Magnesium Oxide Constant 15 Per cent Mg0.—The data on slags containing 15 per cent MgO cover a composition range of 24 to 50 per cent SiO2, 5 to 27 per cent A1203 and 24 to 53 per cent CaO. Variation in composition has been in steps of 2 per cent over much of the area. Because the change in desulphurization power is generally gradual with gradual change in composition, certain sections have been covered in steps of 4 per cent and even

Jan 1, 1938

By W. F. Holbrook

In a previous paper1 a method for the measurement of the comparative desulphurizing power of slags was described and data were presented covering the range of likely slags containing up to 10 per cent MgO. In the present work the range is extended to include slags containing up to 20 per cent MgO, and the effect of temperature on 5 per cent and 15 per cent MgO slags over the range 1475' to 1525' C. is included. The method used was that described in the previous paper except that some of the temperature measurements were made with a noble-metal thermocouple instead of a tungsten-graphite thermocouple. Twelve-gram charges of 0.8 per cent sulphur-metal and 5-gram charges of slag were subjected to heating for 30 min. at a prescribed temperature. The charges were analyzed for sulphur content. For purposes of comparison, desulphurizing power is defined as the ratio of the percentage of sulphur found in the slag to that found in the metal. Six slag and metal charges were made coincidentally in 5/8in. holes in a section of an electrode graphite rod. One slag and metal charge was used as a control by means of which adjustment in the desulphurization value could be made for small variations in temperature and other factors. For convenient presentation of the data, the slags are arranged in groups in each of which one of the four main slag components is constant. Thus, the 15 per cent MgO slags are presented separately from those containing 20 per cent MgO. Slags with Magnesium Oxide Constant 15 Per cent Mg0.—The data on slags containing 15 per cent MgO cover a composition range of 24 to 50 per cent SiO2, 5 to 27 per cent A1203 and 24 to 53 per cent CaO. Variation in composition has been in steps of 2 per cent over much of the area. Because the change in desulphurization power is generally gradual with gradual change in composition, certain sections have been covered in steps of 4 per cent and even

Jan 1, 1938

By Charles H. Jacoby

In 1774 a Swedish chemist, C. W. Schule, first recognized manganese as an element. That same year Schule's associate, J. G. Gahn, isolated the element manganese for the first time. In 1856 the Bessemer process of steelmaking gave birth to the economic importance of manganese. Later, in 1882, Robert Hadfield discovered high manganese steels. Although the primary use of manganese is in the ferroalloy industry, two additional important uses for manganese are making chemicals and dry cell batteries. Manganese is also vital to plant and animal life. Various chemical compounds of manganese are used in fertilizers, feeds, glass manufacture, paints, varnishes, and for numerous medicinal and chemical purposes. For the study of industrial minerals and rocks, only the chemical and battery grade material is of- concern, but for the sake of comparison, metallurgical aspects are included in this presentation. Although currently the world's largest consumer of manganese, the United States is producing only minor amounts of ore at the present time. This is due primarily to the fact that although huge deposits of manganese occur within our borders, all are of such low grade as to be economically unfeasible to mine. For many years various government agencies and segments of private industry have devoted sizable sums of money and time in an attempt to upgrade ores from the various deposits, and also in an attempt to recover manganese from blast furnace slags. In view of current world prices, and the quantity of high grade material available, there is little likelihood that any of these approaches will be found to be economically feasible in the near future. Geology and Mineralogy Mineralogy There are over one hundred minerals that contain manganese. These minerals vary from those with compositions that are predominantly manganese to those having only minor percentages. [Chemical Mineral Composition % Mn Hausmannite Mn304 72 Polianite MnO2, 63.1 Pyrolusite MnO24 60-63 Cryptomelane KR8O16R (R=Mn) Variable PsilomelaneBa Mn Mn8O16 (OH).45-60 CoronaditePb R8O16R (R=Mn) Variable Hollandite Ba R8O16R (R=Mn) Variable Manganite Mn2O3•H20 62 Braunite 3 Mn2O3•MnSiO3 62 Tephroite 2 MnO•SiO2 54.3 Rhodochrosite MnCO3 47 Rhodonite MnSiO3 42 Spessartite 3 MnO•AI2O3•3SIO2 33.3 WadHydrous Mn OxidesVariable Franklinite(Fe Mn Zn)O(Fe Mn)sO3 Variable Asbolan Cobaltiferous wad Variable AlabanditeMnS63.14] Geology From a geological standpoint most manganese deposits are complex. In general, it can be said that all primary deposits of manganese are carbonates or silicates. The most productive and profitable have been those of sedimentary origin and residual concentrations. Examples of these residual types of deposits are associated with the metamorphosed lodes of Madhya, Pradesh, India, and the lateritic deposits of Orissa and Bihar, India; nodules in the residual clays of the Philippine Islands, US southern Appalachians and Arkansas, Ghana, and Brazil. Sedimentary manganese deposits are best exemplified by the Nikopol district of Russia and the Tchiatouri area of Georgia, USSR. Hydrothermal replacements are characterized by the rhodochrosite deposits of Butte and Phillipsburg, MT. In general, the hydrothermal type deposit has not resulted in any large tonnages being produced, but may have given

Jan 1, 1983