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By F. E. Buch

The smelter is designed for a production capacity of 10,000 short tons of blister copper per month, when operating on the present concentrate grade. The :smelter lay-out is shown in Fig I. The major units of equipment comprise two reverberatory furnaces, three 13 by 30 ft Peirce-Smith converters, two straight line casting machines, one being served by a 13 by 30 ft holding furnace and the other by a ladle tilting quadrant, two converter aisle cranes and two converter blowers. The plant is compact and the general arrangement of standard gauge railway tracks and conveyor belts provides for a smooth flow of incoming materials and metallurgical products. Concentrate is received by conveyor belts and fluxes in standard railway trucks. The local track system is covered by an electric trolley locomotive. The Smelter treats a wet (10 pet moisture) flotation concentrate containing approximately 53 pct total copper and 0.9 pet oxide copper. The predominating minerals are chalco-cite, chalcopyrite and bornite accompanied by small quantities of malachite and cuprite. The gangue is highly siliceous and requires limerock as a flux. Metallurgy would be straightforward were it not for the necessity for eliminating bismuth which occurs as an impurity in the ore along with the copper. Directly or indirectly most of the Smelter problems can be traced to the necessity for bismuth removal. Copper recovery, based on new copper treated, averages 97.5 pct. General Description Flotation concentrate, containing 10 Pet moisture, is conveyed from the filter plant to the smelter storage bins by conveyor belts, the material being weighed in transit by a revolving drum type of weigh-hopper manufactured by Samuel Denison and Son, Ltd. The weigher consists of a steel drum with dished ends carried on a horizontal shaft and rotated by an 8 hp squirrel-cage motor through a worm and Spur reduction gear. A feed mouth in the drum permits of filling and discharging. The whole unit is supported on a framework resting on weighing levers, which in turn connect to transfer levers, thence to an indicator of the steelyard type situated 16 ft from the centre line of the drum. The indicator is of the "Denison" patent equilibrium controlled ticket stamping type, insuring mistake-proof records by a combination of electrical and mechanical movements which Prevent the operator from printing until the cover enclosing the steelyard is closed and until the poise-weights have been Set correctly to the weight of the hopper and contents. The machine is capable of weighing 30 short tons at a time but the usual load is 28 tons. After obtaining the gross weight the drum is rotated and discharged into a receiving bin situated below it. The empty drum is weighed and the net weight re-

Jan 1, 1949

By H. E. McKinstry

Movement on a fracture of irregular shape can cause local widening of the fissure and thereby offer freer channelways for circulation of ore-depositing solutions. This influence: coupled with large areas of wall rock available for reacting with ore solutions in brecciated and shattered ground can account for locally active deposition of metals and the resulting ore shoots. Such irregularities in the fracture system may be caused by local variations in the strength of rocks and by pre-existing lines of weakness, especially if these stand at favorable angles to certain components of the fracturing stress. Therefore correct interpretation of the mechanics of fracturing should permit deductions as to structurally favorable places on unexplored portions of the vein system. Introduction It has long been recognized that movement on a curved or irregular fault surface is capable of separating the walls in certain portions of the fault, but until very recent years the importance of this mechanism as a factor in localizing ore shoots has escaped proper recognition. A short time ago W. H. Newhouse' presented a careful analytical study of displacements and their corresponding open spaces. For reasons that will be discussed later, it frequently happens that portions of the vein which are favorably oriented are not merely wider but also richer than the average. In many cases the widening with its accompanying richness coincides with very minor changes in the dip or strike of the vein, irregularities that commonly escape notice unless the vein is mapped in detail and a careful geometrical analysis made. While the relationship between the width of the vein and the changes in dip or strike has been recognized as a matter of observation, the irregularities have been accepted as more or less the result of accident. There has been very little effort except in isolated cases to find out the causes of these changes in dip or strike. Yet it is clear that if the causes can be recognized and expressed in terms of geologic structure the geologist will know where to look for repetitions of these favorable conditions either on extensions of the same vein or on adjoining veins. Any lack of understanding of the causes is due to the limitations of our ability to interpret our observations and not to the sheer capriciousness of

Jan 1, 1941

By H. E. McKinstry

Movement on a fracture of irregular shape can cause local widening of the fissure and thereby offer freer channelways for circulation of ore-depositing solutions. This influence: coupled with large areas of wall rock available for reacting with ore solutions in brecciated and shattered ground can account for locally active deposition of metals and the resulting ore shoots. Such irregularities in the fracture system may be caused by local variations in the strength of rocks and by pre-existing lines of weakness, especially if these stand at favorable angles to certain components of the fracturing stress. Therefore correct interpretation of the mechanics of fracturing should permit deductions as to structurally favorable places on unexplored portions of the vein system. Introduction It has long been recognized that movement on a curved or irregular fault surface is capable of separating the walls in certain portions of the fault, but until very recent years the importance of this mechanism as a factor in localizing ore shoots has escaped proper recognition. A short time ago W. H. Newhouse' presented a careful analytical study of displacements and their corresponding open spaces. For reasons that will be discussed later, it frequently happens that portions of the vein which are favorably oriented are not merely wider but also richer than the average. In many cases the widening with its accompanying richness coincides with very minor changes in the dip or strike of the vein, irregularities that commonly escape notice unless the vein is mapped in detail and a careful geometrical analysis made. While the relationship between the width of the vein and the changes in dip or strike has been recognized as a matter of observation, the irregularities have been accepted as more or less the result of accident. There has been very little effort except in isolated cases to find out the causes of these changes in dip or strike. Yet it is clear that if the causes can be recognized and expressed in terms of geologic structure the geologist will know where to look for repetitions of these favorable conditions either on extensions of the same vein or on adjoining veins. Any lack of understanding of the causes is due to the limitations of our ability to interpret our observations and not to the sheer capriciousness of

Jan 1, 1941

By J. F. Enrietto

It is shown that one cannot approximate the broad internal friction Peaks observed in the Fe-Mn-N system as the sum of a number of subsidiary Peaks and still vetain the concept of a single relaxation time. Furthermore, the approximation of manganese affectirg only nearest neighbor interstitial sites is shown to be incompatible with the experimental results. The results of this experiment show that the influence of manganese in the ferrite lattice extends over 3 to 4 atomic distances. NUMEROUS experiments have shown that the presence of relatively small amounts of substitutional alloying elements can profoundly affect the profile of the damping spectrum in the vicinity of the Snoek peak in bee metals.1-7 Dijkstra and Sladekl observed this phenomenon in Fe-Mn-N alloys where it appeared as a broadening and shifting of the Snoek peak to higher temperatures. The authors interpreted this as being the result of a superposition of two damping maxima—the normal Snoek peak, located at its usual position and having a normal half-width, and an interaction peak having a normal half-width, but occurring at a somewhat higher temperature. They prclposed that the interaction peak was caused by nitrogen atoms jumping from Fe-Mn sites to Fe-Fe sites, the Fe-Mn interstitial sites having one manganese and one iron atom as nearest neighbors, and the Fe-Fe sites having two iron atoms as nearest neighbors. They further suggested that the Fe-Mn sites had a lower energy than the normal Fe-Fe sites because of the presence of the adjacent manganese atoms. From the relative heights of the two postulated damping peaks, the dif-

Jan 1, 1962

By A. Tanaka, K. G. Carroll

The existence of local room-temperature plastic flow in germanium, which has been a subject of controversy for nearly two decades, has recently received renewed attention, albeit no more agreement than hitherto. Phenomenologically one major facet of the problem has been reduced to the question whether or not indentation can be effected in germanium without the introduction of cracks. That plastic flow can be induced at room temperature by fracture appears to have been rather convincingly demonstrated recently by Suzuki and Kamada and by Noble and Henisch.1 The literature contains both direct and incidental references to Vickers and Knoop indentations showing no cracks, within resolution of optical microscopy. Recently, however, following a controversy on the subject,2,3 johnson4 made a study of indentations produced by spherical indenters and concluded that these are accompanied by cracking. This study in-

Jan 1, 1969

By R. M. Brick

AN increased demand for information in regard to the effect of gaseous elements in steel has accompanied the recognition of the importance of grain size. Attempts to correlate grain-size characteristics with gas con-tent, particularly oxygen in solution or in the form of included metallic oxides, have not been universally successful. Certain definite effects of dissolved gases are recognized; specifically, the role of hydrogen in causing internal cracks or "flakes" and that of nitrogen in preventing excessive grain growth of ferritic chromium steels. When irregular behavior or properties are found in a well-known steel and no definite cause for the abnormality may be assigned on the basis of chemical and metallographic tests, dissolved gases are frequently blamed as the culprits. The solubilities of hydrogen1 and nitrogen2 in pure liquid iron are known but of the ternary systems, iron-alloying element-gas, only the Fe-Si-N3 and Fe-Cr-N systems have received attention and here the study was confined to liquid alloys. Krivobok4 published a curve show-ing the solubility of nitrogen in liquid Fe-Cr alloys but gave no informa-tion on the experimental procedure employed. The considerable experimental work reported on the Cr-N binary alloys has been reviewed by Hansen.5 It is generally agreed that the nitride CrN is a stable phase although the existence of nitrides within limited temperature ranges of stability, viz., Cr3N2 and Cr2N, has been disputed, Adcock6 and others7 have reported a eutectic between Cr and CrN at 1580°C., although the supporting evidence is not complete.

Jan 1, 1940

By Wiley C. Buford

Gary Works No. 1 BOP Shop is a three furnace shop which went into operation December, 1965. The heat size is over 200 tons, with a substantial percentage of the production used to feed a Continuous Slab Caster. Vessels are driven by a shaft mounted bull gear and main housing utilizing eight 35 HP flange mounted motors and primary gear reducers. Torque absorption is controlled by two spring actuated torque arms. At 1:00 p.m. on Thursday, August 6, 1970, as "E" furnace was being turned down for a preliminary test, the drive side trunnion bearing failed. The furnace dropped slightly and shifted several inches north in the direction of the drive unit. The decision was made to tap the heat which was done without incident and the vessel uprighted. No attempt was made to completely drain the slag from the vessel, so as to avoid any further damage to the trunnion shaft bearing surface. The bearing failure occurred approximately four years and eight months after start up of the shop. Unfortunately ?M? furnace had gone down for a normal reline two days prior to the bearing failure, leaving the shop with only one operating furnace.

Jan 1, 1972

By C. Altstetter, Y. Huang, E. de Lamotte

Nitrogen was introduced into pure niobium (colutn-bium) and dilute Nb- Zr alloy wires by equilibration with pure nitrogen gas at high temperatures. Room-temperature hardness was correlated with the alloy composition, heat treatment, and microstructure. Hardness was found to be most sensitive to the amount of nitrogen in solution; however, a significant hardening up to 500 Dph look place upon aging of quenched alloys. A coarse dispersion of nitride did not significantly increase the hardness of the material though the nitride was found to have a hardness of 1400 Khn. BY now the marked effect of nitrogen on the properties of bcc refractorv metals is we ll-documented. There are few studies, however, in which the state of the solute has been carefully controlled. Indeed, the composition-temperature-pressure relationships in nitrogen-refractory metal systems have been determined precisely for only niobium and tantalum.'-4 Most investigations on niobium have dealt with alloys High-nitrogen alloys cleaved on (100) planes and had negligible ductility. Precipitation was found to occur in either a discontinuous or a continuous fashion, depending on the composition and cooling rates. Upon cooling, the precipitation first proceeded discontinu-ously by the nucleation of nilride needles at subbound-aries and subsequent growth of a two-phase microcon-stituent. At lower temperatures continuous precipitation occurred in the subgrain interior ahead of the discontinuous precipitation interface. containing nitrogen, carbon, and oxygen in significant but uncontrolled and, in several instances, undetermined amounts. Thus, there has been some uncertainty regarding the presence and the distribution of precipitates. This paper presents results which relate the hardness and microstructure to the heat treatment and nitrogen content of niobium and Nb-Zr alloys. Niobium rod* produced by the Wah Chang Corp.

Jan 1, 1968

By J. D. Hunt, R. J. McDonald

It is proposed that extensive fluid motion occurs between the dendrites of a Partially solid casting and it is suggested the A segregates in steel castings are a direct result of this motion. The fluid flow arises because of density differences between liquid ahead of the dendrites and the interdendritic liquid. Experiments are described on a model system investigating this fluid motion. The importance of interdendritic fluid flow is discussed with reference to longitudinal segregation. SERIOUS macro segregation is often found in large killed steel ingots. Among the most common segregates are those known as A and V, Fig. 1. The A segregates are arranged over the surface of cones, the wide parts being at the base of the ingot. The A segregates are pencil like in shape and extend from the columnar into the equiaxed region. The V segregates are distributed over inverted cones but have a less well defined shape. They occur at the center of the ingot. Because of the commercial importance of macro inhomogenities these segregates have attracted wide-scale attention. The segregates contain alloying elements and impurities which depress the freezing temperature and are thus the last liquid to freeze. A number of explanations have been proposed to explain their presence. It has been suggested1'' that the segregates are the result of the equiaxed zone growing towards the columnar region together with the interaction of convection within the bulk liquid. It has also been proposed that the segregates are the result of nucleation and rapid growth ahead of the dendritic front.3 Neither of these explanations is completely satisfactory because A segregates are pencil shaped and are not found as continuous cones. In this paper an alternative mechanism is proposed, and experiments are described on a model system to determine whether the mechanism occurs in practice. It is thought that A and V segregates are not peculiar to steels but should occur in many other large castings. Fluid motion within the bulk liquid region of a casting has been extensively discussed. Little attention has been paid to fluid motion within the partially solid regions. The work415 that has been done has been mainly concerned with the fluid motion which results from the volume contraction on freezing. The volume contraction is used to explain various types of macro segregation. The present authors suggest that in many cases the fluid flow resulting from volume contraction will be small compared with that due to other causes. When the columnar region is growing, the liquid still remaining between the dendrites has a much lower temperature near the ingot walls than at the dendrite tips. The composition of the liquid in contact with solid will vary with temperature. The density of the liquid will thus vary both because of changes in temperature and composition. The layers of different density liquid will give rise to a slow but steady liquid flow through the interdendritic regions. If there is no density change with composition, the temperature gradient within the dendritic region should give rise to a downward flow between the dendrites, shown schematically in Fig. 2. When the liquid density changes appreciably with alloy concentration this motion could either be en-

Jan 1, 1970

By J. Handin

Triaxial compression tests with independently applied external confining pressures and internal pore pressures show that the ultimate compressive strengths of representative oil well cements are nearly linear functions of effective pressure — the difference between external and internal pressures on the jacketed cylindrical specimens (to 15,000 psi). The strengths are little affected by the test temperature to 350F (not to be confused with the curing temperature). At an effective pressure of 15,000 psi, strengths are in the rage of 30,000 to 50,000 psi, comparable to those of sedimentary rocks under similar conditions. The cements become very ductile even under low effective pressures; permanent shortenings of 30 per cent or more are attainable without rupture. INTRODUCTION Since the pioneering work of Richart, Brandtzaeg and Brown1 on the failure of cement under combined compressive stresses, it has been recognized that ultimate compressive strength is greatly enhanced by the application of confining pressure. More recently, Mc Henry2 showed that the strength of concrete was a linear function of the effective pressure (the difference between the external confining pressure on a jacketed specimen and the internal fluid pore pressure), at least for a range of 0 to 1,500 psi. The effect of temperature had not been investigated, and no previous systematic triaxial compression testing of naterials used for oilwell cementing seems to have been done. The present work was suggested by the late J. hi. Bugbee3 who stated that "consideration of the common application of high-pressure hydraulic fracturing to the initial completion or recompletion of wells, and the large pressure drawdowns in some producing wells, particularly those in abnormally high-pressure gas-condensate reservoirs, raises the question of what is a suitable cement strength for various completions. The intuitive belief exists that cement strength need be no greater than formation strength. Tests should, however, be conducted at downhole conditions." The ultimate compressive strengths of rocks penetrated by the borehole must rise several fold with increasing depth.4 This marked enhancement of strength is due to the influence of the effective pressure, the total weight per unit area of the overburden less the hydrostatic pore pressure. (The effect of temperature due to the geothermal gradients is relatively small for depths to 30,000 ft.) .A significant comparison of the strengths of rocks and cements at downhole conditions requires knowledge of the confined compressive strengths of cements as well. EXPERIMENTAL PROCEDURES The theory and technique of triaxial compression testing are fully discussed in earlier reports.4-6 Briefly, cylindrical specimens 1-in. long and 0.5-in. in diameter are jacketed in thin copper tubes of negligible strength, placed in the test chamber and subjected to an external confining pressure of kerosene and loaded axially by the piston at a strain rate of 1 per cent per minute. Pore pressures of water (or kerosene) are applied independently through the hollow piston and are maintained constant during the shortening of the specimen, Tests at sensibly 0 pore pressure are arranged so that any free water in the cement can escape to the atmosphere. (If egress of water were denied, pore pressure would rapidly attain the value of the external confining pressure because of reduction of pore space.) The test chamber can be heated for high-temperature experiments. Unless otherwise noted, the cement samples were air dried for about a week. Recorded during a test are pore and confining pressures, shortening and axial differential force (total force less the product of the confining pressure and the area of the piston). True stress-strain curves are constructed by dividing the measured differential force by the actual cross-sectional area of the specimen at a given

Jan 1, 1966

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By N. Schapiro, R. J. Gray, G. D. Coe

A petrographic and chemical investigation was conducted to determine the occurrence and distribution of the organic and inorganic forms of sulfur in various size and specific gravity fractions of a high volatile, A-rank, Pittsburgh seam coal. The investigation was conducted to aid in the resolution of the problem of how metallurgical coke of lower sulfur content can be produced from high sulfur coals. The Pittsburgh raw coal contains about 2.4% S in two dominant forms: pyritic and organic. Pyritic sulfur constitutes about 57% of the total sulfur in the raw coal and occurs in macroscopic and microscopic-size particles. A plant cleaning process mechanically separates between 50 and 60% of the pyritic sulfur, mainly the macroscopic particles. The organic sulfur constitutes 41% of the total sulfur in the raw coal and 55% of the sulfur in the washed coal. Thus, organic sulfur is not reduced by physical methods of separation. Organic sulfur occurs in all the coal entities, but in general, increases as the exinoid content of the coal increases. In this study, it was found that carbonizing certain selected low gravity coal fractions containing an average of 0.45% pyritic sulfur and 1.01% organic sulfur produced cokes containing an average of 0.22% pyritic sulfur and 0.91% organic sulfur. However, the organic sulfur in the coke is probably derived in part from the heating of pyrite in the presence of carbon. Thus, the total sulfur in the coal carbonized is the most important factor affecting the sulfur content of the coke produced. Concentration of microscopic pyritic and organic sulfur in the middling-type coal indicates the necessity for rejecting as much of this material as is economically feasible. Most of the sulfur introduced into the blast furnace originates from the coke. Although the sulfur content of the hot metal can be controlled by the addition of flux, the flux used restricts the productivity of the furnace by displacing ore and requires first to be smelted; therefore, low sulfur coke is highly desirable. Since the sulfur content of coke is dependent upon the sulfur content of the coals from which the coke is produced, low sulfur coals are required to produce low sulfur coke. In the western Pennsylvania area, large quantities of good coking coal are available from the Pittsburgh seam, but this coal unfortunately contains relatively large quantities of sulfur. To provide information that might be useful in reducing the sulfur content of this coal in the cleaning process, an investigation was conducted to determine the physical and chemical forms in which this sulfur occurs and with what petrographic components it might be associated. The Pittsburgh seam coal, like most other coals, contains two dominant forms of sulfur: one occurs as the minerals pyrite and/or marcasite and is referred to as pyritic sulfur; the other is combined with the coal substance and is called organic sulfur. Pyritic sulfur is amenable to physical methods of separation, whereas organic sulfur is not. Pyritic sulfur particles must be freed from the surrounding coal if they are to be removed in the washing process. Generally, this requires crushing; the required degree of crushing being a function of the size and distribution of the pyrite. The present investigation was conducted to 1) determine the size, distribution and association of sulfur-bearing minerals in the coal and 2) to determine whether the organic sulfur has a preferential association with specific coal entities. If a preferential association exists, this knowledge may be useful in devising a method for organic sulfur reduction. In addition, a study was made to determine the extent to which pyritic and organic forms of sulfur in the coal contribute to the sulfur in the coke produced from this coal. A representative 3%-ton sample of raw coal was crushed to —3 in. and screened into square-mesh sizes: 3 to 1 in., 1 to % in., % to % in., % in. to 10 mesh, 10 to 35 mesh, and 35 to 200 mesh. Separate samples of the -200-mesh fraction and the all-size composite were also collected. Each size fraction (except the -200 mesh) was fractionated on heavy liquids of the following specific gravities: 1.280, 1.300, 1.325, 1.350, 1.375, 1.400, 1.425, 1.450,

Jan 1, 1963

By R. F. Favreau, G. E. Larocque

The objective of the study is development of an analytic process based on rock and explosive properties which allows the prediction of the stress distributions and fracture zone around explosive charges. A computer program has been written for this purpose, using a finite difference approximation to the momentum equation, to describe the motion of the surrounding rock by step-wise integration. Its application provides ground motion data such as stress components, displacement and particle velocity as a function of position and time with respect to a spherical charge. The effect of tensile and shear failure on these ground motion parameters can be included. The analytic procedure contained within this program has been used to predict peak stress as a function of distance in rock for rock-explosive combinations for which field data exists to determine peak stress levels directly. Two methods have been used for the spherical charge which in the analysis replaces the actual cylindrical charges: instantaneous application of peak pressure to a charge having a radius equivalent in contained volume to a charge having a length to diameter ratio of 1, and gradual pressure build up to peak pressure with a charge radius equivalent in contained volume to the total charge used in the field test. The agreement with field data would appear best with the latter treatment. The peak stresses obtained are in closer agreement with field measured peak-stress and a better approximation to field stress wave duration exists in the case of gradual pressure build up. One of the assumptions made in the analysis is that, in the case of cylindrical charges, the explosion pressure rather than the detonation pressure of an explosive establishes the peak stresses in the

Jan 1, 1971

By E. V. Potter, E. T. Hayes, H. C. Lukens

LARGE volumes of hydrogen are liberated at the cathode during electrolytic precipitation of manganese. Most of the gas escapes from the electrolyte, but a considerable amount may be entrapped in the manganese plate. Gas has been observed to escape from manganese melts in puffs that ignite at the surface. It has been reported that castings made with electrolytic manganese tend to rise in the molds; for this reason the manganese is often treated to remove hydrogen before the melt is made or it is premelted and used as cast manganese in making the alloys. The effect of hydrogen on the properties of manganese and its alloys is not known, but its effect on iron and iron alloys has been studied extensively.1.2 The close relationship between iron and man¬ganese suggests that hydrogen may have a similar effect on the properties of manganese and its alloys. The purpose of this investigation was to determine the amount of hydrogen or other gases in typical commercial electrolytic manganese sheet and to investigate ways of removing it most conveniently. APPARATUS The apparatus used is shown schematically in Fig. I. It consists of a chamber A in which the metal sample is placed, a vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The specimen chamber was made of two concentric quartz tubes. The outer one, a, connects with the closed gas system and is surrounded by the furnace G. A second tube, b, fits closely inside a and has a small end that projects into the space for the specimen and holds the thermocouple for measuring the temperature of the sample. The inner tube is joined to the outer tube outside the furnace, with rubber tape and sealing wax, to prevent gas leakage into or out of the closed system. This type of specimen container is loaded very easily and can be used several times if molten metal does not come in contact with the quartz. An ordinary mercury manometer B is used to measure the pressure in the system. The volume gauge C is essentially another mercury manometer, but the volume of the column is much larger than normal and the height of the mercury can be varied by raising or lowering the well H. In this apparatus the tube had a volume of I00 c.c. for a 60-cm. length. For larger changes in gas volumes; auxiliary containers F were used to increase the volume of the system by known amounts. Valves were arranged so that these auxiliary containers could be filled from the system and evacuated by the pump as often as necessary to accommodate the increases in the volume of gas in the system. The furnace G, used to heat the samples, was equipped with an automatic temperature controller, which maintained the desired temperatures within ± 5°C.

Jan 1, 1945

By D. M. Kehn

A method has been devloped for chromatographic analysis Of the vapor and liquid phases Of a a system containing methane to components having 20 or more carbon atoms. The method uses a windowed equilibrium cell in which volumetric phase behavior of the system can be observed accurately and from which small samples of gas or liquid can be withdrawn for analysis. Analyses are made using two chromatographs, one for the lighter and one for the heavier components in a sample. Combination of the two analyses yields a detailed analysis of the gas or liquid sample. The complexity of the condensate heavy ends is evident from the chromatograms of these fractions, and the predominance of the paraffin hydrocarborn serves as a useful marker in interpreting the chromatograms. The K-values obtained in this analytical method are presented for a high-pressure condensate system and predict closely the observed volumetric behavior of the system. INTRODUCTION Quantitative analysis of hydrocarbons from natural gas reservoirs is necessary for several reasons—to calculate the amount of sales gas produced, to calculate the amount of natural gasoline produced, to plan a liquid recovery system, or to calculate the potential economic value of a reservoir produced under one or more of several different conditions. Analysis of natural gas fluids produced to the surface consists of identifying and computing the mol fraction of each component of the mixture. Although methane is the predominant component, varying amounts of ethane, propane, butane, pentanes and heavier components are also present. Materials containing up to 30 carbon atoms occur in amounts which decrease with increasing molecular weight. However, the quantities of components in the 20 to 30 carbon atom range are usually so small that their importance is negligible, and they are undetect-able in natural gas by ordinary analytical methods. All the components up to those having 20 carbon atoms may sigsficantly affect phase behavior, however. Commonly, only the methane-through-pentane fraction is analyzed quantitatively for each component, while components heavier than Pentane are lumped and repored as "hexane- plus". Expensive, tedious techniques are required for analysis of this fraction. Consequently the detailed analyses needed for prediction of reservoir behavior are usually undertaken only when major gas fields are being developed. The need for complete analyses of condensate systems is apparent when it is recalled that most gas fields are produced by pressure depletion. As the pressure declines, some of the heavier hydrocarbons are lost as liquids which are in the reservoir. In many instances the amount of liquid in equilibrium with the gas phase at high pressure constitutes only 1 or 2 mol per cent of the total system. Flash calculations generally must predict the actual amount of liquid with an accuracy of a few per cent in order to be useful. This retrograde condensation has been understood for years, but accurate correlation methods to permit quantitative prediction of phase behavior in the retrograde region are not presently available. The increasing importance of natural gas has made accurate prediction of phase behavior and composition of produced natural gas streams an economic necessity. The work reported here was undertaken to provide a rapid, economical method for obtaining the vapor-liquid equilibrium information needed to predict accurately the composition of the fluids produced from a gas reservoir throughout its life. TO develop this method, a pressure cell equipped with windows was designed and built for observing the volumes of liquid and gas present at reservoir pressures and temperatures. Use was made of established chromatographic methods for rapid and detailed analysis of both phases. This paper describes the equipment and techniques developed for obtaining vapor-liquid equilibrium data, presents the results of analyses of a condensate system, and indicates the usefulness of these data in predicting hydrocarbon phase behavior. DESCRIPTION OF EQUIPMENT USED The equipment used in obtaining the required information on phase behavior and the complete analysis of hydrocarbon mixtures through C, will be described first, followed by a discussion of the operation of the equipment. It will be helpful, however, to consider first a brief outline of the technique used. A sample of separator gas and liquid is charged to the windowed cell (see Figs. 1 and 2) where volumetric equilibrium phase behavior at reservoir pressures and temperatures can be determined. Then samples of the coexisting phases are withdrawn. The methane-through-pentane fraction is analyzed with a chromatograph equipped with a hot-wire detector, and the pentane-plus fraction is analyzed with a second chromatograph equipped

Jan 1, 1965

By D. C. Bard

THESE notes are based on the megascopic study of a suite of 2,400 specimens of minerals and ores from the Butte mines, combined with field observations at intervals over a period of several years. The estimate of average vein composition is based on field acquaintance with the veins. It is probably correct in its broader proportions, and should be of use for comparison. Chemical and Mineral Composition of Butte Sulphide Vein. Matter. Per Cent. Oxygen 43.00-Quartz, rhodonite, rhodochrosite, barite, calcite, and hübnerite. Silicon 36.00-Quartz, rhodonite, and willemite (very rare). Sulphur 5.00-Sulphides of. iron, zinc, copper, lead,. and sulphates of barium and rarely calcium. Iron 5.00-Ferric sulphides (pyrite, bornite, chalcopyrite), also in sphalerite, tetrahedrite, and rarely hematite and siderite. Manganese, . . . . 2.00-Rhodonite, rhodochrosite, and hübnerite. Zinc, . . . . 1.00-Spha erite, very rare wurtzite and willemite, and tetrahedrite and tennantite.

Jan 8, 1913

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps : 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. .These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the molecules will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1964

By J. H. Hollomon, L. D. Jaffe

The hardenability concept has become widely used during the last few years for the choice and substitution of steels. Before the work of Grossmann,1 the systems for predicting hardenability from chemical composition could be used only over a narrow range of composition. Grossmann introduced a comprehensive system, which has been effective in calculating the hardenability of most types of moderate or low-alloy steels. However, occasions often arise that require the calculation of the hardenability of high-alloy steels from their chemical compositions. Experimental determinations of the hardenabilities of such steels indicate that the Grossmann system predicts much greater hardenabilities than are realized. The fact that cases do arise in which the Grossmann method does not apply indicates that the fundamental hypothesis of the system may not be generally applicable. It seems advisable to re-examine not only Grossmann's system but also the concept of hardenability itself. Hardenability If steel parts are to possess a martensitic structure after quenching, they must first be austenitized and then cooled through the pearlite and bainite transformation ranges sufficiently rapidly to avoid the formation of pearlite, bainite, and pro-eutectoid products.* If, on cooling, these transformations are avoided, the resulting structure can consist only of martensite (and retained austenite). The hardenability of a steel is measured in terms of the severity of the cooling conditions necessary to avoid the pearlite and bainite transformations. The less rapid is the cooling necessary to prevent the formation of bainite and pearlite, the higher is the hardenability. The pearlite and bainite reactions appear to be differently affected by the alloying elements. Not only is this indicated by the published isothermal transformation data, but recent work by Zener2 affords a rational interpretation of the differing effects of the alloying elements. Manganese,3 for example, appears to decrease the rates of the pearlite and bainite transformations by equal percentages, while molybdenum45 is approximately 10,000 times more effective in retarding the pearlite than in retarding the bainite transformation, on the basis of isothermal measurements. In some steels, the formation of bainite restricts the formation of martensite while

Jan 1, 1947

By L. D. Jaffe, J. H. Hollomon

The hardenability concept has become widely used during the last few years for the choice and substitution of steels. Before the work of Grossmann,1 the systems for predicting hardenability from chemical composition could be used only over a narrow range of composition. Grossmann introduced a comprehensive system, which has been effective in calculating the hardenability of most types of moderate or low-alloy steels. However, occasions often arise that require the calculation of the hardenability of high-alloy steels from their chemical compositions. Experimental determinations of the hardenabilities of such steels indicate that the Grossmann system predicts much greater hardenabilities than are realized. The fact that cases do arise in which the Grossmann method does not apply indicates that the fundamental hypothesis of the system may not be generally applicable. It seems advisable to re-examine not only Grossmann's system but also the concept of hardenability itself. Hardenability If steel parts are to possess a martensitic structure after quenching, they must first be austenitized and then cooled through the pearlite and bainite transformation ranges sufficiently rapidly to avoid the formation of pearlite, bainite, and pro-eutectoid products.* If, on cooling, these transformations are avoided, the resulting structure can consist only of martensite (and retained austenite). The hardenability of a steel is measured in terms of the severity of the cooling conditions necessary to avoid the pearlite and bainite transformations. The less rapid is the cooling necessary to prevent the formation of bainite and pearlite, the higher is the hardenability. The pearlite and bainite reactions appear to be differently affected by the alloying elements. Not only is this indicated by the published isothermal transformation data, but recent work by Zener2 affords a rational interpretation of the differing effects of the alloying elements. Manganese,3 for example, appears to decrease the rates of the pearlite and bainite transformations by equal percentages, while molybdenum45 is approximately 10,000 times more effective in retarding the pearlite than in retarding the bainite transformation, on the basis of isothermal measurements. In some steels, the formation of bainite restricts the formation of martensite while

Jan 1, 1947

By R. H. Hopkins, R. W. Kraft

X-ray and metallographic analysis reveal that the preferred cryslallograPhic relationships in direc-tionally solid~fied Pb-Sn eutectic specimens can be stated: interface growth direction, Experiments in which tin single-crystal seeds were used to nucleate the eutectic demonstrate that the normal lamellar structure observed at steady state can be forced to break down initially to a semide-generate structure when the crystallograPhic direction of the tin seed does not lie within the preferred eutectic interface plane. A normal structure eventually develops by preferred grain growth. X-ray topo-graphs and rocking curves substantiate that the perfection of eutectic samples increases as growth proceeds until steady-state conditions prevail. RECENT years have seen substantial progress made in the understanding of eutectic solidification through both intensive theoretical1'' and experimental investigations (see Ref. 7 for a review and extensive bibliography of both aspects). Several important observations concerning the nucleation and growth aspects of binary eutectic solidification have been brought to light. Briefly some of these include the nonrecipro-cal nucleation of one phase upon another,'j9 the tendency for a specific low-index direction of one or both phases of the eutectic to be aligned in the growth direction during unidirectional solidification,'0711 and the production of lamellar microstructures having a preferred interface plane between "11-13 phases. Questions quite naturally arise as to the mechanism by which preferred grain growth evolves during eutectic solidification and what relationships (if any) connect the initial nucleation of one phase upon another with the preferred growth directions and interface planes observed after a few centimeters of growth in many systems. This study was initiated in an attempt to answer these questions. An experiment was devised in which both the nucleation and growth steps in the crystallization of a binary eutectic, Pb-Sn, could be correlated with subsequently developed eutectic morphology and crystallography. This was accomplished by nucleating the eutectic upon a tin single crystal seed and then causing the eutectic to grow from the seed by directional freezing. The morphology of the structures produced in this manner was then monitored metallographically and the orientation relationships and substructural perfection determined by X-ray analysis. The information thus ob- tained was correlated to the growth history of the samples. EXPERIMENTAL DETAILS The eutectic of composition 38.1 wt pct Pb and 61.9 wt pct sn14 was prepared by accurately weighing lead and tin of 99.999+ (from ASARCO and Lytess Metals and Chemicals, respectively), melting in a clean Pyrex beaker under an argon blanket, and casting into the proper crucible for resolidification as described below. Tin seeds were grown by the method of ~halmers," saw-cut, oriented by the Laue method, and soldered to the pull rod of the Czochralski puller. All seeds were given a final electropolishing (to assure the removal of any deformed material from the cutting operation) and acetone degreasing immediately prior to the nucleation experiment in which they were to be used. Eutectic samples were unidirectionally solidified in a horizontal graphite boat1' or by pulling from the melt16 with tin (or graphite) seeds. A flowing argon atmosphere was employed in all experiments and growth rates and temperature gradients, constant for a given run, varied from 2 to 4 cm per hr and 8" to 15°C per cm over the course of all the experi-

Jan 1, 1969