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By S. Stutz

Three years ago, at the Philadelphia meeting, in February, 1881, the author had the pleasure of presenting to the Institute a paper on coal-washing machinery.* Since that time many new machines, with important improvements and labor-saving apparatus, have been introduced, the construction and description of which may be of interest to some of the members of the Institute. By referring to the above-mentioned paper, and more especially to Plate IV., representing a vertical section of a coal-washer, it will be noticed that the bottom of the plunger-box B is made level or horizontal, and supports a spring-buffer F for the purpose of limiting the down-stroke of the plunger P and receiving the impacts of the latter. Althongh the construction of the box, in view of these impacts, received from the start the proper attention (the bottom of the chamber 3 being made of three thicknesses of 3-inch planks, resting on 6-inch sqnare columns), yet, through careless working of the machinery, without the necessary water in the box, it proved in several instances not strong enough, and had to be changed. To prevent such interruptions in future, it became necessary to devise some means for relieving the machine from the impacts of the plunger altogether. This has been accomplished by the arrangement shown upon Plate I. of this paper, representing a new waesher; and not only has the difficulty been overcome, but also sorne other advantages have been obtained, as will be seen further on. The compartments +, A' of the separator-box have been set upon heavy cast-iron brackets B, leaving sufficient space below the bottom for the buffer F and the sediment-valve K. By means of the plunger-rod 6 passing through the stuffing-box s to the outside, and provided at its lower end with a shoe a, the impacts of the plunger are now transmitted from the buffer F directly to the foundation. At the same time a better guide for the plunger P in its up and down movement has been obtained. The plunger of the former machine had only the guide I and the yoke Y, whereas the new machine has an additional guide in the stuffing-box s, thus preventing wear and friction of the plunger against the lining of the box. Further-

Jan 1, 1884

By G. D. Boozer, W. H. Somerton

RESEARCH CORP., LA HABRA, CALIF. Thermal diffusivities of some typical sedimentary rocks have been measured by a rapid unsteady-state technique. Thermal data including diffusivity and conductivity are presented for the temperature range of 200" to 1,800°F. Diffusivities calculated from steady-state conductivity rneasurernents compared favorably with unsteady-state data at the lower temperatures. Unsteady-state data are less reliable at higher temperatures; reported values may be as much as 20 per cent high at temperatures in excess of 1,500°F. This is caused partly by the simplified method used in calculating diffusivity from experimental data and partly by the many thermal reactions which occur at the higher temperatures. The marked decrease in thermal diffusivity and conductivity at elevated temperatures indicates the importance of considering the temperature dependence of thermal properties in subsurface heat-transfer calculntions. Knowledge of the effects of liquid saturation, overburden and pore pressures, and heats of reaction of reservoir materials will be required before complete subsurface thermal analyses may be made. INTRODUCTION Heat-transfer calculations are becoming increasingly important in the analysis of in situ combustion and underground nuclear explosions. Thermal data for natural rock materials at elevated temperatures are generally unavailable. Calculations at high temperatures may be grossly inaccurate if temperature-dependent thermal properties of rocks are not considered. It is known that the heat capacities of rocks increase with temperature. Heat capacities may be calculated from chemical or mineralogica1 analyses of the rock system. Thermal bulk expansion of rocks is believed to be small, although few data are available. Thermal conductivities of most natural rock materials decrease with increased temperature. Thermal diffusivity, defined as the thermal conductivity divided by the product of the heat capacity and the bulk density of the material, is used in unsteadv-state heat-transfer calculations. It is apparent that thermal diffusivity decreases markedly with increased temperature. A new method, which gives a nearly continuous record of thermal diffusivity within the temperature range of 200° to 1,800°F and requires less than 1.5 hours for the run,' was used to measure the diffusivity of several sedimentary rocks. Thermal conductivities were calculated from measured bulk densities, heat capacities calculated from chemical analysis and the measured diffusivity values. Thermal conductivities were measured at lower temperatures by a steady-state technique1 to test the agreement of data obtained by the two methods.

By D. Mizer, J. B. Clark

In a recent investigation of the entire magnesium-yttrium phase diagram, Gibson and Carlsonl report the maximum solid solubility of yttrium in magnesium as 8.0 wt pct Y at 1050°F (565°C). However, independent studies of the precipitation in magnesium-yttrium alloys, 2 conducted prior to the publication of the above phase diagram, indicated a greater solid solubility of yttrium in magnesium. Accordingly, the magnesium-rich region of the diagram was re-investigated to determine more accurately the liqui-dus, solidus, and solvus of the magnesium solid solution in this system. Metallography and thermal analysis were chosen as the best corroboratory methods for accurately determining this region of the diagram. A magnesium-yttrium master alloy was prepared from yttrium of 99.9 pct purity and singly sublimed magnesium of 99.9 pct purity. Subsequently, the twelve magnesium-yttrium alloys shown in Fig. 1 were prepared using standard alloying procedures for magnesium. Metallographic samples of the alloys were heat treated under an SO, atmosphere in an electric furnace capable of control within ±3oF of the desired temperature. Alloy samples for the metallographic determination of the solvus, and for the precipitation studies were solution treated at 1000° F for 16 hr. Subsequent aging times for the solvus determination varied from a minimum of 6 hr for the higher temperatures up to 816 hr for lower temperatures. Periods of 30 min at temperature were used to generate liquation for the metallographic placement of the solidus and eutectic horizontal. The liquidus and the eutectic horizontal were determined by thermal analysis. Simple time-temper- ature heating and cooling curves were obtained from 10-g alloy samples heated and cooled in a well-insulated electric furnace. An Iron-Constantan thermocouple was placed in direct contact with the sample. The thermocouple did not contaminate the alloy sample since metallographic examination showed that the alloy melt did not wet or attack the thermocouple. The heating and cooling rates were approximately 5 to 8OF per min. The standard metallographic procedures for magnesium were used in polishing and etching the magnesium-yttrium alloys studied. Glycol etchant* was etchant was used to reveal precipitate in the solvus determination. The redetermined magnesium-rich region of the magnesium-yttrium diagram is shown in Fig. 1. The

Jan 1, 1962

By J. T. Williams

The equilibria in the V-Zr alloy system were investigated by solidus temperature determinations, thermal analysis, dilatometry, electrical resistance measurements, microscopic examination, and X-ray diffraction analysis. There is a eutectic reaction at 1230°C between a compound, V2Zr, and a solid solution containing 10 pct V in ß zirconium. V2Zr decomposes at 1300°C into liquid and a solid solution containing about 10 pct Zr in vanadium. The eutectic composition is probably about 30 pct V. A eutectoid reaction between V2 Zr and a zirconium takes place at 777°C at a very high rate. The eutectoid composition is 5 wt pct V. The limit of solubility of zirconium in vanadium was estimated to be 5 pct at 600°C. No attempt was made to determine the liquidus for the system. THE recent availability of large quantities of high purity zirconium has stimulated the study of zirconium binary systems. The equilibrium diagram for the V-Zr system has received little attention, however. Wallbauml appears to have made the first report concerning the equilibria in these alloys. He reported the existence of a compound, V2Zr, having the MgZn2 ((214) type of structure with a, = 5.277 kX and c° = 8.647 kX. Anderson, Hayes, Roberson, and Kroll2 made a survey of some potentially useful zirconium binary alloys and found that zirconium probably dissolves a small amount of vanadium. They reported the probable existence of a compound between the two elements and suggested that the zirconium-rich solid solution undergoes a eutectic reaction with this compound. Pfeil," in a critical review of the existing information, estimated that the solubility of vanadium in zirconium is less than 4.7 pct and probably less than 1.8 pct. Rostoker and Yamamoto' proposed a partial diagram for the V-Zr system in a survey paper on vanadium binary alloys. Their diagram indicates the compound, V,Zr, a eutectic reaction at 1360°C, a peritectic reaction at 1740°C, and a limit of solubility of zirconium in vanadium of about 3 pct. They obtained no information on the equilibria in the zirconium-rich alloys. In view of the potential utility of the V-Zr alloys and the incomplete knowledge concerning the equilibria in the system, an attempt was made to establish the constitutional diagram. Preparation of the Alloys Raw Materials: The vanadium for making up these alloys came from the Electro Metallurgical Corp. Zirconium came from two sources. In the beginning of the investigation, sponge zirconium from the Bureau of Mines was used in making some of the alloys. Later, iodide metal made at the Westinghouse Atomic Power Development Laboratories became available. This material was used in the preparation of all the dilatometric and resistance specimens and about two-thirds of the solidus temperature specimens. A typical manufacturer's analysis of the vanadium is shown in Table I. No other analysis of the vanadium was made. The metal contained a dispersed second phase and did not have a sharp melting point. Typical results of spectrographic analysis of the Westinghouse zirconium are shown in Table 11. These data indicate a very high purity. The Bureau of Mines sponge metal was probably less pure but had good ductility. Melting: All of the alloys used in the investigation were made by melting pieces of vanadium and zirconium together in a dc electric arc furnace similar to those of Geach and Summers-Smith, craighead, Simmons, and Eastwood," and others. Melting was done in an atmosphere of helium scavenged of residual air by the preliminary melting of a separate charge of zirconium. Each ingot was turned over and melted at least three more times before removal from the furnace to aid in the attainment of homogeneity. Alloys prepared for use in the investigation are listed with the results of solidus determinations in Table III with the exception of the following compositions upon which no solidus determinations were made: 0.29, 0.54, 4.57, and 5.55 pct V. Analysis: The weight of each ingot made from iodide zirconium was within 0.1 g of the total weight of the initial charge, about 90 g. Since each component of each charge was weighed to the nearest 20 mg for amounts less than 10 g and to the nearest 0.1 g otherwise, the gross composition of an ingot could be calculated accurately. Chemical analysis for the vanadium content of several alloys agreed

Jan 1, 1956

As knowledgeable men in the industry know, a mineral occurrence is found through prospecting but an ore deposit is "made" -made through, first, imaginative and effective exploration; thence through efficient engineering, sales and management. There are two main phases of exploration-reconnaissance and target investigation-each of which can be further divided into two additional stages (see accompanying table). The search for a new ore deposit within a known and geologically mapped mining district involves only the last two stages, whereas the search for a new orebody in a virgin geologic environment involves at least three stages and often the full sequence. Of course, some of the exploration stages may be bypassed depending on available results of previous mineral surveys and/or exploration by individuals, business concerns, and governments.

Jan 10, 1967

By D. L. Kelley

High-viscosity water injection has been proposed for use in reservoirs containing high-viscosity crude oils. Previous publications have largely ignored the possible effects of the connate water on the proposed process. This paper describes experimental work which indicates that the connate water will be forced ahead of the injected water to form a bank of low-viscosity water. This decreases the oil recovery which would be expected if such a bank were not formed. These effects are shown for a range of fluid mobilities and connate-water saturations for a five-spot injection system. In general, oil recoveries using viscous water are significantly greater than for untreated water even though they are less than would be expected if no connate water bank were formed. INTRODUCTION The effect of mobility ratio on the oil recovery of wa-terfloods has been known for many years. Muskat first pointed out that the fluid mobilities (k/µ) in the oil and water regions would affect the performance of the water-flood, and he estimated the general effect of these variables.' Since this early work, studies of the effect of mobility ratio on secondary recovery have been reported where mathematical,' potentiometric3 and scaled flow models' were used. These studies have shown that a reduction in the mobility ratio between the oil and the displacing fluid would cause additional oil recovery when water-flooding reservoirs containing viscous crude oils. Studies reported by Pye- nd Sandiford 8 have indicated that chemicals to increase injection water viscosity are now available and can be used to reduce the over-all mobility ratio of a waterflood. Where mobility ratios are controlled by the injection of viscous fluids, the connate water of the reservoir can play an important part in the displacement of the reservoir oil. The purpose of this study was to determine the effect of the connate-water saturation in waterfloods where viscous waters are used for injection. DISPLACEMENT OF THE CONNATE WATER Russell, Morgan and Muskat7 were the first to recognize the mobility of connate waters in waterflooding. They conducted waterfloods on oil-saturated cores containing 20 and 35 per cent irreducible water saturations, and found that from 80 to 90 per cent of the "irreducible" water was produced after only one pore volume of water was injected. However, their experiments were conducted at rates of flow significantly higher than those ordinarily occurring in waterfloods. Also, the cores were only from 4.0 to 8.5 cm long. Brown 4 studied a 100-cm linear sand pack which had been prepared to contain connate water and oil. He used 140- and 1.8-cp oils with injection water of essentially the same viscosity as the connate water. He found that all of the connate water was displaced by the injection water in both cases. However, the injection volumes required for complete displacement of the connate water were considerably higher in the case of the more viscous oil. To verify the results of the foregoing experiment, a 10-ft-long linear model was constructed by packing 250-300 mesh sand in a 1/2-in. diameter nylon tube. The model was evacuated, saturated with a brine of 1-cp viscosity, and flooded with a 41-cp mineral oil to the irreducible water saturation of 10.9 per cent. The model was then waterflooded by the injection of a water solution which had an apparent viscosity of 42.6 cp. The solution consisted of 0.5 per cent methylcellulose in distilled water. The viscosities of the oil and connate water were measured with an Ostwald viscosimeter. The viscosity of the polymer solution was calculated by Darcy's law using pressures measured during actual flow conditions. The ratio of the mobility in the oil region to the mobility in the inject ion-water region was approximately 0.32. The mobility ratio of the oil region to the connate-water bank was approximately 14. The mobility ratio between the connate-water bank and the injection water region was 0.024. Approximately 84.5 per cent of the recoverable oil was produced before water breakthrough. Immediately following breakthrough, oil and connate water were produced at an increasing water-oil ratio until the viscous injection water broke through. At viscous-water breakthrough, 96 per cent of the original connate water had been produced. After breakthrough of the viscous water, there was no additional production of connate water or oil. The near-

Jan 1, 1967

By J. P. Morris

PREVIOUS investigations1,2 have shown that alloying elements in liquid iron influence the thermodynamic activity of sulphur and thereby affect the partition of sulphur between metal and slag in the desulphurization process. For example, the greater efficiency of desulphurization in the blast furnace as compared to the open hearth can be attributed in part to a higher level of sulphur activity in blast-furnace metal due to the higher concentration of carbon and silicon. In the present investigation, a short study was made of the influence of manganese on the activity of sulphur in liquid iron and iron-carbon alloys. In contrast to carbon and silicon, manganese was found to decrease the activity coefficient of sulphur; and in iron-carbon alloys it counteracts to some extent the influence of carbon. However, at manganese concentrations normally present in the blast furnace or open hearth, the effect of manganese is small. Since manganese sulphide has a limited solubility in iron, manganese can act, under certain conditions as a desulphurizing agent. Considerable data on the manganese-sulphur product in carbon-saturated melts were obtained in the investigation and have been included in this report. The experimental procedure was the same as that used in the earlier investigations on the effect of silicon' and carbon' on sulphur activity. Briefly, the method was as follows: The molten alloy, contained in a graphite or sintered alumina crucible, was brought to equilibrium at a constant temperature with a mixture of hydrogen and hydrogen sulphide of constant composition by bubbling the gas through the metal. Samples of' the melt were taken for analysis at regular intervals by suction through a 2 to 3 mm bore silica tube dipped into the metal. The experiments were run in a graphite spiral resistance furnace with melts weighing 50 to 60 g. The gas bubbling tubes were made of sintered alumina and were 5/16 in. OD, 1/16 in. ID, and 24 in. long. Equilibrium was assumed to have been attained when the sulphur content of the liquid metal reached a constant value. During an experiment there was a rapid loss of manganese from the melt by volatilization. To offset this loss, small additions of manganese were made periodically. The rate of manganese addition needed to maintain a constant manganese concentration was determined in preliminary tests. In all of the experiments, deposits of manganese sulphide formed above the melts in a cooler region of the furnace. Apparently, these deposits resulted from a reaction between manganese vapor and hydrogen sulphide in the gas. To prove that manganese sulphide did not volatilize from the melts to a measurable extent, an experiment was run in which helium was bubbled through liquid iron containing both manganese and sulphur. Although manganese volatilized rapidly in this test, there was no appreciable loss of sulphur. Volatilization of manganese sulphide from a melt would have led to an apparent equilibrium condition in which the sulphur content of the metal was lower than the true equilibrium value. The experimental results are shown in the first seven columns of Table I. The data in the last two columns were obtained from the previous work on the effect of carbon' and show what the results would have been in the absence of manganese but with temperature, gas composition, and carbon content of the metal remaining the same. Comparison of the last four columns show that, in the presence of manganese, the sulphur content of the metal increased at equilibrium and the activity coefficient of sulphur decreased. However, the results show that, for manganese concentrations below 3 pct, the effect of manganese is small. The values for activity coefficient of sulphur given in Table I were calculated from the following relations: S (in liquid metal) + H2 (gas) = H2S (gas) [l] K ph2s/?s X %S X phg = 0.00251 [2] where K is the equilibrium constant for the reaction, PH2S and ph2 are the partial pressures of hydrogen sulphide and hydrogen, respectively, and ?s is the activity coefficient of sulphur. The standard state for sulphur was taken to be a 1 pct solution of sulphur in pure iron. The numerical value for K at 1600°C was determined in the earlier work. For the purpose of showing graphically the results of the tests run at 1600°C, the activity coefficients of sulphur were recalculated so as to correspond to a manganese concentration in the metal of 2 pct in each case. In the calculation it was assumed that the increase in sulphur content of the metal at equilibrium caused by the presence of manganese

Jan 1, 1953

By Richard A. Pomeroy

This mine, known also as the A very Mine, is situated on Petite Anse Island, Iberia Parish, Louisiana. The island is about four miles from Vermillion Bay, an arm of the Gulf of Mexico, and is one of four islands or hills surrounded by the sea-marsh, as shown in the accompanying map. (Fig. 1.) A fifth, Joe Jefferson's Island, or hill, is some distance from the sea-marsh. These five islands: Belle Isle, Cote Blanche,Grand Cote, Petite Anse and Jefferson, appear to be the tops of submerged hills, and occupy a line having nearly a northwest trend. To the north are a series of hillocks that extend at intervals to the hills of Northern Louisiana, which in turn appear to run into the Ozarks of Arkansas. Near the mine there is sandstone, also a thick vein of lignite. Bones of the mastodon have been

Jan 1, 1889

By L. A. Roe, John Jan

Iodine is a soft, lustrous, grayish-black nonmetallic element with a density of 4.9. It is the least active of the four members of the halogen family. The other members are, in order of increasing activity, bromine, chlorine, and fluorine. Iodine is a solid at ordinary temperatures, while bromine is a liquid and chlorine and fluorine are gases. Iodine melts at 113°C and volatilizes at 184.4°C to a blue-violet gas with an irritating odor. It occurs in nature only as iodates and iodides or other combined forms. It was discovered by Bernard Courtois in France in 1811, who noticed its presence as an unknown substance in crude soda ash obtained from burning seaweed. Gay-Lussac recognized it as a new element and named it iode, from the Greek word "ioeides or iodes" for violet color (MacMillan, 1970). The world production is not known with any great certainty, but it is probably between 25 and 35 million lb per year, of which about 30% is consumed in the United States. Geology and Mineralogy Iodine compounds occur as a minor constituent as a mineral in the Chilean nitrate deposits and in solution in brines and seawater. According to the US Geological Survey, it is the 47th most abundant element in the earth's crust. The minerals lautarite, Ca (I03)3 (calcium iodate), and dietzeite, Cat (103)2 (CrO4), (calcium iodate-chromate) are found in Chilean nitrate deposits which are located in Antofagasta and Tarapaca provinces on the eastern slope of the coast range in a desert area. Various brines contain iodine compounds. Seawater contains about 0.05 ppm of iodine and some seaweeds will extract and accumulate it up to 0.45% on a dry basis. Some coals in West Germany also contain iodine compounds. The known and potential sources of iodine reported in 1968 are given in Table 1. Table 2 lists estimated world iodine reserves. Iodine has been recovered from brines in Java, Indonesia, France, England, and the USSR. Iodine has also been recovered from seaweed in Ireland, Scotland, France, Japan, Norway, and the USSR. The indicated reserves and future resources of iodine are large but have never been adequately measured. Analysis Iodine as the free element can be detected by the characteristic blue color it gives to a starch solution. Quantitatively it is determined as the free element by titration with standard thiosulfate solutions using starch as an indicator. Colorimetric methods are also applicable. Markets and Prices Iodine and its compounds are generally marketed in the form of: iodine, crude; iodine, resublimed; calcium iodates; calcium iodide; potassium iodide, sodium iodide, and numerous organic compounds. Product Specifications Crude iodine, World market: 99-99.5% 12. Crude iodine, US produced, average: 99.8% 12. Crude iodine, USP XVII Specs: not less than 99.8% percent I2. Resublimed iodine is usually 99.9% and ACS specifications call for not over 0.005% total bromine and 0.020% nonvolatile materials (Anon., 1971). Prices, c.i.f. United States, for iodine have been steadily increasing from $1.18 per lb of crude in 1967 to $6.37-7.27 in January 1981 (Anon., 1981). In 1980 the price of iodine increased by 50%.

Jan 1, 1983

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Notched and unnotched tensile specimens of wrought and recrystallized, oxygmted and hydro-genated tantalum and columbium were tested over a range of temperatures selected to encompass the ductile-to-brittle transition. Increasing the oxygen content of tantalum and columbium increased their strength, and raised their ductility transition temperature, but did not cause a marked deterioration of notch properties below that of commercially pure material. The adverse effects of oxygen were more pronounced for recrystallized structures than for wrought material. The effects of hydrogen are complicated by strain aging or slow strain rate hydrogen embrittlement at -105°F. However, in general, hydrogen had only a minor effect an strength, but markedly increased the effective transition tem-terature and caused a deterioration of notch properties . BCC metals including the refractory metals in Groups Va and VIa (V, Cb, Ta and Cr, Mo, W) can be expected to undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures.' Notch embrittlement is associated with this phenomenon, and can be a serious design problem. Table I compares the tensile transition behavior and notch sensitivity of commercially pure Group Va and VIa refractory metals. The Group VIa refractory metals have considerably higher transition temperatures, and become notch sensitive at higher temperatures, than do the Group Va refractory metals. In addition, the Group VIa refractory metals are sensitive to metallurgical structure. Recrystallized structures generally have higher transition temperatures than wrought material of the same composition. The relatively poor transition behavior of the recrystallized structures of these metals is generally attributed to the segregation of interstitial impurity atoms at grain boundaries. Pronounced sensitivity to structure is not evident with commercially pure Group Va refractory metals, however. Since these metals have higher solubilities for interstitial elements than do the Group VIa metals ,4 it can be expected that higher total interstitial concentrations are necessary to develop a comparable degree of grain boundary segregation and to produce a similar sensitivity of transition temperature to structure. Increasing only the concentration of interstitial atoms in solution would tend to increase the flow stress of a metal in relation to its cleavage fracture stress and thereby raise its transition temperature, but would not be expected to cause a marked sensitivity of transition temperature to structure. A research program has been conducted at the Battelle Memorial Institute to evaluate the effects of interstitial oxygen and hydrogen on the transition behavior and notch sensitivity of tantalum and columbium, and to evaluate the effects of structure on "contaminated" material. EXPERIMENTAL PROCEDURES Notched and unnotched tensile specimens of oxygenated and hydrogenated tantalum and columbium with both wrought and recrystallized structures were tested over a range of temperatures selected to encompass the ductile-to-brittle transition Oxygen levels selected for study in both tantalum and columbium were nominally 500 and 1000 ppm, whereas nominal hydrogen contents were 150 and 500 ppm in tantalum and 150 and 300 ppm in columbium. Oxygen and hydrogen additions were made directly to 6-in. lengths of 1/2-in.-diam electron beam melted wrought bar stock, in a Sieverts Apparatus. Subsequent high-temperature annealing was required for homogenization of the oxygenated material, but was not necessary in the case of hydrogenated stock. The oxygenated and hydrogenated bars were then swaged to 1/4-in.-diam rods. Tensile specimen blanks were cut from the 1/4-in.-diam rods and annealed to achieve stress-re-

Jan 1, 1963

By P. Payson

Intergranular corrosion in corrosion-resistant chromium-nickel steels has been widely discussed in the last few years. So far as the author knows, nothing has been published which definitely shows that this tendency can be eliminated, although suggestions have been made that a remedy is possible if certain specifications are satisfied. Strauss, Schottky and Hinnüberl suggested an increase in chromium content to an extent that would prevent the impoverishment of chromium on carbide precipitation sufficient to cause impaired corrosion resistance in the matrix. Pilling2 suggested an increase in nickel, so that the stability of the austenite matrix would be increased. Aborn and Bain3 say that "intergranular attack—may be eliminated by preventing carbide precipitation (e. g., by lowering the carbon content or somehow raising its solubility) or by precipitating it permanently under conditions which will not remove chromium from solid solution so drastically at any points." In a later paper Aborn and Bain4 state that many different metallic elements, tungsten, vanadium, copper, aluminum, molybdenum, titanium and zirconium, have been added in small percentages to increase the stability of these alloys, but that it has been reported that according to the copper sulfate test these added elements act only to retard the intergranular corrosion. and that increased nickel and chromium contents have similar effects. Newell5 showed that the lower the quenching temperature before reheating, the less severe was the intergranular attack.

Jan 1, 1932

By Donald L. Katz, Leslie J. Noaker

Experimental data are presented for hydrate formation conditions for mixtures of hydrogen sulfide and methane. Vapor-solid equilibrium constants for hydrogen sulfide are also presented. Equilibrium constants, defined here as the ratio of the mole fraction of hydrogen sulfide in the vapor phase (dry basis) to the mole fraction of hydrogen sulfide in the solid phase (dry basis), were calculated using the vapor-solid equilibrium constants for methane presented in an earlier paper. The conditions at which a natural gas will form gas hydrates with water may be computed from its composition, when hydrogen sulfide is present in addition to carbon dioxide and the paraffin hydrocarbons. INTRODUCTION Many gases are known to form solid hydrates in the presence of liquid water at temperatures above 32°F. This hydrate formation is of importance to the natural gas industry inasmuch as most of the constituents found in natural gases will form hydrates. The attention of the industry was called to hydrates by Hammer-schmidtl0 in 1934. A number of papers have been written giving the temperatures and pressures at which these hydrates will form3,4,5,6,7,8,9,10,13,14,15,18,19 and a bibliography on the subject has been compiled13. Deaton and Frost4,5,6,7,8 report work for various pure gases and for some natural gases. Katz and co-workers3,4,13,14,18,19 have reported data for various gases at high pressure. They developed a method of predicting conditions for hydrate formation from equilibrium constants3,19 and from gab gravity." The effects of anti-freeze agents on the formation of hydrogen sulfide hydrate were reported by Bond and Nelson.' The hydrogen sulfide-water system, including hydrate, has been the subject of recent investigation by Sage and co-workers." Mixtures of hydrates behave as solid solutions and an equilibrium exists between the vapor phase and the solid phase that appears to be comparable to the equilibrium between vapor and liquid phases.3,10 By means of the vapor-solid equilibrium constants which have been published for methane, ethane, propane, iso-butane, and carbon dioxidel6 it is possible to determine the temperature and pressure at which hydrates will form for a specific gas mixture when water is present. Hydrogen sulfide which is frequently found in natural gases has a very strong tendency to form hydrate and must enter the solid solution when present in a natural gas forming a hydrate. To determine the effect of hydrogen sulfide when computing the conditions for gas hydrate formation, it is necessary to have the equilibrium constant giving the ratio of the concentration of hydrogen sulfide in the gas phase to the concentration in the solid phase. This paper presents data on hydrate formation for mixtures of hydrogen sulfide and methane and presents the equilibrium constants which were calculated from these data. EXPERIMENTAL PROCEDURE The apparatus used to determine the conditions of hydrate formation for the methane-hydrogen sulfide system was similar to that employed by previous investigators.3,18,19 A charge gas cylinder was used to supply the hydrogen sulfide-methane mixtures, called the charge gas, and to supply the pressure up to 1.000 psia. This

Jan 1, 1955

By N. Cabrera

IN a recent paper Kuczynski' studied the rate at which the crack between a metallic plane and a spherical particle of the same material is filled up gradually when heated at temperatures near the melting point. If x is the radius of contact between plane and sphere (fig. I), Kuczynski shows experimentally that x5 = At [1] where t is the time. Assuming that the mechanism of transport of matter is the volume diffusion of vacant lattice sites, he is also able to prove Eq 1 theoretically. The constant A contains as a factor the self-diffusion coefficient of the metal and he shows that the values for this coefficient deduced from his experiments yield the same activation energy as that calculated by other methods, which is a confirmation of this point of view. Kuczynski has also considered theoretically the law of growth of x which would be expected if surface diffusion were the important mechanism. He suggests that x should then obey a law of the form x7 = At, and claims to be able to decide the mechanism involved from the observed law of growth., The purpose of this note is to prove this incorrect. On the contrary, when the mechanism is surface diffusion Eq 1 is also obeyed, but with a different constant A. Following Kuczynski, we suppose the bottom of the crack (surface A A) to have an average radius of curvature p. As a result of this curvature the concentration of adsorbed atoms in this surface, n(p) per cm2, will be smaller, and the concentration of vacant lattice sites in the neighborhood, N(p) per cm3, will be larger than the corresponding concentrations, n(w) and N(w), for a flat surface. For all practical cases we can write Thomson's formula in the form n(co)— n(P) N(P)—N(cc) _ 2a-a" n(oo) JV(co) kTp [2] where u is the surface energy of the metal and a the interatomic distance. 1. Let us now consider the mechanism of surface diffusion. We suppose the concentration of ad-

Jan 1, 1951

By R. K. Waring

A KNOWLEDGE of the mutual liquid solubility of zinc and lead is of importance in various phases of zinc metallurgy. The determination of this solubility has been the subject of numerous investigations, but unfortunatel, the results vary widely, particularly at higher tempera-tures, and it has been impossible to decide what data are most reliable. It was decided to investigate the matter and in view of the disagreement in the published results, it was felt necessary to take rather unusual precautions to insure the reliability of the data. For this reason deter-minations were made by four different methods, and the procedures of several of the previous investigators were duplicated. The previously used methods can be divided into two classes: methods involving freezing the entire melt and taking samples of the lead-rich and zinc-rich phases in the solid state, 1,2 and methods in which the. samples are taken while the bath is liquid and at the desired temperature. 3,4 Data obtained by methods involving freezing the entire melt show much lower solubility of lead in zinc than methods in which the liquid is sampled at temperature. The latter method was used by Spring and Romanoff5 and by Hass and Jellinek.6 The results of these two investi-gations are in agreement at temperatures near the melting point but at higher temperatures Hass and Jellinek find a higher mutual solubility.

Jan 1, 1934

By I. Iwasaki, P. L. De Bruyn

Electrical double-layer properties of the silver sulfide-solution interface in different electrolytes and the influence the properties exert on the adsorption of dodecylammonium acetate (DAA) were studied using an electrochemical titration technique. The flotation behavior of silver sulfide was observed using DAA as collector and the results were correlated with adsorption measurements. Silver and sulfide ions were identified as the potential determining ions and their adsorption densities were measured as functions of the pAg and of the ionic strength at two different pH values. The point-of-zero-charge (PZC) was observed to be at pAg 10.2, the value being independent of pH and of the nature and concentration of the electrolyte used. The surface charge of silver sulfide in these electrolytes was positive for pAg values less than 10.2 and was negative for pAg values greater than 10.2. The adsorption of amine on silver sulfide surfaces at pH 4.7 was found to be strongly dependent on the pAg. A shift in the PZC towards a lower pAg due to the adsorption of amine indicated a specific affinity of dodecylammonium ion towards silver sulfide surfaces. At pH 9.2 a strong adsorption of the undissociated amine molecule was indicated. The PZC shift towards a higher pAg and the adsorption of the amine was virtually independent of the interfacial electrical conditions.

Jan 1, 1972

By D. L. Harris, A. M. Gaudin

THE following results, presented here in condensed form,1 were obtained in a preliminary study of the adsorption of n-hexane thiol, hexyl mercaptan, on sphalerite, zincite, willemite, and quartz, from aqueous solution and from a gas. Interest in this subject was aroused by a Belgian report2 of effective use of hexyl mercaptan for flotation collection of oxidized zinc minerals. The relatively low boiling point, 149°C, of the mercaptan3 suggested the desirability of extending the usual measurements of partition of collector between aqueous solution and gas and between gas and mineral. It is believed that this paper presents the first measurements of this type on a flotation system. Attempts were made to carry out the measurements at equilibrium, but as the work progressed it became increasingly doubtful that this desirable condition had been achieved. To control composition and extent of the gas phase, the apparatus was a wholly-enclosed thermally-controlled glass system. Because of these constraints and the desirability of dealing with pure minerals, a scale of operations was chosen in which a few grams of deslimed mineral were used in each test. It was also necessary to choose a particularly sensitive method for mercaptan analysis, and in fact a method that would permit the experimenters to follow the approach to equilibrium. For these reasons mercaptan marked by radiosulphur 35 was used. An analysis was made for the radiosulphur by a modification of the method of Gaudin and Carr.4

Jan 9, 1954

By GUY C. RIDDELL, Donald M. Liddell

THE electronic arts today constitute the outstanding development in the field of rare metals, if not indeed in the arena of scientific progress at large. The year 1930 may become known as the year in which the electronic tube took hold of the wheels of industry; it is the year in which the tube's emancipation from the art of communication was proclaimed. The little tube which made a $500,000,000 industry out of a vacuum has now been applied to mining, manufacturing, transportation, chemistry, and other industries. Not many appreciate the extensive utility that e1ectroni.t tubes have already found in transportation, where they control the speed and security of express trains, as well as operate traffic lights on important highways-in the case of the Detroit-Windsor bridge counting the traffic and instantly turning the reports into the superintendent's office some distance away. In an Ohio steel mill, ten-ton ingnts 'rash back and forth through the rolls, reversed by their own shadows. The vacuum tube also starts, stops, and levels, fast passenger elevators.

Jan 1, 1931

By P. A. Flinn

ALTHOUGH many physical properties of superlat-tices have been studied intensively, relatively little attention has been paid to their mechanical properties until recently. Even for the well-known transformation in 0 brass, the effect of the transformation on plastic behavior has only lately been extensively investigated.''' A partial analysis of dislocation structure in superlattices has been given by cottrel13 and his theory agrees well with the experimental results on CU3AU.4,5 His analysis, however, is implicitly limited to low-temperature effects, since it does not include the behavior of dislocations at temperatures high enough for diffusion, and hence climb, to occur. The work of Herman and Brown2 on the creep of 0 brass indicates that important effects occur under such conditions, and consequently, the theory should be extended to include them. Such high-temperature effects cannot be observed in Cu3Au, since it disorders below the temperature at which diffusion occurs at a reasonable rate. There are materials of the same structure, however, such as Ni3A1, which retain their order up to, or close to, the melting point. GEOMETRY OF THE COMMON SUPERLATTICES The two best-known ordered structures are the 0 brass type, B2, shown in Fig. 1, and the Cu3Au type, Ll2, shown in Fig. 2. In the B2 structure the (000) and (1/2, 1/2, 1/2) sites are different in that they are occupied by different types of atoms. The symmetry of the structure is then lowered from a body-centered cubic, A2, in which the sites are equivalent, with atoms located randomly in the sites, to simple cubic. This lowering of symmetry has the consequence that two types of regions may occur within a crystal: regions where A atoms are in the (0, 0, 0) sites, and regions where they are in (1/2, 1/2, 1/2) sites. The boundary between two such regions will contain bonds between like atoms, and be a surface of higher energy. These regions are known as antiphase domains and the boundary as antiphase boundary. In the B2 structure, boundary formed during the ordering process should disappear as a result of domain growth, since any domain growing to the boundary of two others will join one and engulf the other.' In any well annealed crystal, only a single domain should exist, with antiphase boundary present only in connection with dislocations, as discussed below. The L1, structure is related to the A1 (face-centered cubic) in much the same way as the B2 is to the A2. The face-center sites are occupied by A atoms, and the corner sites by B atoms. The symmetry is again lowered to simple cubic, and antiphase domains can exist. In this case, however, there are four initially equivalent sites in the unit cell: (0,0,0), (0, 1/2, 1/2), (1/2,0, 1/2) and (1/2, 1/2, 0). In the ordered structure any one may be occupied by a B atom and the other three by A atoms. Thus four types of antiphase domains can occur in this structure. This is sufficient to permit a metastable "foam structure" to exist within a crystal.''7 Antiphase boundaries along three different planes are shown in Figs. 3, 4, and 5.* *The presence of a layer of disordered material between antiphase domains, as suggested by Jones and Sykes8 does not seem likely. Such a layer would be a region of unnecessarily high energy which could readily be reduced by the formation of the type of boundary discussed here.__________________________________________________________ The notation (111) [110] means a boundary lying along a (111) plane between antiphase regions related by a 1/2 [I10] translation. It may be seen in Figs. 3 and 4 that an antiphase boundary usually results in incorrect nearest neighbors (shown connected by braces). However, as pointed out by Wilson, a boundary of the (001) [I101 type can exist

Jan 1, 1961

By G. Kimmel, A. Bar-Or

The rate of nucleation and the rates of both lateral and longitudinal growth of martensite plates (needles) in b—a transformation were determined as a function of temperature, in various U-Cr alloys. The activation energies for nucleation and both modes of growth were calculated from the experimental results. The identical values for lateral and longitudinal growth clearly indicate that both are controlled by the WHITE,' Mott and Hines and Holdeen3 showed that characteristic martensite plates (needles) appear in U-Cr alloys during the transformation 8 —0 in the lower temperature range (up to -300°C). Holden pointed out that the rate of growth of the individual martensite plates under isothermal conditions is same mechanism. Lomer's suggestion that single-atom movement over subatomic distances controls the specially slow growth of martensite receives further support from the present kinetic study, which shows that the growth rate can be described quantitatively by known formulas for the growth rate in processes involving single-atom movement. very slow, and suggested that this is due to the slowness of the relief of the stresses engendered during the growth of the individual plates. lomer4 attributed the slow growth to the complexity of the atomic adjustment at the growing interface b/(u. In the present work the rates of nucleation and growth of martensite plates in U-Cr alloys were studied by direct observation, in order to elucidate the mechanism which controls their characteristic slow growth.

Jan 1, 1968

H. 0. HOFMAN, Boston, Mass (written discussion*).-The paper by Mr.. Pyne gives clear evidence of the difficulties the metallurgist is likely to encounter when he tries to recover in the blast furnace the metal from old chromite lining used as a refractory material in the copper reverberatory furnace. It appears that chromite cannot be fluxed at temperatures which usually prevail in copper blast furnaces. This calls to mind the freezing-point curve drawn by M. Simonis1 of mixtures of chromite and kaolinite. The chromite used in the experiments contained 52.9 per cent. Cr203, 22.6 FeO, 4.8 AI203, 9.6 Si02, .10.1-MgO; FIG. 1. the kaolinite was clay from Zettlitz with 98.5 per cent. clay-substance: The accompanying curve shows that the eutectic mixture with 35 per cent. kaolinite and 65 per cent. chromite freezes at Seger cone No. 15 (1435° C.), while kaolinite fuses at cone No. 35 (1770° C.) and chromite at cone No. 42 (2000° C.). The curve indicates that the difficulty in the blast furnace can be overcome by having at the smelting zone a temperature much higher than is usual in copper smelting; a charge composition similar to that prevailing at the Mansfeld copper smeltery -which gives with 23 per cent. coke a, slag of the composition Si02, .49.09; .(FeMg)0, 5.58; (CaMg)0, 16.02; A1203,-16.02-might flux and fuse chromite.

Jan 3, 1918