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By A. L. Bailey, B. A. Landry

W. W. ANDERSON and G. E. KELLER*—We want to compliment the authors on this very thorough paper. It gives information which the coal industry has needed for some time. We hope that the additional information which the authors are collecting will he available shortly. The mixing and riffling procedure that was followed for experimental purposes is obviously not practical in routine float-and-sink testing because of the particle size degradation which would result in handling the sample so many times. It is important to obtain our tloat-and-sink fractions with a minimum amount of handling of material. A statement is made in the paper (p. 80) that "the variable most likely to affect the size of sample required to meet a given preassigned accuracy would be the state or degree of mixing of the coal." We agree that this is a large factor, but do not believe it is the most important factor. Our own opinion is that the most important single factor governing the total gross weight of sample that must be collected is the percentage of the weight of material in the smallest fraction that results from the screening and float-and-\ink operations. In other words, size of sample is governed by the total number of fractionations that must he made, and the distribution of material within the fractions. We can imagine a coal with perfect mixing, but with such a small amount of material in some float-and-sink fraction in one of the coarse sizes that a much larger sample would have to be taken than would be the case with very poorly mixed material, but with a large percentage of coarse material more evenly distributed in all float-and-sink fractions. Our own observation of many float-and-sink tests that we have run in our own organization on many types of coal is that the size of sample that must be used on fine size float and sink is governed more by the requirements for weight of material to be used for analysis in the laboratory than by weight of material necessary to obtain accurate float and sink percentage of weight values. In other words, it is our opinion that very small samples can be used for float-and-sink fractionation in the fine sizes, but that accurate analysis of the fractions will depend on a larger weight of sample being pulverized for the laboratory than is necessary to establish the float-and-sink distribution with respect to weight. A. L. BAILEY and B. A. LANDRY (authors' reply)—The authors thank Messrs. Anderson and Keller for their comments based on long experience. It is agreed that the involved mixing and riming technique used may be disadvantageous from the standpoint of degradation. Fortunately, the paper does point out that the extended riming was unrewarding in causing further mixing. Two large unknowns remain, however: (1) how much of the mixing from the presumed highly unmixed state in the bed was achieved toward the random state during blasting, loading, transportation, screening, and further transportation to the point where the gross sample was taken, and (2) how much of the mixing took place during the preparation described preceding riming. As has been pointed out by one of the authors.6 the degree of mixing has a very large effect on the size of sample required and there are still too few experimental data to show at what stage of coal handling most of the mixing occurs. The discussion states that the weight of material in a screened fraction, or in a float-and-sink fraction, is more important than the mixing factor. We do not believe that these factors are comparable in this instance inasmuch as our purpose was to give minimum sampling requirements to achieve a preassigned accuracy in the percentages of float, middlings, or sink, and nothing more. The gross sample had already been screened and no further division by screening was made or contemplated; also, it was not intended that the middlings and sink fractions would necessarily be adequate for percentage ash or other determination. In other words, the sample obtained by the method outlined is not intended for washability studies but only for preparation plant control. Further experimental work has been done, since the paper was prepared, to investigate the effect of increasingly larger top and bottom sizes on the variability of float, etc., of a double-screened coal from Western Pennsylvania. Results will be published and eventually attention is to be given to the preparation of sampling specifications. E. H. M. BADGER*—I should like the authors to explain more fully the fundamental assumptions on which their Eq 4 is based. The equation is of the form s2 = p(l - p) which is the usual expression for the (standard deviation)2 when the chance of finding a particular kind of particle in the sample is proportional to the number fraetion, p. But instead of the number fraction, the authors have used the weight fraction, WF/W. The chance of finding a particular kind of particle in the sample can only be proportional to the weight fraction, if the average ?eig?ts of all kinds of particles, that is, float, midlings, or sink, are the same. Surely a much more justifiable assumption would be that the average volumes of the particles are the same, and, if this is so, Eq 4 would not be true. This may be demonstrated as follows: Let be the weight fraction of float, middlings, or sink, dl the density of this fraction, and d2 the density of the rest of the coal. Then assuming that the average volumes of the pieces in the three classes are the same, the number fraction, p, is given by ? P = d1/l-?/d2 + ?/d1 = ?d2/d1 + ?(d2-d1) The weight fraction, w, in terms of p is given by ? = pd1/(l-p)d2 + pd1 = pd1/d2 + p(d1-d2) _____ [61

Jan 1, 1950

By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By T. E. Watkins, M. D. Nelson

INTRODUCTION Deeper drilling for oil is becoming more and more the rule rather than the exception. With deeper drilling come additional problems, perhaps the greatest being those brought on by the higher temperatures encountered down the hole. particularly in the Gulf Coast region of Texas and Louisiana. Temperature gradients of the order of 1.8° to 2.0°F/100 ft are not unusual, and a gradient of 2.3"F.'100 ft is found in some areas of Texas. With a mean surface temperature of 74oF, the following temperatures could be expected for a geothermal gradient of 2.0°F; 100 ft: at 10,000 it. 271°F. 12,000 ft, 314°F: 14,000 ft, 354,oF; and 16.000 ft. 394°F. Severe gelation of lime-base drilling fluid in wells that have high bottom hole temperatures has become perhaps the most serious difficulty enconntered in drilling under such conditions. Lime-base drilling fluids have been very succesefully and widely used in the drilling of wells in the Gulf Coast region because of their inherent stability toward contaminants. their ability to suppress the swelling dispersion of bentonitic shales, and their ease of maintainance. The gradual recognition: during the past few years, that these muds were. in themselve. the cause of many difficulties experienced in drilling has led to wide-pread efforts by the drilling industry. to determine the reasons for the failure of these mud systems and to develop mud systems capable of performing satisfactorily under high-temperature conditios. MANIFESTATIONS OF HIGH-TEMPERATURE GELATION it is generally possible to recognize the symptons of high-temperature gelation early enough that advance predictions can be made of serious difficulties. in mud control, and the useful life of the drilling fluids can be extended by proper treatment. Following i.; a list of the manifestations of high-temperature gelation: (1) The drill string 'takes weight' while going in the hole after a trip. In early stages of high-temperature gelation it is possible to notice a slight reduction in drill string weight as the drill pipe is lowred near the bottom of the hole. (2) Excessive pump pressure is required to .tart the circulation of drilling fluid at or near the bottom of the hole when going hack to bottom after a trip. As the severity of the gelation increases it may be necessary to break circulation a number of times when going in the hole. (3) The drilling fluid from the bottom of the hole is thick and often granular or lumpy when pumped up after making a round trip. In a severely gelled drilling fluid system such a condition may be irreversible; that is, it cannot be stirred or chemically treated to produce a satisfactory drilling fluid. (4) Completion tool.. such as logging tools or perforating guns will not sink to the bottom of the hole. On some occasions completion tools will become stuck and require a fishing job to retrieve them if the wire line attached to them is broken. It is often difficult to determine whether the condition of the drilling fluid is responsible for sticking the tool or whether the wire line becomes key seated in a crooked hole and causes the allow difficulty. When there are 110 other symptoms of high-temperature gelation. then the difficulty may usually be attributed to the latter cause. (5) In extreme cases of high-temperature gelation it is necessary to "wash" and "ream" when going back to bottom after coming out of the hole. (6) In many -instance. it has been found to be extremely difficult and expensive to 1111 production packers 2nd tubing in moderately deep oil wells which had been drilled with a lime-base drilling fluid. In such instances-the original mud had apparently "set" to a consistency approaching that of a weak cement. CAUSES OF HIGH-TEMPERATURE GELATION Extensive test; have indicated that a lime-base mud does not develop a highly gelled condition at temperatures below 250°F. whereas above that temperature such condition often develops rapidly. (Fig. 1) concurrently. the following changes are evident ill the mud: (1) The alkalinity of the mud decreases to a very low value. with both caustic soda and lime being consumed. (2) The quartz content of the mud decreases sharply. (3) The bentonitic content of the mud decreases or di-appears, with concurrent decrease or loss of base exchange capacity of mud solids. (4) New compounds formed in the mud have been found to be cal-cium silicate, calcium aluminum silicate, and calcium sodium aluminum silicate. (5) The mud loses the ability to form a filter cake of low permeability. The above characteristics have been discussed, in part. by other authors

Jan 1, 1953

Map

Jan 1, 1938

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Jan 1, 1938

By E. H. Crabtree, Neil S. Parker

THE custom milling plant of the Eagle-Picher Mining and Smelting Co. is at Sahuarita, Arizona, approximately 20 miles south of Tucson. It is connected by a 2-mile railroad spur to the main line of the Southern Pacific Railroad between Tucson and Nogales. The capacity of the plant is 500 tons per day. The mill is conventional except perhaps in the rather wide variety of ores treated. These vary from straight copper ores, from which only one concentrate is produced, and lead-zinc or copper-zinc ores from which two concentrates are produced, to complex gold-silver-copper-lead-zinc ores, which require the simultaneous production of three or four concentrates. Custom ores are received in lots varying in size from a few truckloads to several carloads. Similar ores, after crushing and sampling, may be commingled, or individual lots may be milled individually. The ores are first dumped either into one of two 200-ton railroad bins, or into one of the two 75-ton truck bins. From these bins the lot of ore is individually crushed in a 24 by 16-in. jaw crusher to 3-in. size, and then to 1/2-in. size in a 3-ft Symons shorthead crusher. After crushing to 1/2-in., the ore is conveyed to the automatic sampling plant. This consists of three Vezin samplers in series, each successively cutting out 10 pct, to pct and 5 pct of its feed. After No. 1 sampler, the material passes through a mixing barrel and is then crushed to 1/4-in. in a set of rolls before passing to No. 2 sampler. Between No. 2 and No. 3 samplers, the ore is again mixed in a mixing barrel. The final sample, consisting of one pound per ton of ore, is taken to the laboratory, where it is further crushed to 1/8-in. in a coffeemill, and then riffled down to the size required for grinding in a pulverizer. The capacity of the crushing and sampling plant is up to too tons per hour, depending upon the character of the ore. After sampling, the ore is stored in five ore-storage bins, consisting of four 200-ton bins and one 175-ton bin. Each of these bins is discharged by means of belt feeders and conveyor to the ball mills, so that ores may be composited for milling in any required ratio, or milled separately by themselves. Fine grinding is done in one 6 by 4-ft Allis-Chalmers ball mill and one 8-ft by 36-in. Hardinge mill. These two mills both discharge to one 54-in. Akins Simplex Highweir classifier. The classifier sands can be returned to either or both mills, so that flexibility in grinding for different ores is easily obtained. Flotation equipment consists of four 66-in. Fagergren machines for copper-lead roughing and six similar machines for zinc roughing. Lead-copper bulk concentrate is cleaned and recleaned in eight No. 18-S Denver machines, and zinc concentrate is cleaned in three 66-in. Fagergrens. Copper-lead differential separation

Jan 1, 1947

By T. R. Wright

THE Corporation operates concentrators in four camps: Casapalca. Morococha, Cerro de Pa-co, and Mahr. The present concentrator at Cerro de Pasco is the newest having been completed in 1943. and that at Casapalca the oldest, having been built originally as a gravity concentrator, in 1889. Prior to 1925 the Corporation's milling operations were confined to the beneficiation of silver-bearing copper ores, and treatment of these ore: by flotation was started in 1918. Although fairly large deposits of complex, fine-grained lead-zinc ores existed, little progress had been made in the treatment of such ores--in Peru or elsewhere-until the early 'twentics. The Casapalca concentrator began the selettive concentration of complex leadzinc ores by all-flotation methods in 1925, or contemporaneously with the commercial development of selective lead-zinc flotation in the United State:.

Jan 1, 1945

By A. Tremari, Paul I. Eimon

Photogrammetrists are studying with new interest the problems of mine mapping and mining engineers are beginning to see what photogrammetry can do for them. Administrators in a number of European and U. S. mines have tried photogram- metric methods and are finding that better maps and data, needed for mine development, can be produced with savings of time, men, and money. In addition to wide use in small scale mapping projects, photogrammetric methods are now used for producing large scale plans and maps in German coal and lignite mines, in some U. S. open pit mines, to inventory TVA coal stock piles, and to compute highway excavation volumes. In each case surveying and map compilation has been made more efficient and accurate by photogrammetry and at significant savings over ground methods.

Jan 5, 1959

By I. Fatt, D. N. Saraf

A method is described for measuring two- and three-phase relative permeabilities in sandstones or sand packs using a nuclear magnetic resonance (NMR) technique to determine fluid saturations. Two- and three-phase relative permeabilities have been determined on Boise sandstone using the NMR technique of saturation measurement. Three-phase relative permeability to water was found to depend only on the water saturation, whereas three-phase permeability to oil depended on both the water and oil saturations. Relative permeability to gas in three-phase flow was found to depend only on the total liquid saturation. INTRODUCTION Three-phase relative permeabilities are extremely useful in calculating field performance for reservoirs being produced by simultaneous water and gas drives. Three-phase relative permeability data are also needed for analyzing solution gas-drive reservoirs which are partially depleted and are being produced by water drive. Some thermal recovery processes involve three-phase flow which require three-phase relative permeability data for predicting reservoir behavior. Unfortunately, three-phase relative permeability measurements have rarely been made. Also, because of the scarcity of three-phase data, it has not been possible to date to relate other measured rock characteristics to the relative permeabilities with a great certainty. Leverett and Lewis,l Reid2 and Snell3 have reported three-phase relative permeability data on unconsolidated sands. Leverett and Lewis used ring electrodes spaced along the length of the sand sample to measure the resistivity of the sample which was assumed to be monotonically related to brine saturation. Gas saturation was determined from pressure-volume measurements. Oil saturation was obtained by material balance on the cell containing the sand sample. This method is involved and time consuming. Another difficulty arises from the fact that the resistivity of the sand is a function not only of saturation of brine but also of the distribution and saturation history of the brine in the pore spaces. Reid2 used a gamma ray absorption technique for measuring liquid saturation. This method has the disadvantage that total liquid saturation rather than oil or brine saturation is all that can be measured and still another method is required to determine the saturations of individual components. snel13 used a neutron bombardment method which also required a separate determination of the individual component saturations. Caudle et al.4 measured three-phase relative permeability on consolidated sandstones using vacuum distillation for determining fluid saturations. Distillation after each reading makes this technique very lengthy and time consuming. Corey et a1. 5 and Naar and Wygal 6 measured three-phase relative permeability on sandstones by the capillary-pressure method. Semipermeable diaphragm assemblies were used at each end of the core specimen to keep the water phase in the core. Gravimetric methods were used to determine fluid saturations. Sarem7 recently reported an unsteady-state method for measuring three-phase relative permeability on sandstones. This method is an extension of Welge's method8 for measuring two-phase relative permeability. Although Sarem's method is simple and comparatively fast, the assumptions involved may oversimplify the problem. Sarem's assumption, that in all rocks relative permeability to each fluid will depend only on the saturation of that fluid, seems to be rather unrealistic. Neglecting capillary effects at the end of the core is also a weak assumption. Donaldson and dean9 measured three-phase relative permeability using a method similar to Sarem's.

By A. CHESTER BEATTY

MAGNESIUM oxide is by far the most refractory of the common oxides, since it has a melting point of 5072 deg. F. as compared with 3110 deg. F., the melting point of silica (crystobalite) ; 3722 deg. F., the melting point of alumina (corundum) ; and 4127 deg. F., the melting point of chromite (Cr2O33FeO). Its large-scale use in the lining of metallurgical furnaces dates back to the latter part of the nineteenth century, when extensive deposits of magnesium carbonate were discovered in southern Austria in the province of Styria. Before the development of Austrian magnesite, calcined dolomite, a mixture of lime and magnesia, was used in basic steel-making furnaces. The lime in the dolomite was quite objectionable, since it slaked on exposure to the atmosphere, and dolomite therefore could not be made' .into permanent furnace bottoms or into brick. The Austrian magnesite, with its very low lime content, was free from these objections and soon displaced much of the dolomite. With the extensive development of basic steel-melting, the rise of the copper industry, and other metallurgical and chemical processes which dealt with chemically basic substances, the use of magnesite grain and magnesite brick increased rapidly.

Jan 1, 1931

By S. R. Balajee, I. Iwasaki

The interaction between British gum 9084 and dode-cylammonium chloride (DAC) at quartz and hematite surfaces was established from coadsorption studies and streaming potential measurements. The cationic DAC interacts with the somewhat anionic British gum 9084, leading to the formation and adsorption of a binary complex of DAC-British Gum 9084 at the interface. The parallel ability to depress quartz along with hematite as a result of the interaction between DAC and British gum appears to be the main reason for the ineffective depressant action of starches and starch derivatives in the cationic flotation of iron ores. Amines are not particularly selective collectors for the flotation' of siliceous gangue from iron ores and, therefore, a suitable iron oxide depressant is needed for a satisfactory separation. Various starches and their derivatives have been extensively tested with oxidized iron ores,'-3 and it has been empirically established that British gums and dextrins are preferable. However, for the flotation upgrading of magnetite-taconite concentrates from 8 or 8.5% Si O2 to about 5% Si 02, British gums, which have been used so successfully on oxidized iron ores, have been found to have no effect and oftentimes are actually deleterious.4 In previous articles,5-7, starches were shown by adsorption measurements, flotation tests, and floccula-tion tests to interact with calcium ions in solution, and it was thought that a study on the interaction between starches and dodecylammonium ions would be able to shed some light on the anomalous flotation behavior described above. In fact, starches are known to interact markedly with paraffin-chain-type surface active agents and, thereby, to precipitate the starch or inhibit the iodine-starch reaction.8 From X-ray diffraction studies and viscosity measurements, the formation of a helical complex between mylose and a surface active agent has been postulated.9 The interaction with other types of hydrophilic colloids, such as synthetic polymers and proteins, has also been investigated and is usually explained in terms of van der Waals' force interaction and/or ion-ion interaction. In the present investigation, the interaction of British gum and dode cylammonium chloride on quartz and hematite was studied by adsorption and streaming potential measurements in an attempt to establish the mutual adsorption behavior of British gum and dode-cylammonium chloride on mineral surfaces and to clarify the anomalous depressant activity of British gum in the cationic flotation of iron ores. All the measurements were carried out at a natural pH of near 7 because dodecylammonium chloride gives maximum selectivity of flotation separation at this pH2 and to avoid any third parameter in the system. EXPERIMENTAL MATERIALS AND METHODS Minerals: The quartz and hematite samples used for the adsorption tests were prepared as described in a previous paper,"J except that the specific surfaces of the samples were increased to 5,860 and 16,000 Sq cm per gm, respectively. For the streaming potential measurements, the 48165-mesh fractions screened out of the original samples were etched with hydrochloric acid, washed repeatedly with water, and stored under water in Pyrex bottles. Reagents:DodecyIammonium chloride (DAC) was prepared1 1 by bubbling dry hydrogen chloride gas through a benzene solution of high-purity dodecylamine supplied by Armour and Co. British gum 9084, received from Corn Products Co., was solubilized by first dispersing it in water to produce a 0.05% solution and then homogenizing it in a blender for 5 min. Distilled water was used in the preparation of the samples and the solutions and for all test work. Adsorption Measurements: The procedure for the adsorption density determinations was also the same as that described in the previous paper.1° The residual concentrations of the British gum and the DAC in the supernatant solution were analyzed colorimetrically by the phenol-sulf uric-acid and amine-picrate methods, respectively. The validity of the mine-picrate method for the colorimetric analysis of DAC in the presence of British gum and the analysis of British gum in presence of DAC were checked by establishing calibration curves between optical density and concentration. Streaming Potential Measurements: The cell assembly for the streaming potential measurements was similar to that described by Fuerstenau.' The streaming potential

Jan 1, 1970

By Elton A., Youngberg

The Holden mine operated by the Chelan Division of the Howe Sound Co. is on the east slope of the Cascade Range in north central Washington on the south slope of Railroad Creek valley at an elevation of 3500 ft. The mine may be reached by a 40 mile boat trip from the town of Chelan which is at the southern tip of Lake Chelan, to Lucerne at the mouth of Railroad Creek and an 11 mile bus ride up Railroad Creek to Holden. All freight and concentrate is moved over this route to Chelan Falls on the Columbia River which is on the railroad four miles below the town of Chelan. The mine is now producing 2000 tons of gold, copper, and zinc ore per day which is treated in the Holden mill. Gold-copper and zinc concentrates are made, the first of which is shipped to Tacoma, Wash., and the latter to Kellogg, Idaho, for smelting.

Jan 1, 1949

By Arthur H. Leigh

Anode mud, the residual material collected from the bottom of the electrolytic cells during the refining of copper is leached, roasted, fire-refined and cast into Dore1 metal anodes. Dore1 metal is a gold-silver-copper alloy containing 80 percent silver. The metal is processed electrolytically using the Moebius system to refine silver and separate gold, platinum and palladium. The Moebius cell cathodes receive a deposit of silver crystals which are melted and cast into 1000 ounce silver bars with 999 Fine minimum purity. Gold mud is collected in fabric bags and cast into gold anodes for further refining in the Wohlwill cells. Wohlwill cells are unique in that gold, the noble metal, can be put into solution electrolytically without the use of aqua regia. Gold is collected on high purity gold foil cathodes and cast into 400 ounce bull ion with 999.7 Fine minimum purity. Platinum and palladium remain in the electrolyte progressively increasing in concentration and are finally separated and purified by precipitation.

Jan 1, 1973

By A. F. Peterson

MUCH has been said and written about the engineer shortage. The mining branch in engineering has lagged during the past several decades. I can think of two institutions, formerly prominent in that field, that have discontinued this department and another that has branched from a purely mining school into various forms of engineering. Conversely, I do not recall any institutions that have added mining to their curricula. I believe that this action is in direct response to the demands of incoming students. But I also believe that while there is a specific demand for civil, mechanical, and electrical engineers in the highly complicated mining operations of today, our need for mining engineers capable of assuming top responsibility for mining operations is unchanged.

Jan 3, 1957

By M. J. Marcinkowski, K. S. Raghavan, A. S. Sastri

A detailed transmission electron microscopy investigation was carried out in connection with a manganese Hadfield Steel. At small plastic strains, numerous individual intrinsic stacking faults are observed. With increased plastic deformation, the stacking faults thicken into twin lamellae which in turn subdivide the original austenite matrix into smaller domains. The twin boundaries act as strong barriers to subsequent dislocation motion and is in a sense equivalent to grain refinement. It is this "grain refinement" which is believed to be the cause of the very high work hardening rates in the Hadfield Steels. In many cases, especially where an hcp phase is the stable one at low temperatures, the stacking fault energy in fcc metals and alloys decreases with decreasing temperature.' Since stacking faults of the intrinsic type are precursors of both twins as well as the hexagonal close packed structure, both of these entities should become more frequent as the temperature of a fcc crystal is lowered. In the case of the twin, there is no chemical driving force for its formation and it is generally necessary to provide the required driving force by an applied stress, i.e., strain energy. In the case of the hcp structure the transformation from the fcc modification can occur spontaneously (marten-sitically) since a decrease in chemical energy does in fact occur; however, an applied stress will provide an even greater driving force toward complete transformation. Since the transformation products mentioned above occur in an inhomogeneous manner throughout the crystal and since these can act as potential barriers to further plastic deformation2 marked strengthening effects can be anticipated. Also because metal and alloy strenghening is in general proportional to the shear modulus, these effects should be greatest in steels of the austenitic type (y), i.e., the fcc types. Perhaps the two most important steels in this category are the austenitic stainless steels and the Hadfield manganese steels. Both may be quenched from elevated temperatures so as to retain the austenitic states characteristic of those temperatures. The effect of subsequent deformation at lower tem- peratures has a profound effect on the stress-strain curves of these alloys. In particular Fig. 1 shows the compressive stress-strain curves obtained with an 18-8 stainless steel which was quenched from 1850°C after annealing for 1 hr so as to produce all y. As the temperature is lowered, the work hardening rate increases markedly. Although some hcp or c mar-tensite can be generated by plastic deformation as the temperature is lowered,~ it is believed to be a transition phase4 and most of the martensite produced is of the bcc or a variety.3 It is this stress induced martensite which gives rise to the very low initial work hardening at 77°K as can be seen in the stress-strain curve in Fig. 1. Similar low initial work hardening rates have been observed in the stress induced Ni-Ti martensites.5 Fig. 2 shows that an even more rapid rate of work hardening occurs in the Hadfield steels treated in the same way as that described for the 18-8 stainless steels a; the temperature is lowered. It is this ability to work harden to such high stress levels that makes the Hadfield steels particularly suitable for armor plate and heavy construction equipment. However, unlike the case of Fig. 1, no initial low rate of work hardening is observed in any of the curves in Fig. 2. Thus the stress induced formation of any low energy martensite phase in any significant quantity must be ruled out. This observation is in accord with the X-ray findings of Otte.~ On the other hand, small quantities of the E phase have been observed by other investigators using transmission electron microscopy (TEM) above Even more significant was the fact that large numbers of deformation twins were observed in the deformed Hadfield steels,678 which were postulated to be one of the reasons for the high work hardening ability of this class of steels.8 It is the purpose in what follows to discuss a series of experimental observations pertaining to the stress induced transformation in a Hadfield steel and to formulate a dislocation mechanism which adequately accounts for the observed results. EXPERIMENTAL PROCEDURE The stainless steel used to obtain the curves shown in Fig. 1 was of the AISI Type 303 containing approximately 18.0 pct Cr and 8 pct Ni. On the other hand, the Hadfield manganese steel used to obtain the curves shown in Fig. 2 contained between 1.00 to 1.25 pct and 11.5 to 13.5 pct Mn. In all cases the samples were in the form of compression cylinders 0.220 in. in diam and 0.370 in. long. Prior to testing the samples were annealed for a hr at 1050°C and rapidly quenched into a brine solution. This treatment was sufficient to preserve the y phase for subsequent testing at lower temperatures. All samples were compressed in an Instron testing machine using a cross head speed of 0.02 in.

Jan 1, 1970

By B. C. Mariacher, I. Hoffman

In 1952, beneficiated phosphate ore first began to move from the Oron plant of Negev Phosphates Ltd. in the Negev Desert to the super-phosphate plant at Haifa, Israel. Since that time this company has continually sought to overcome its natural handicaps affecting the operating efficiency and quality of the product in an effort to bolster the agricultural program of Israel and the development of an exportable commodity. The most serious deterrent to the development of a beneficiation process was the total absence of water. The Oron plant lies approximately 30 miles south of the irrigated regions of Israel with the nearest producing water well located about 10 miles to the northwest. The urgency of early phosphate production made it necessary to consider only dry processes in the initial operation. Fortunately, the ore was amenable to a dry process which yielded a usable concentrate assaying about 28.5 pct P2O5; but phosphate recovery was low. A description of the characteristics of the Negev ore should help to clarify the principles upon which the dry concentration is based.

Jan 5, 1961

By R. A. Graham, R. W. Rohde

The effect of hydrostatic pressure upon the austenite start temperature of a commercial Fe-28.4 at. pct Ni-0.5 at. pct C alloy has been determined. For pressures to 20 kbar, the austenite start temperature decreased from its atmospheric pressure value of 380°C at the rate of about 4°C per kbar. These data are analyzed by two different thermodynamic approaches; first, considering the transformation as an isothermal process, and second, considering the transformation as an isentropic process. It was found that both these approaches fit the experimental data equally well. The effect of hydrostatic pressure upon the austenite start temperature is best described by considering the mechanical work done during the transformation as that work obtained by multiplying the applied pressure with the gross volume change of the transformation. It is widely recognized1 that strain has an important effect on the initiation of martensitic transformations.* For example, the martensite start tempera- *In this paper, use of the term martensitic transformation implies the reversal of martensite to austenite as wen as the formation of martensite from austenite. ture, M,, may be increased by plastic deformation. Similarly, plastic deformation is observed to lower the austenite start temperature, A,. The effect of uniaxial stress on the M, of iron-nickel alloys has been studied by Kulin, Cohen, and Averbach.2 They found that the martensite start temperature was significantly changed by stresses well within the elastic region. Moreover, the effect of tensile and compres-sive stresses differed. These effects were explained in terms of the interaction of the applied stress with both the dilational and shear components of the transformation strain. The magnitudes of the influence of uniaxial tension, compression and hydrostatic pressure on Ms were measured in 30 pct Ni 70 pct Fe by Pate1 and Cohen.3 Their thermodynamic calculations and similar calculations by Fisher and Turnbull4 predicted the experimental results when the transformation was assumed to occur isothermally at some fixed driving force. This driving force was assumed to be supplied by a combination of the chemical free energy difference between the austenitic and martensitic phases and the work performed during transformation by the applied stress. More recently, Russell and winchel15 reported the effect of rapidly applied shear stress on the reversal of martensite to austenite in iron-nickel-carbon alloys. They performed a thermodynamic analysis of this transformation based upon the assumption that the re- versal occurred adiabatically. They concluded that the applied shear stress did not significantly interact with the transformation strain and thus did not assist in inducing the reversal. Rather they concluded that the reversal was effected by localized strain heating which resulted from the gross local shear deformation of the experiment. In either the adiabatic or isothermal analysis it is necessary to compute the work performed by the interaction of the applied stress and the transformation strains. In the case of hydrostatic pressure this interaction has been treated by two different methods. In either case the applied pressure is assumed to remain constant during the transformation. In one treatment the applied pressure is assumed to interact directly with the dilatational strain associated with the formation of an individual martensite plate.3'4 This local strain has been measured at atmospheric pressure in iron-nickel alloys by Machlin and Cohen.6 In the above treatment this local strain is assumed invariant with temperature and pressure changes. In the other treatment the applied pressure is assumed to interact with the gross volume change of the transformation.7,8 The usefulness of this latter treatment has been demonstrated by Kaufman, Leyenaar, and Harvey7 who calculated the effects of pressure upon the martensite and austenite start temperatures of Fe-10 at. pct Ni and Fe-25 at. pct Ni alloys. Excellent agreement was obtained between their calculations and their experimental data on an Fe-9.5 at. pct Ni alloy. However, this treatment suffers from the fact that the data required to calculate the volume change of the transformation (i.e., the initial specific volumes, the thermal expansion and compressibility data for both the austenitic and martensitic phases) is, in general, not available for any material except pure iron. Thus the calculations of Kaufman et al.7 were necessarily performed by assuming that the volume change of the martensitic transformation in the iron-nickel alloys was that same volume change occurring during the a-? transformation in pure iron. While this approximation may suffice for very dilute alloys it is likely to be inaccurate in high nickel alloys. We have performed measurements of the effect of hydrostatic pressure to 20 kbar on the A, temperature of an Fe-28.4 at. pct Ni-0.5 at. pct C alloy. The composition is similar to the alloy used by Pate1 and Cohen3 to determine the effect of pressure upon the M, temperature. The present measurements permit calculation of the interaction between the applied pressure and the transformation strain. Additionally, measurements have been made which allow precise determination of the gross volume change of the transformation. The data allow direct comparison between the alternate hypotheses of the interaction between the applied pressure and a dilatational transformation strain characterized by either the formation

Jan 1, 1970

By P. E. Rider, K. A. Gschneidner, O. D. McMasters

The solid solubilities for thirteen rare-earth metals in gold were determined by using the X-ray parametric method. Solubilities ranged from 0.1 at. pct for lanthanum in gold up to 8.8 at. pct for scandium in gold. The solubilities from lanthanum to gadolinium were very small and essentially constant, but a sharp increase occurred from gadolinium to scandium. The large solubilities for the heavy rare-earth metals were not expected because of the large size and electrochemical differences between rare-earth atoms and the gold atom. Contributions from first- and second-order elasticity theory plus an electronic contribution were found to reasonably account for a more favorable size factor. Electron transfer from the rare-earth metal to the gold Is thought to occur such that the resultant rare-earth and gold electronegativities are favorable for solid-solution formation. It was also found that this mutual adjustment of size and electronegutivity does not occur if the pure-metal size factors are greater than a critical value of 25 pet. The eutectic temperatures for ten systems were determined and these remained fairly constant at approximately 809 "C for the lighter lanthanide metal-gold systems until the Er-Au system was reached, at which Point the eutectic temperature successively increased reaching a maximum of 1040°C in the Sc-Au system. This rise was correlated to the size factor becoming more favorable for solid-solution formation at erbium. The valence state of ytterbium was found to change from two in the pure metal to three when ytterbium is dissolved in the gold matrix. RECENT results1 reported concerning the solubility of holmium in copper, silver, and gold, showed that the solubility of holmium in gold was quite large, 4.0 at. pct, compared with 1.6 in silver and 0.02 in copper. The small solubilities of holmium in silver and copper are quite reasonable in view of the large size difference (22.2 and 38.2 pct, respectively), large electronegativity difference (0.59 for both systems), and possible unfavorable valency factor (assuming one for silver and copper and three for holmium). The large solubility in gold, however, is unexpected because these same factors are also unfavorable for holmium and gold (22.5 pct size difference and 0.69 electronegativity difference), and because the light rare-earth metals, lanthanum, cerium, and praseodymium, have negligible solid solubilities in gold.2 In view of this unexpected behavior, it was felt that a study of the solid solubilities of most of the rare-earth metals in gold would be desirable to better understand the factors involved in the formation of solid solutions. Of the rare-earth metals added to gold in this study, only ytterbium is divalent in the pure metallic state (the other rare-earth metals are all trivalent) and many of its physical properties (such as the metallic radius, electronegativity, and so forth) are much different from those of the normal trivalent rare-earth metals.' The properties of ytterbium are such that one would expect solid-solution formation to be less favorable for ytterbium in gold than for any of the normal trivalent rare-earth metals. But chemically ytterbium is known to possess a stable trivalent state, and it is quite possible that ytterbium may alloy as a trivalent metal under certain conditions rather than as a divalent metal. Because of the dual valency nature and because so little is known about the alloying behavior of ytterbium, the gold-rich ytterbium-gold alloys are of special interest. EXPERIMENTAL PROCEDURE Materials. The gold used in this investigation had a purity of 99.99 pct with respect to nongaseous impurities. In general the rare-earth metals were prepared by reduction of the corresponding fluoride by calcium metal.3 The impurity contents of the metals used in this study are given in Table I. Preparation of Alloys. Two- or 3-g alloy samples were prepared by arc melting. The samples, with the exception of some of the Er-Au alloys, had weight losses of 0.5 pct or less. All alloy concentrations noted in this paper are nominal compositions. After arc melting, the alloys were wrapped in tantalum foil, sealed off in quartz tubing under a partial atmosphere of argon, homogenized for approximately 200 hr at 780°C, and then quenched in cold water. X-Ray Methods. The X-ray parametric method was used in determining the solubility of the rare-earth metals in gold. filings were sealed in small tantalum tubes by welding under a helium atmosphere. The tantalum tubes were then sealed in quartz tubing under a partial argon atmosphere, and annealed for times ranging from 1/2 to 3 hr (the length of time was inversely proportional to the an-

Jan 1, 1965

By R. E. Shinkosk

This paper outlines the development of a program for increasing the life of woolen bags used for filtering Dwight-Lloyd gases by treating the bags and gases with hydrated lime. Methods and apparatus are described for determining alkalinity of dusts, acidity and breaking strength of bag cloth. Procedure and results, based on several years of operation, are presented. DURING 1939, additional facilities were constructed in the Dwight-Lloyd Blast Furnace and Baghouse departments at the Selby, California, Plant of the American Smelting and Refining Co. In order to handle adequately the increased volume of gases from the resultant increase in production, it was necessary to increase gradually the amount of water used for cooling gases ahead of the sinter machine baghouse. As a result of this increased water cooling, the average bag life dropped from 27 months in 1939 to 14 months in 1941. (Table I). This drop in life meant an increased. bag cost, as well as lower recovery of dust and some curtailment of operation. During 1941, it was found new bags showed as high as 0.3 pct acidity* after two weeks of opera- tion and as much as 2.0 pct acidity after some months of operation. This high acidity was present in spite of the fact that free oxide or relative alkalinity of the unburned dust ran from 5 to 6 pct. In view of these circumstances, a twofold program was started in Nov. 1941.t Part one of this program consisted of vigorously dipping all new bags in a weak lime solution, containing 50 lb of hydrated lime per 50 gal of water. Part two consisted of feeding fine, dry, hydrated lime into the gas stream intake of the sinter baghouse fan. Apparatus for feeding this lime is shown in fig. 1. All baghouse chambers are shaken in rotation about once each hour. On alternate hours, the baghouse operator places 50 lb of hydrated lime (one sack) into the lime feeder, starts feeder and immediately starts the bag shaking machinery. The rate at which lime is fed is set to coincide with the approximate time necessary to shake all sinter bag-house chambers, or about 15 min. It is felt this method of lime addition is most effective for getting lime into the woolen bag fabric. The amount of lime so fed averages about 600 lb per day. The amount of lime fed per day is varied to keep a minimum relative alkalinity of 9 pct in the unburned sinter dust. A daily dust sample is taken for alkalinity by allowing dust to accumulate in a sample pipe over a 24-hr period. This sample pipe, placed in any chamber cellar, is 2 in. in diam, 4 ft long, is sealed on the inner end, and capped on the outer end. It has a 1/2 in. slot cut for 18 in. along the tip end. This slot faces upward and allows the pipe to fill gradually with dust as bags are shaken. Breaking strength of bags has, in most cases, been the deciding factor in bag replacement. Bags that normally test 100 psi breaking strength when new are replaced when they test under 35 lb. The method for determining breaking strength is shown in the description accompanying fig. 2. Since the start of the liming program in 1941, bag life has increased from 14 months to an average of over 23 months, with a consequent material decrease in bag cost per year. Acidity, as per cent sulphuric acid, may be determined by means of a Beckman pH meter as follows: From a piece of bag cloth. which has been thoroughly cleaned of dust, a 5 g sample is weighed on a balance. Cut the sample into fine pieces and place in a 400 cc beaker. Add 100 cc (measured) of distilled water and stir vigorously. Filter on suction funnel, holding cloth pulp in beaker with a stirring rod. Wash cloth sample and filter wash water four additional times, each time with 20 cc distilled water, the last time squeezing cloth pulp over funnel. Discard pulp and rinse funnel and filter paper. Pour wash solution jnto measuring graduate and make up to exactly 300 cc with distilled water. Place into clean 600 cc beaker and measure the pH on meter. The per cent acid in bag cloth is read from the following table:—

Jan 1, 1951

By S. E. Maddigan, B. R. Zimmerman

MOST metallurgists are well acquainted with the contributions already made to the study of metals by the use of X-rays. On the one hand, the radiographic method is constantly becoming of increasing importance as a nondestructive testing procedure, while on the other hand the techniques of X-ray diffraction have made important contributions to the fundamental knowledge in studies of phase diagrams, stress conditions, and so forth. A new, and as yet insufficiently appreciated, tool exists in the application of microradiography to alloy structures. This new procedure in many respects bears the same relation to microscopic investigations as does macroradiography to the gross inspection of metal surfaces. However, where macroradiography is used ordinarily to determine the soundness of the metal structure, this new method can be used not only to investigate micro-un- soundness but also to examine the distribution of the constituent elements within the body of the alloy. When combined with the normal procedures of microscopy, this offers a technique of great potential power. It is intended in this paper to present a few examples of copper-base alloys demonstrating the additional knowledge obtained from the microradiographic method. The detection of micro-unsoundness is demonstrated in Fig. I for a sample of cartridge brass as cast. The sample appeared quite sound when viewed under the microscope, but in reality was thickly populated with minute voids. This application of the method conforms in every way to conventional large-scale radiography and has been used to facilitate production of metal for vacuum devices.1 The true potentialities of the technique are revealed by comparison of Figs. 2a and 2b, which are respectively a- photomicrograph and a microradiograph of a cast alloy of 80 per cent Cu, 10 per cent Sn, 10 per cent Pb. The remarkable difference in appearance provides some concept of the additional information this method may yield when used as an auxiliary to microscopic studies. Fig. 2a shows two phases of the copper-tin system plus segregated lumps of lead. Fig. ab, on the other hand, shows with exceptional clarity the actual dendritic growth of the metal crystals during solidification. The practice of microradiography depends upon the laws of absorption of X-rays. This subject has been reviewed thoroughly in recent papers,1,2,3 but for clarity a brief resumé will be given here. As is well known, when a beam of X-rays is transmitted through a layer of homogeneous material, the intensity is reduced according to the relation:[ ]

Jan 1, 1944