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By Robert I. Jaffee, Bruce W. Gonser, Eugene M. Smith

There has been little investigation of the gold-germanium binary alloys. Haughtonl does not mention any work on the system. In a review article commemorating the fiftieth anniversary of the discovery of germanium, E. Einecke2 mentioned a gold-germanium eutectic at 24 atomic per cent Ge (10.4 weight per cent) melting at 359°C., but did not give the source of his information. From measurements of electrical conductivity, J. 0. Linde3 estimated that at least 0.6 weight per cent germanium is soluble in gold. The recent availability of germanium in this country in commercial quantities has led to interest in its properties and its alloys. This study is part of a program of investigation on germanium alloys; work on ternary alloys involving germanium and gold will be reported later. In this investigation, the composition and melting point of the Au-Ge eutectic reported by Einecke has been found to be substantially correct. Eutectic composition has been placed at I2.0 per cent germanium, however. An alloy of 10.4 per cent Ge, Einecke's value, was found to have a few gold dendrites in it. The cutectic temperature has been determined as 356.0 6 ± 0.5°C., slightly less than the temperature of 359°C. reported by Einecke. The liquidus curves and the solid solubility of ger- manium in gold have been determined, and are shown in Fig. I. Materials and Alloying The germanium used in this investigation was prepared by the Eagle-Picher Lead Co. from pure germanium oxide, by reduction in clay crucibles with sodium cyanide. The regulus is quite pure, assaying over 99.9 per cent Ge. High-purity gold obtained from Handy and Harmon was used. Alloying was carried out in graphite crucibles in an atmosphere of purified hydrogen. The temperature was brought up to 1050" to iioo°C., and the metal was allowed to freeze in the crucible. Prepared in this way, the gold dendrites in hypoeutectic alloys were somewhat segregated at the bottom and sides of the ingot, and on the hyper-eutectic side the lighter primary germanium tended to gather at the top. Most of the alloys were made from virgin metal. Low-germanium heats were made by alloying pure gold with the eutectic. Melting losses were consistently a few milligrams or less, and the composition could safely be taken from the intended analysis. The 30 per cent and 50 per cent germanium heats for thermal analysis were made in part from remelted higher germanium heats, and they may be OR composition as much as one per cent. Because of the high cost of materials, the weight of heats for thermal analysis were 15 to 20 grams and heats for metallo-graphic, X-ray, and hardness specimens were 2 to 4 grams.

Jan 1, 1945

By N. J. Grant, A. W. Mullendore, Y. Ishida

Creep tests were performed at 500°F on polished specimens of A1-3 pct Cu at stresses of 2000, 4000, and 6000 psi. The effects of the size and distnbution of the second phase were studied in connection with the mechanisms of deformation, especially grain boundary sliding. Although the amount of grain boundary sliding varied considerably for the different heat treatments, yestriction of grain boundary sliding is not due primarily to precipitate on the grain boundary. NUMEROUS prior investigations of grain boundary sliding, notably those of McLean, 1 Rachinger, 2 Rhines, Bond, and Kissel, 3 and Brunner and Grant,4 have established the importance of this phenomenon in the deformation of pure aluminum and its solid-solution alloys at elevated temperatures. An extension of this kind of study to the case of a simple two-phase structure is an important step towards understanding the deformation behavior of more complex alloys. A two-phase A1-3 pct Cu alloy was selected for this study. The creep behavior of alloys in this system has been studied by Sully and Hardy,5 by Underwood, Marsh, and Manning,' and by Pelloux, Chaudhuri, and Grant.7 In these studies, the prior heat treatments were such that some precipitation took place during the tests in most cases. Pelloux, Chaudhuri, and Grant7 studied the creep of A1-2 and 3 pct Cu alloys in the overaged condition. Their results indicated that the structure most effective in promoting high-temperature strength consisted of a fine, closely spaced grain precipitate and large, widely spaced particles on the grain boundary. The present work consists of quantitative meas- urements of grain boundary sliding during creep of an A1-3 pct CU alloy with four different precipitate distributions. The aims were to quantitatively define the role of the second phase on grain boundary sliding, and to obtain information regarding the mechanism of grain boundary sliding. MATERIALS AND PROCEDURE A high-purity A1-3 pct Cu alloy, kindly supplied by Alcoa, was used in this investigation. The composition of the alloy in weight percent was as shown in Table I. This composition is such that A12Cu exists as a second phase at temperatures below 850°F. A homogeneous grain size of 0.6 to 0.8 mm was obtained by annealing the machined test bars for 5 min at 1000°F, furnace cooling to 930°F, and homogenizing for 5 hr. Following the recrystalli-zation and homogenizing anneal, four different heat treatments shown in Fig. 1 were utilized. The F7 and F5 treatments utilize a furnace cool to the aging temperature while Q7 and Q5 have a water quench from the homogenization temperature before aging. Figs. 2 to 5, and Table 11, show the size and shape of precipitate dispersions obtained with the above heat treatments. The heat treatments produce variations in the dispersion both in the grains and along the grain boundaries. Precipitate particles along the grain boundaries are rounded and large (about 1.5 p diameter) in the F5 and F7 structures (Figs. 3 and 5). The grain boundary precipitate was somewhat smaller (0.9 p diameter) in the Q7 structure and no grain boundary precipitate was detected in the Q5 structure using light microscopy. The pre-

Jan 1, 1964

By B. J. Reid, J. N. Greenwood

It has been shown1 that cavities are formed in the grain-boundaries of copper and 70:30 brass (as well as in magnesium) by the application of tensile stresses at elevated temperatures. For a given rate of strain, cavities are formed in brass at a lower temperature than in copper, and they are larger; it was thought that this earlier onset of cavitation in the alloy might be caused by the distortion produced in the metal lattice by the alloying element. If the cavitation is caused by the vacancy-migration mechanism, ' the distortion of the lattice would reduce the energy required for vacancy formation, and thus provide vacancies more readily to assist in the cavitation process. It was decided to study a range of alloys to find out whether increasing amounts of an alloying element would cause any progressive increase in, or modification of, the cavitation in copper. Nickel was chosen for this purpose, since it is soluble in copper throughout the whole range of alloys. A further advantage was its low vapor pressure, which enabled the preparation of the alloys in vacuum and the consequent reduction of their hydrogen content. It has been suggested that cavities may be nucleated by the migration of hydrogen atoms to the less regular atomic spacing at the boundary, and their combination to form molecules. The latter being too large to diffuse back into the lattice, form stable cavities into which vacancies could condense. PREPARATION OF ALLOYS All alloys, ranging from pure OFHC copper to 43.7 at. pct of nickel (carbonyl), were prepared in a vacuum furnace employing high-frequency induction heating. When a charge was melted, vigorous gas evolution occurred initially, after which the pressure was reduced to 10-4 mm Hg, using an oil-diffusion pump. After remaining molten for a further 1/2 to 1 hr to aid degassing, the melt was allowed to solidify in the crucible. In this way contamination by gases evolved from the surface of a separate mold was avoided. The list of alloys prepared is shown in Table I. The percentage of hydrogen present in the OFHC copper was reduced from 0.0054 at. pct to 0.0012 at. pct, as measured by a vacuum-fusion method. The alloys were cold-rolled to 0.03-in.-thick strip, and were homogenized in vacuum for 1 hr at 900°C after every 30 pct reduction. At a thickness of 0.05 in., the strip was held at 450°C for 24 hr under high vacuum (10-5 mm Hg) in an attempt to reduce the hydrogen content still further. Tensile specimens were prepared with a gage length of 1 in., and were finally annealed for 2 hr at 800°C to give an average grain diameter of 0.1 mm. TENSILE DEFORMATION The specimens were deformed in a tensile straining machine operated by a synchronous motor at a constant rate, equivalent to 1.7 pct per hr on a 1-in. gage length. The specimen and grips were contained in a vacuum jacket. A pressure of 10-2 mm Hg was maintained, which was sufficient to prevent surface tarnishing of a specimen held at 650°C for 24 hr. Tests were made between 20. and 650°C and the temperature was controlled to within ±3° over the gage length. The load was measured by the deflection of a cantilever spring. a) Mechanical Properties-The ductility curves shown in Fig. 1 fall into two groups. Figs. 1(a) and (b) for copper and the 5 pct nickel alloy, respectively, show a continuous fall in ductility with a steep fall between 200° and 400°C. Figs. l(c) to (f) show the same sudden loss of ductility between 200° and 400°C. With higher temperatures, however, there is a recovery in ductility values to a maxi-

Jan 1, 1959

By J. C. Swartz

New measurements of graphite and cementite solubilities in ferrite have been obtained to resolve disagreements among previous data. To measure graphite solubility, specimens of iron were equilibrated with rarious carburizing atmospheres at temperatures be-twee~z 480" and 1435°C. The carbon activity of each atmosphere relative to graphite was taken from published data. After quenching from each equilibration treatment the concentration of carbon (typically 10 pprn by wt) was determined from the height of the Snoek peak in the internal friction spectrum. A few inclividual analyses by combustion support the reszdts of Smith on the solubility of graphite near the eutectoid temperature. Combination of these combustion and internal friction analyses determines In a, (at 0.01 wt pct) = 24,000/RT - 12.72, where a, is the activtity relative to graphite in ferrite at fixed cornposition. The same specimens were used to determine the solubility of self-stressed cementite precipitates. The results indicate solubilities of 6.3, 23.2, and 68 pprn carbon by wt at respectively 400°, 500". and 600°C. The once large discrepancy between the cementite solubility determined by internal frictiori and that calculated from flee energy data has been almost completely resolved. A recent study1 (hereafter designated I) on the solubility of cementite in a iron did not fully resolve the disagreement among previous data. The remaining disagreement is illustrated by the phase diagram in Fig. L The data of I are represented by the line labeled "stress-free" cementite. They determine a heat of solution of cementite of (14.8 * 0.2) kcal per mole which contrasts with the (20 * 1) kcal per mole derived from Smith's graphite solubility2 and the formation energy of cementite.3 Toward resolving this disagreement we have obtained new data on the solubilities of graphite and cementite. METHODS As in I the Snoek peak in the internal friction spectrum was used to measure the concentration of carbon dissolved in ferrite. This method relies on the relation C=kQ-1 [1] in which C is the concentration of dissolved carbon, Q-I is the Snoek peak height, and k is a proportionality factor which is a function of the peak temperature, polycrystalline texture, and other parameters characteristic of the ferrite lattice. To determine true heats of solution via Eq. [1], it is necessary to establish that k is independent of the temperature from which the specimen is quenched. Some evidence on this point is contained in a separate report.* Additional evidence is shown by the data points in Fig. 1. These represent the Snoek peaks of two specimens carburized to about 10 ppm C, copper plated, and quenched first from 888º then from 588°C. The copper plate was removed before each Snoek peak measurement. These data show that there is no detectable dependence of k on quenching temperature. The solubility of graphite was determined by repeatedly carburizing various specimens of iron wire with gas mixtures of known carbon activity relative to graphite. To cover a wide temperature range within the a phase boundaries it is desirable to use as low a carbon concentration as is compatible with reasonable precision. With the present internal friction apparatus the best compromise of these desires is a concentration near 10 wt ppm. The dashed line in Fig. 1 was used to approximate the activity of carbon* for

Jan 1, 1970

By G. E. Steudel

THE study of the possibility of effecting a lower cost in the manu-facture of pig iron reveals the importance of the ever present question of slag chemistry and volume. Factors that determine slag chemistry and volume are the impurities in the ore available, the ash-sulphur content of the coke, and a flux material necessary to promote removal of sulphur. Of these, the ores present by far the major source of impurities and what may prove to be the lowest practical slag volume with desired chemistry in one locality may be considered low or high in some other center of iron manufacture. The Chicago district is not only blessed with ores of high quality, but with excellent coke and flux materials as well. It is the intent of this paper to discuss slag problems at the South Works only, where burdens consist of Mesabi ores, Michigan stone, and coke ranging from 7 to 9 per cent ash and containing an average of 0.57 per cent sulphur. Early in the development of modern blast-furnace practice, the con-sideration of slags was secondary to the many adjustments of mechanical difficulties, such as furnace lines, stock distribution, stove design for obtaining higher blast temperatures, improved chemical segregation and size of raw materials. Furnace operators, after making these improve-ments, turned their attention to the study of other refinements in practice, of which slag chemistry appeared to be the most important. It is only within the last two decades that operators have become familiar with the various aspects of slag compositions. The industry, while rather slow in its recognition, is indebted to such investigators as Rankin,1 Wright,1 Feild,2 Royster,2 McCaffery,3 Kinney,4 Holbrook,5 and Joseph5, whose researches concerning the elimination of sulphur within the blast furnace and the effect of slag composition upon melting point, viscosity, and desulphurizing power have established criteria for the selection of slags of the requisite quality.

Jan 1, 1939

By Y. M. Chang, C. H. Pitt

A jet slurry apparatus has been constructed to test corrosive/erosive wear properties of grinding ball metal. Plain high carbon steel heat treated to a hardness of about 60 Rc was used. Slurries of quartz and chalcopyrite ore concentrate were used as the jetting media. Weight loss due to pure corrosion was determined by the linear polarization technique. Weight loss due to pure erosion was determined by jetting while cathodically protecting the sample. By comparing the total weight loss with the sum of the weight losses from pure corrosion and pure erosion, it was found that there was a synergistic effect between corrosion and erosive wear. Corrosion rate, erosion rate, and total erosion/corrosion rate are given as a function of pH and mineral type.

Jan 1, 1986

By Richard H. Rein, John Chipman

The activity of SiO2, in the entire liquid system SiO2-CaO-Mg0-A12O3 at 1600°C is calculated from the distribution of silicon between these slags and Fe-Si-C alloys saturated with either graphite or silicon carbide, the activity coefficient of silicon in these alloys, and the requisite thermodynamic data. The activities of the other components in the ternary systems SiO2-CaO-A12O3, SiO2-MgO-CaO, SiO2-MgO -A12O3 are computed from these data by the IrON blast-furnace slags can be regarded as consisting of the four major oxide components, SO2, CaO, MgO, and A12O3 along with minor proportions of other oxides and of sulfur. The purpose of this study is to measure the activity of silica in the liquid solutions of these four oxides at iron-making Gibbs-Duhem equation with the aid of the known free energies of several of the interoxide compounds and the accepted phase diagrams. Based on these activities, new data are Presented for the free energy of formation of a number of the interoxide compounds. The free energy of mixing the liquid metasilicates of CaO and MgO shows slight positive deviations from the ideal. temperatures and to obtain activities of the other components by application of the Gibbs-Duhem equation and the properties of several interoxide compounds. Recent investigations on the activity of silica in the SiO2-CaO-A12O3 system1-3 and recogntion of a serious error in older data for the free energy of formation of SiO2 (Ref. 4) have succeeded in bringing a fair degree of concordance into the results of different investigators. In the present study, the activity of silica is obtained from the silicon-distribution experiments described in a previous paper,' the revised activity coefficient of silicon

Jan 1, 1965

By Charles B. Dudley

THEO. N. ELY, Esq., Superintendent of Motive Power. DEAR SIR: It is now nearly three years since my first report to you on the subject of steel rails was written. That report, as you will remember, dealt principally with the question of the relation between the chemical composition and physical properties of steel rails and their power to resist crushing and fracture in actual service. Other matters were referred to or touched upon in that report, but the main question was, Why do some rails crush or break in service while others do not? You will doubtless remember that the principal conclusion arrived at was, that the softer rails are less liable to crush or break in service than the hard ones. Or, in other words, so far as conclusions could be drawn from the chemical analysis and physical test of 25 samples of steel rails which had actually been in service, these conclusions were that those rails which have the smaller amounts of carbon, phosphorus, silicon, and manganese are less liable to crush or break in service than those which have larger amounts of these elements. Or, again, looked at in the light * At the Lake George meeting of the Institute in October, 1878, I had the honor of presenting to the Institute, through the kind permission of the officers of. the Pennsylvania Railroad Company, the results of a study of twenty-five samples of steel rails, which had all been in actual service. Considerable discussion followed the publication of that paper, and there seemed to be a strong disinclination, especially on the part of the steel-rail manufacturers, to accept the conclusions presented. One of the principal objections urged against the conclusions drawn was, that they were based on too few samples; in other words, that no conclusions safe to act upon could be drawn from the examination of twenty-five rails. In view of this criticism it was decided to repeat the investigation with a larger number of samples, and with the aid of the experience gained in the first investigation. The results of this second study of steel rails are, by the permission of the officers of 'the Pennsylvania. Railroad Company, herewith presented to the Institute, with the sincere desire that they may aid in adding to our knowledge of this most important product. Like the previous paper, this is in the form of a report to one of the officers of the company, which will account for the style, and the manner of presenting the data

Jan 1, 1881

By C. E. Meissner

The need for a practical method of deciding upon new alloy steel analyses to widen its markets was the problem facing the Chrome Steel Works at the beginning of 1927. In addition to determining the physical properties of the alloys under consideration, it was necessary to test their value in service. Small melts of steel in a crucible, from which test specimens could be made, were insufficient to determine more than physical properties, therefore actual castings and ingots had to be made before the products could be placed in service. Furthermore, to save further experimental work, it was desirable that these heats should be made on a "pilot" basis; that is, actually duplicating regular open-hearth furnace practice. Therefore a one-ton (2000-lb.) acid open-hearth furnace was built. Furnace Design There are no special features in the design of this furnace. Standard acid open-hearth practice is followed, with the reproportioning of the dimensions necessitated by its small size; notably, a considerably increased length in proportion to width in order to get proper flame propagation. After the first heat was made it was found that the check-ers were insufficient. The checker chambers were increased in size and the checker openings were made much smaller. The furnace was started late in March, 1927, and made 65 heats. Experimental work was then stopped unti1, the data accumulated could be worked up and summarized. The run was resumed in November and the furnace is still operating, having made at this writing 60 additional heats. For the last series of runs, there was some rebuilding of both the furnace itself and the checkers. Slag pockets were added. Fig. 1 shows details of construction; Fig. 2, the general appearance. All designing was done by the operating and engineering staff. Construction materials were those available around the plant. The reversing valve is a standard butterfly type taken from an old furnace. The slag pockets and checkers are cleaned by digging down to arched openings which have been bricked up.

By C. H. Mathewson, A. U. Seybolt

As is well known, many questions affecting the properties and uses of a metal cannot be answered without careful consideration of the state of purity realized in the various operations of preparation, refining, or special treatment that have brought the product to its final state. The occurrellce of an impurity in minute quantity offers no guarantee that its effect will be inconsiderable because dissolved substances often modify the properties of a metal quite out of proportion to their concentration. In such cases the determination of solid solubility must be accepted as a problem of considerable difficulty, requiring the use of especially purified materials and methods not ordinarily used in the metallurgical laboratory. This aspect of the equilibrium between metals and their oxides is especially important and a search for fundamental data reveals little except conflicting opinion even concerning the systems of common occurrence and interest. Rhines and Mathewson1 in 1934 studied the solubility of oxygen in solid copper by annealing to equilibrium in air and gave reasons for the failure of other methods, notably the ordinary procedure of heat-treatment followed by microscopic examination, to yield reliable results. In this paper, a similar study has been made of the solubility of oxygen in cobalt. The simple theory of this method is outlined below. Conditions of Equilibrium between a Metal and Dissolved Oxide at Different Temperatures and Pressures The general conditions of equilibrium in any system are conveniently summarized in a projection of the triple curves of the P, T, X space

Jan 1, 1935

By A. U. Seybolt, C. H. Mathewson

As is well known, many questions affecting the properties and uses of a metal cannot be answered without careful consideration of the state of purity realized in the various operations of preparation, refining, or special treatment that have brought the product to its final state. The occurrellce of an impurity in minute quantity offers no guarantee that its effect will be inconsiderable because dissolved substances often modify the properties of a metal quite out of proportion to their concentration. In such cases the determination of solid solubility must be accepted as a problem of considerable difficulty, requiring the use of especially purified materials and methods not ordinarily used in the metallurgical laboratory. This aspect of the equilibrium between metals and their oxides is especially important and a search for fundamental data reveals little except conflicting opinion even concerning the systems of common occurrence and interest. Rhines and Mathewson1 in 1934 studied the solubility of oxygen in solid copper by annealing to equilibrium in air and gave reasons for the failure of other methods, notably the ordinary procedure of heat-treatment followed by microscopic examination, to yield reliable results. In this paper, a similar study has been made of the solubility of oxygen in cobalt. The simple theory of this method is outlined below. Conditions of Equilibrium between a Metal and Dissolved Oxide at Different Temperatures and Pressures The general conditions of equilibrium in any system are conveniently summarized in a projection of the triple curves of the P, T, X space

Jan 1, 1935

By definition the word "grout" means a thin mortar, or a kind of plaster or cement, and "grouting" means to fill up or finish with grout. The words "cement," "plaster" and "mortar" mean a substance that is used in a soft state which subsequently hardens. Thus, grouting is the filling of void space with a substance that hardens. Construction cements are the most common substances used, either by themselves or in mixtures, but the term grouting is applied quite correctly when other substances such as plastics and certain chemicals are used. Also, the use of the term grouting to cover the filling of voids with materials that do not actually become hard, such as the flotation tailings used in grouting in the southeast Missouri lead district, should be considered correct, as some stiffening does take place and, anyway, it is a better descriptive term than any substitute. Engineers are interested in grouting because some of the materials with which they must work contain voids, and certain conditions can be improved if these voids can be filled with something solid and permanent. Grouting is done to accomplish several purposes: I. To stop the passage of fluids and gases, 2. To cement materials together to make them stronger, and 3. To prevent consolidation of materials by filling void space with something solid as a replacement for the air and water that could be forced out under load. The construction industry uses grouting extensively for all three purposes. Grouting is used to stop water percolation under and around dams. It is used to control water flow in tunnel driving and in shaft sinking. It is used to improve foundation conditions under civil engineering structures by permanently filling void space and thereby reducing settlement, or by cementing broken rock together and increasing its supporting strength. The oil and gas industry does a lot of grouting, primarily to stop the passage of gases and fluids. The search for oil at increasingly greater depths has meant greater investment per well, and the oil industry has spent large sums on development of improved drilling methods. This

Jan 1, 1949

By J. Leja, J. H. Schulman

FROTH flotation is usually effected by the addition of a collector agent and a frothing agent to an aqueous suspension of suitably comminuted mineral ores. The action of collectors is to adsorb onto the surfaces of minerals to be separated, sensitizing them to bubble adherence. The action of frothers has, in the past, been accepted as that of froth formation only, brought about by a lowering of the air/water interfacial tension. Substances capable of producing froth are classed1a,b according to their relative capacities for production of froth-volume and froth stability in the simple frother-water system. The purpose of this paper is to show that the surface active agents acting as frothers become effective only when there is a suitable degree of molecular interaction taking place between collector molecules and frother molecules at the air/water and solid/ water interfaces. Further, the discussion will demonstrate that the actual mechanism of adherence of an air bubble to a suitably collector-coated particle is due to the molecular interaction collector-frother. This leads to the formation of a continuous interfacial film of associated molecules, anchored to the mineral by polar groups of the collector, and enveloping the whole bubble. The tenacity of adhesion mineral-to-bubble results from the strength and the visco-elasticity of this mixed film. Some 20 years ago Christman2 postulated mutual dependence of collector and frother in effecting flotation. This view was, however, strongly opposed by Wark,3 who pointed out that an addition of frother had no effect on the value of contact angle once this was established in the solution of collector. More recent work by Taggart and Hassialis' indicated that the presence of frother, namely, cresol, leads to the immediate establishment of a contact angle on sphalerite, partially coated with xanthate, whereas an air bubble fails to make contact in potassium ethyl xanthate solution alone, even after 60 min induction time. Wrobel5 raws attention to the selectivity of frothers in flotation. Many instances of antagonistic effects of certain mixtures of frothers (or collectors and frothers) on flotation froth have been known to flotation operators and have been reported in literature. Taggart6 and Cooke7 give several examples of incompatibility of certain ratios of frothers and collectors, e.g., oleate and long-chain sulphates, pine oil and soaps. Monolayer Penetration. Properties of insoluble films produced by molecules of surface active agents orientated at the air/liquid interface are conveniently studied by the Langmuir trough technique, described fully by Adam.' Using the trough technique Schulman and Hughes" and Schulman et al.10a. b, c, d,e established the existence of molecular interactions occur- ring between certain types of surface active agents. Their experiments revealed the phenomenon of penetration of an insoluble monolayer (e.g., a film of a long-chain alcohol) by a soluble agent (e.g., sodium alkyl sulphate) injected into the substrate (water or salt solution). The degree of molecular interaction taking place on penetration is determined by changes in the surface pressure of the resulting film, changes of its surface potential and its mechanical properties (viscosity and rigidity). When the interaction takes place between both polar groups and both hydrophobic groups of the two participating amphipathic molecules a molecular complex is formed. Complexes formed on penetration of the monolayer at interfaces are not necessarily true chemical compounds: they are labile in solution, the activity and reactivity of individual components are greatly different from those of the molecularly associated complex, and on crystallization they usually separate out into components. However, when formed in the orientated state at interfaces they are found to be very stable, although some mixed films spread as monolayers of stoichiometric complexes can show further penetration by subsequent additions of the soluble component injected into the substrate.'" The degree of association between two or more types of surface active agents is very sensitive even to small changes in electric (dipole) moment of the polar groups of the amphipathic molecules as influenced by magnitude and position of neighboring ions or dipoles, their size, concentration, and stereochemistry. In addition, the molecular association is greatly influenced by concentration and type of inorganic salts in the substrate, by its pH, and by temperature. The nonpolar groups of interacting molecules greatly affect the stability of molecular complexes. Progressive shortening of the aliphatic chain of one of the reacting molecules weakens (at an increasing rate) its tendency to form stable complexes. Similarly, introduction of a double bond of cis-form into one of the reacting chains, which changes the straight hydrocarbon chain into a kinked one, or introduction of a branched chain, reduces the stability of the associated complex. Monolayer Adsorption. Using the trough technique and injecting metal ions into the substrate (water or salt solution) underlying insoluble films of fatty acids, alkyl amines, and sulphates, Wolsten-holme and Schulman11a,b,e. ' and Thomas and Schulman" have established conditions, namely, pH, concentration. and steric factors, under which molecular interactions take place between the polar groups of the surface active agents and the metal ions. These interactions are marked by great changes in the solubility and mechanical properties of the monolayer of the agent; no surface pressure increases are observed as in monolayer penetration experiments. The results of these adsorption studies, correlated with flotation experiments, indicated that in the case of fatty acids and alkyl sulphates their adsorption onto minerals of base-metals takes place by a similar

Jan 1, 1955

By M. E. Wadsworth

The region about the south shore of Lake Superior is to geologists one of the most interesting districts of the United States, embracing as it does, in a limited area, old crystalline rocks, together with forms that are almost in their original condition of a beach sand and mud. In this region was first established the base of the geological column, the Azoic (" without life") System of Foster and Whitney, or the Archæan (" the beginning ") of Dana. Overlying this system are found the sandstones and limestones of the Paleozoic (" ancient life "), and their associated lava-flows (Algonkian ?). These systems possess a strong economic interest, owing to the stores of iron in the Azoic and of copper in the Paleozoic or Eozoic of this district, which forms one of the most important mining regions in America. The geology of this section is so difficult and complicated that, in its general discussion, perhaps no proposition can be stated concerning any portion of it to which exceptions cannot be taken. Indeed, out of the general discussion of different points comes in time the truth, and various geologists, even now, are working over this region in the endeavor to arrive at some consensus, or at least to determine upon what points they can agree, and upon what points difference of opinion will have to exist between them at present, until further evidence can be obtained. The writer will endeavor to give in a brief form that which appears to him at present to be the most correct statement of the geological structure of the region, admitting that from time to time, as more complete evidence shall be obtained, he expects to change his views in the future, as he has done in the past, if that evidence shall cause him to believe that he has been mistaken.

Jan 1, 1898

By R. P. Agarwala, M. S. Anand

Using residual activity technique, the diffusion of palladium, silver, cadmium, indium, and tin in alunzinum has been studied in the temperature range of 400" to 630°C. The diffusivities (in units of square centimeters per second) have been expressed as: IMPURITY diffusion in aluminum,1-9 silverand lead5 for cases of low solid solubility of the impurity in the host metal has yielded frequency factors in the range of l0-6 to l0-9 sq cm per sec whereas the activation energy is practically half the self-diffusion activation energy value. From the observed values of frequency factor, activation energy, and entropy of activation, it has been suggested' that these solutes are not diffusing by vacancy or interstitial mechanisms but by a mechanism which should be consistent with such low values of the diffusion parameters (Do and Q). However in spite of extensive work on these types of systems, the mechanism of diffusion is still not well understood. The present investigation on the diffusion of palladium, silver, cadmium, indium, and tin in aluminum has been carried out to throw further light on the diffusion mechanism in systems, where the solid solubility is very low (except for the case of silver). The results are discussed on the basis of solid solubility and the structural changes involved owing to the presence of the solutes in aluminum solid solution. An attempt has also been made to apply the existing theories of charge5-8 and size8 difference between the solute and the solvent. EXPERIMENTAL PROCEDURE Specimens (1/2 in. diam by 3/8 in. high) were machined out of pure aluminum (99.995 wt pct) rod obtained from Johnson Mattheys. They were sealed under vacuum in quartz tubes and annealed at 620° C for several hours; the grains thus developed were sufficiently large to eliminate the possibility of diffusion along the grain boundaries. The flat ends were prepared carefully after polishing as described previously,10 Radioactive nitrates of cadmium, indium, and tin and chloride of palladium containing, respectively, cd115, 1n114, sn113, and pd103 were dissolved in distilled water and mixed with 30 pct acetone. By means of a micropipet a drop of this solution was placed on a smoothly polished and lightly etched surface of the specimen. Due care was taken to see that the solution spread uniformly on the surface of specimen without trickling down its sides. Radioactive silver was elec-trodeposited using a AgCN-KCN bath. The amount of sample deposited in all the cases was not more than 0.1 µ thick. The samples were then sealed in quartz tubes in vacuum. The cadmium samples were sealed in a purified argon atmosphere to avoid evaporation. The samples were then diffusion-annealed. The temperature of annealing varied between 400° and 630°C and was controlled to ±5°C. On heating to -400°C,the deposits of cadmium, indium, and tin, which were of the order of 0.1 p in thickness, were converted to their respective oxides. The contribution of oxygen present in the lattice of aluminum due to these oxides has been calculated and found to be less than 10 ppm in all cases. Oxide method has already been used by other workers11'12 in diffusion studies without any controversy on the issue. However, in some of these investigations, metallic deposition was also tried. The diffusivities calculated from these measurements were found to agree very well with the diffusivities obtained by using the oxide method. Thus it is assumed that the measured diffusivities represent true diffusion coefficients. Since palladous chloride decomposes at about 500°C, the deposited samples which were to be diffusion-annealed below 500°C were heated in vacuum for a very short time at 500°C to allow the decomposition of palladous chloride to palladium metal. Time taken in decomposition of nitrates to oxides and chloride to metal was negligibly small as compared to the period of the diffusion anneals. The residual activity technique13 was used to study the diffusion profiles where thin layers from the specimen surface were removed by grinding it parallel to a flat surface on a 600-grade carborundum paper. The specimen was washed, dried, and weighed, the differ -ence of the weight being the measure of the thickness of the layer removed. After each such abrasion and weighing, the total residual activity on the surface of the specimens was measured by counting 0.656, 0.94,

Jan 1, 1968

By Thomas H. Clagett

ThE Pocahontas coal field comprises the area in Tazewell County, Va. and Mcrcer and McDowell counties, W. Va., in which Nos. 3 and 4, Pocahontas seams of bituminous coal are mined. It is a mountainous region with ridges rising 300 to 1000 ft. (91 to 305 111.) above the very narrow valleys and, except for some poorly kept farms along the tops of the ridges and the area occupied by the mining and coking plants and villages, is wooded throughout. First shipments were made from Pocahontas in 1883. There are now about 100 mines, 95 per cent. of which are drift mines. At the end of 1920, approximately 298,000,000 gross tons of coal had been produced and 35,000 acres of coal mined. No. 3 seam is from 4 to 10 ft. (1.2 to 3 m.) thick, but the change is gradual and the thickness fairly uniform in any particular locality. It has a streak of bone, about 2 in. (5 cm.) thick, to which the coal adheres on both sides. In parts of the field this bone is replaced by hard slate, usually from 2 to 4 in. thick. The seam has a slate or fireclay bottom and a draw-slate top. No. 4 seam is from 65 to 80 ft. (19.8 to 24 m.) above No. 3 seam, and of minable section only in the western part of the field. It is from 3 to 8 ft. thick and has two streaks of bone, cach from 1 to 2 in. thick. It has a fireclay or slate bottom and is overlaid by from 4 to 24 in. of a laminated coal and slate, locally termed "black rash," which is separated from the coal seam by about 3 in. of slate. This "black rash" averages about 2.5 per cent. ash, but contains some clean coal. The coal in both seams is quite soft. Cleavage sufficieiltly well defined to exert an influence on the mining is rare. Overlying strata arc slates, shales, and sandstones, the sandstones predominating, extending from 30 to 1000 ft. above No. 3 seam. The strata directly above the draw slate of No. 3 seam, or "black rash" of No. 4 seam, and up to the first sandstone are usually slates or shales, about 10 ft. thick over the.

Jan 1, 1923

By Thomas H. Clagett

ThE Pocahontas coal field comprises the area in Tazewell County, Va. and Mcrcer and McDowell counties, W. Va., in which Nos. 3 and 4, Pocahontas seams of bituminous coal are mined. It is a mountainous region with ridges rising 300 to 1000 ft. (91 to 305 111.) above the very narrow valleys and, except for some poorly kept farms along the tops of the ridges and the area occupied by the mining and coking plants and villages, is wooded throughout. First shipments were made from Pocahontas in 1883. There are now about 100 mines, 95 per cent. of which are drift mines. At the end of 1920, approximately 298,000,000 gross tons of coal had been produced and 35,000 acres of coal mined. No. 3 seam is from 4 to 10 ft. (1.2 to 3 m.) thick, but the change is gradual and the thickness fairly uniform in any particular locality. It has a streak of bone, about 2 in. (5 cm.) thick, to which the coal adheres on both sides. In parts of the field this bone is replaced by hard slate, usually from 2 to 4 in. thick. The seam has a slate or fireclay bottom and a draw-slate top. No. 4 seam is from 65 to 80 ft. (19.8 to 24 m.) above No. 3 seam, and of minable section only in the western part of the field. It is from 3 to 8 ft. thick and has two streaks of bone, cach from 1 to 2 in. thick. It has a fireclay or slate bottom and is overlaid by from 4 to 24 in. of a laminated coal and slate, locally termed "black rash," which is separated from the coal seam by about 3 in. of slate. This "black rash" averages about 2.5 per cent. ash, but contains some clean coal. The coal in both seams is quite soft. Cleavage sufficieiltly well defined to exert an influence on the mining is rare. Overlying strata arc slates, shales, and sandstones, the sandstones predominating, extending from 30 to 1000 ft. above No. 3 seam. The strata directly above the draw slate of No. 3 seam, or "black rash" of No. 4 seam, and up to the first sandstone are usually slates or shales, about 10 ft. thick over the.

Jan 1, 1923

By Bruce A. Kennedy, Richard M. Stewart

Slope stability has now become a practical tool in the design and operation of open pits. The selection of slope angles is a critical decision that can have far-reaching effects on the accumulated cash flow and the overall profitability of a mining project. Slope failures can now be dealt with in a number of ways. Two methods - the total removal and the partial unloading of a failing zone-have been practiced for many years. However, with the refinement of monitoring techniques, open pits can now learn to live with a slide and even turn a potential loss into a gain. There are various techniques, such as presplit blasting, drainage systems, and artificial stabilization, which can be applied immediately in an existing open pit to improve the stability of the pit slopes. The technology of slope stability will play an important part in the future mining of low grade, previously marginal orebodies, which will have to be exploited if the mineral needs of the world are to be met.

Jan 1, 1971

By C. S. Yust, J. W. Smith, J. R. Walsh, R. E. Simpson

This paper presents the results of a complete reservoir studv designed to determine a sound economic program for the conservation of oil and gas in the Pickton field, Hopkins County, Texas. The Pickton field produces from the Bacon Lime with all indications of the study being that production is predominately by dissolved-gas drive. Calculations of the total ultimate recovery to be expected under primary operations indicated only 16.7 per cent of the oil originally in place would be recovered. This unusually low recovery is due to the type of drive operating and the extremely high dissolved gas-oil ratio and shrinkage. Results are presented for six plans of returning gas to the reservoir, evaluated to determine (1) comparative recoveries and economics of (a) returning gas at a constant rate by supplementing Pickton gas with extraneous gas during the early portion of the operation, and (b) conventional gas-return operations without using extraneous gas, and (2) the optimum size of compressor plant for each type of pressure maintenance. The over-all economic program considers, for either type pressure maintenance operation. a gasoline plant to process the unusually rich casinghead gas. Since pressure maintenance will disturb equities, pooling of royalties is in the case of Pickton a prerequisite to conservation of oil by this type of operation, both from an economic and legal standpoint. In the event pooling of royalties cannot be achieved, the study considers a gasoline plant to operate under a modified primary production operation which will make the conservation of gas possible. INTRODUCTION The Pickton field, located in Hopkins County, Texas. was discovered in November, 1944. by the completion of Humble's C. D. Nichols 1, in the Bacon lime of the Lower Glen Rose formation, through perforations from 7,888 to 7.896 feet. The well initially produced 50.2 API gravity oil with a gas-oil ratio of 1,350 cubic feet per barrel. Subsurface samples of the reservoir fluid obtained soon after completion of the discovery well showed that the Pickton crude is unique in that it has an extremely high dissolved gas-oil ratio and is subject to very severe shrinkage. Calculations of the future behavior of the Pickton reservoir indicated that ultimate oil recovery by primary operations would be 3,269,000 barrels, representing only 16.7 per cent of the oil in place (19,577,000 stock-tank barrels), and that recovery could be substantially increased by returning the produced gas. The cumulative production of 1,382,694 barrels on November 1: 1947, amounted to 42.3 per cent of the estimated ultimate oil recovery from primary operations. The purpose of this study is to determine and evaluate the optimum program for conservation of oil and gas in the Pick-ton field, including the desirability of conducting gas-return operations and of installing a gasoline plant. LOCATION AND DESCRIPTION Pickton Field, The Pickton field, as shown in Fig. 1, is located in southwest Hopkins County, Texas, 12.5 miles southwest of the New Hope field, 2.7 miles northeast of the Coke field, 16 miles southwest of Sulphur Springs, and 8 miles northwest of Winnsboro, Texas.

Jan 1, 1949

By C. S. Yust, J. W. Smith, J. R. Walsh, R. E. Simpson

This paper presents the results of a complete reservoir studv designed to determine a sound economic program for the conservation of oil and gas in the Pickton field, Hopkins County, Texas. The Pickton field produces from the Bacon Lime with all indications of the study being that production is predominately by dissolved-gas drive. Calculations of the total ultimate recovery to be expected under primary operations indicated only 16.7 per cent of the oil originally in place would be recovered. This unusually low recovery is due to the type of drive operating and the extremely high dissolved gas-oil ratio and shrinkage. Results are presented for six plans of returning gas to the reservoir, evaluated to determine (1) comparative recoveries and economics of (a) returning gas at a constant rate by supplementing Pickton gas with extraneous gas during the early portion of the operation, and (b) conventional gas-return operations without using extraneous gas, and (2) the optimum size of compressor plant for each type of pressure maintenance. The over-all economic program considers, for either type pressure maintenance operation. a gasoline plant to process the unusually rich casinghead gas. Since pressure maintenance will disturb equities, pooling of royalties is in the case of Pickton a prerequisite to conservation of oil by this type of operation, both from an economic and legal standpoint. In the event pooling of royalties cannot be achieved, the study considers a gasoline plant to operate under a modified primary production operation which will make the conservation of gas possible. INTRODUCTION The Pickton field, located in Hopkins County, Texas. was discovered in November, 1944. by the completion of Humble's C. D. Nichols 1, in the Bacon lime of the Lower Glen Rose formation, through perforations from 7,888 to 7.896 feet. The well initially produced 50.2 API gravity oil with a gas-oil ratio of 1,350 cubic feet per barrel. Subsurface samples of the reservoir fluid obtained soon after completion of the discovery well showed that the Pickton crude is unique in that it has an extremely high dissolved gas-oil ratio and is subject to very severe shrinkage. Calculations of the future behavior of the Pickton reservoir indicated that ultimate oil recovery by primary operations would be 3,269,000 barrels, representing only 16.7 per cent of the oil in place (19,577,000 stock-tank barrels), and that recovery could be substantially increased by returning the produced gas. The cumulative production of 1,382,694 barrels on November 1: 1947, amounted to 42.3 per cent of the estimated ultimate oil recovery from primary operations. The purpose of this study is to determine and evaluate the optimum program for conservation of oil and gas in the Pick-ton field, including the desirability of conducting gas-return operations and of installing a gasoline plant. LOCATION AND DESCRIPTION Pickton Field, The Pickton field, as shown in Fig. 1, is located in southwest Hopkins County, Texas, 12.5 miles southwest of the New Hope field, 2.7 miles northeast of the Coke field, 16 miles southwest of Sulphur Springs, and 8 miles northwest of Winnsboro, Texas.

Jan 1, 1949