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By A. D. Zunkel, A. H. Larson

Equilibrium arsenic contents of Pb-As alloys in contact with PbO-As2O3 slags containing less than 30 mol pct As2O3, were determined at 650°, 700: and 750 C in an inert at?rzosphere. In this temperature range, the arsenic content of the alloy increased with increasing temperature in the single-phase liquid slag region and decreased with increasing temperature in the two-phase slag region and the single-phase solid-solution slag region. The PbO-As2O3 phase diagram below 22 mol pct As2O3 was determined by thertrzal analysis and by application of a log ?As2O3/?PbO vS log XAs2o3 /x3pbO plot determined from the equilibrium actiuity data. The resulting phase diagram was not well-defined since the eutectic temperature was not detected in the thermal analysis experiments, although a region of terminal solid solubility of As2O3 was found. Results from the phase diagram determination are compared with an existing diagram in the literature. THIS experimental investigation is an extension of a study by the authors1 on the slag-metal equilibria in the systems concerned with commercial lead refining processes such as softening and dross fuming. The first part of this investigation was a study of the slag-metal equilibria in the Pb-PbO-Sb2O3 system. The only experimental work previously done on the Pb-PbO-As2O3 system was by Pelzel2,3 in which the phase diagram for the PbO-As2O3 system was determined below 50 wt pct As2O3 and the equilibrium constant for the reaction 3Pb + As2O3 + 3PbO + 2As was determined as a function of temperature. No slag-metal equilibrium data have been determined. It is due to the scarcity of information regarding the Pb-PbO-As203 system that this work was undertaken. This paper describes the determination of the slag-metal equilibria in the Pb-PbO-As203 system by equilibrating Pb-As alloys with PbO-As2O3 slags in an inert atmosphere, the effect of 1 wt pct additions of bismuth and copper on the slag-metal equilibria, and the PbO-As2O3 phase diagram both by thermal analysis and the use of the slag-metal equilibria data. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade and assayed as follows: 1) 99.8 pct PbO (0.014 pct insoluble in CHJCOOH, 0.02 pct not precipitated by H2S, 0.1 pct CaO, and 0.08 pct SiO2); 2) 99.95 pct As2O3; 3) 99.99 pct Pb; 4) 99.0 pct As; 5) 99.99 pct Cu; and 6) 99.97 pct Bi. Room-temperature X-ray patterns revealed no detectable impurities in any of these materials. Apparatus for Equilibrium and Thermal-Analysis Determinations. The resistance-heated crucible furnace used in this investigation employed nichrome elements and was mounted so that it could be raised to surround the reaction tube during each experiment and, subsequently, lowered. A schematic diagram of the apparatus is shown in Fig. 1. Each charge was heated in a 3+-in.-OD by 31/2-in.-high 416 stainless-steel crucible placed in a 41/4-in.-1D by 18-in.-long fused-silica reaction tube which was closed at one end. On a shoulder around the crucible was placed a 3: -in.-OD by 12-in.-long open-end fused-silica condenser tube. The open end of the reaction tube was covered by a water-cooled brass cap with ports for 1) admitting an inert atmosphere to the system through a stopcock, 2) introducing a stainless-steel, motor-driven, paddle stirrer into the crucible, 3) evacuating the system with a mechanical vacuum pump, and 4) sampling the melt with Vycor sampling tubes. The brass cap was fitted to the open end of the reaction tube with a silicone gasket and collar clamp. The furnace temperature was controlled by a Barber-Coleman Capacitrol controller and a chromel-alumel thermocouple. Due to the corrosiveness of the melt, the controlling thermocouple also served as the measuring thermocouple. The temperature of the melt was calibrated against the controller temperature and was checked periodically during each test with a Vycor-enclosed calibrated chromel-alumel thermocouple. The temperature measurement and control can be considered accurate to ±3°C. Procedure. The charge placed in the crucible for each experiment consisted of 1000 g of Pb-As alloy and 300 g of PbO-As2O3 slag. The crucible was then placed in the reaction tube, the condenser tube was placed on the shoulder of the crucible, the silicone gasket and brass cap were fitted on the open end of the reaction tube, and the entire system was evacuated and filled with argon ten times. After the last flushing, a positive argon pressure of 1 psig was impressed on the system. The furnace was then raised to sur-

Jan 1, 1968

By L. L. Swift

.It the present time there are four base metals being used for automo-tive bearing alloys. Of course there are numerous variations in the amounts of alloying elements added to each base metal and nearly all of these alloys have the conventional, if not classical, duplex structure; that is, they are composed of a hard constituent embedded in a soft matrix. The well-known theory is that the former will wear well, while the latter will be plastic enough to allow the bearing to be broken in and conform to the contours of the shaft. The requirements of the modern bearing have been most aptly described by W. M. Corse: In order to meet the engineering demands of today a good bearing metal must be able to carry the weight of the shaft and stand up under steady or suddenly applied loads, or even blows ill sorne types of service. A certain amount of plasticity is desired to compensate for minute irregularities in the shaft or bearing surface, and to permit yielding, thereby avoiding dangerous stresses in bearing and shaft and pre-venting overheating and rapid wear of parts. Less plasticity is required in a bearing tuetal if the surfaces of bearings and journals are machined accurately, aligned, and kept in alignment. It is desirable, of course, that a bearing metal have a low coeffi-cicnt of friction. Under most operating conditions the friction depends on the unit, pressure of the bcaring, the speed, the temperature, and the properties of the lubricant. A good bearing metal must have a low rate of wear to reduce the necessity for frequent replacements, and adjustment of the bearings. It must wear more rapidly, however, than the journal or shaft running on it, because replacement of the journal or shaft is more difficult and costly than replacement of the bearing.' The hardness of the bearing alloy is a property closely related to several of the foregoing. With a duplex microstructure, the measurement of hardness with any of the usual commercial devices means little. The Bierbaum method of measuring the hardness of the individual canstituents was developed to fill this need. MICROCHARACTER The Bierbaum MicroCharacter~,~ measures the scratch-hardness of a solid by pulling a weighted diamond point over the surface. The diamond point is ground so that it is the corner of a cube, and Mounted

Jan 1, 1939

By L. L. Swift

.It the present time there are four base metals being used for automo-tive bearing alloys. Of course there are numerous variations in the amounts of alloying elements added to each base metal and nearly all of these alloys have the conventional, if not classical, duplex structure; that is, they are composed of a hard constituent embedded in a soft matrix. The well-known theory is that the former will wear well, while the latter will be plastic enough to allow the bearing to be broken in and conform to the contours of the shaft. The requirements of the modern bearing have been most aptly described by W. M. Corse: In order to meet the engineering demands of today a good bearing metal must be able to carry the weight of the shaft and stand up under steady or suddenly applied loads, or even blows ill sorne types of service. A certain amount of plasticity is desired to compensate for minute irregularities in the shaft or bearing surface, and to permit yielding, thereby avoiding dangerous stresses in bearing and shaft and pre-venting overheating and rapid wear of parts. Less plasticity is required in a bearing tuetal if the surfaces of bearings and journals are machined accurately, aligned, and kept in alignment. It is desirable, of course, that a bearing metal have a low coeffi-cicnt of friction. Under most operating conditions the friction depends on the unit, pressure of the bcaring, the speed, the temperature, and the properties of the lubricant. A good bearing metal must have a low rate of wear to reduce the necessity for frequent replacements, and adjustment of the bearings. It must wear more rapidly, however, than the journal or shaft running on it, because replacement of the journal or shaft is more difficult and costly than replacement of the bearing.' The hardness of the bearing alloy is a property closely related to several of the foregoing. With a duplex microstructure, the measurement of hardness with any of the usual commercial devices means little. The Bierbaum method of measuring the hardness of the individual canstituents was developed to fill this need. MICROCHARACTER The Bierbaum MicroCharacter~,~ measures the scratch-hardness of a solid by pulling a weighted diamond point over the surface. The diamond point is ground so that it is the corner of a cube, and Mounted

Jan 1, 1939

By Robert E. Allen

The organized curtailment of California oil production is not yet one year old but during its first year it has accomplished so much that it is now firmly established as an agency of economic efficiency. The principle of cooperative curtailment has been adopted by other states and it is safe to say that the principle will continue as long as the demand for petroleum is notably less than the potential production. It' is interesting to note that this same principle of regulating supply to meet demand is now being urged for other industries, such as agriculture and mining. Since Oct. 31, 1929, when curtailment was instituted by the oil producers of Santa Fe Springs and Long Beach in an effort to avert the disaster of ruinously low prices which confronted them, there has been a constant and increasingly effective curtailment program in California. Prior to that time a notable effort toward the restriction of oil production was made under the direction of F. C. Van Deinse during the early summer months of 1929. A considerable reduction of oil output was recorded as the result of this effort, but because of incomplete cooperation and the discovery of still deeper zones at Santa Fe Springs the effort was abandoned; flush field production became unrestrained and prices soon fell to low levels. This initial curtailment movement was educational and experimental. It showed all operators a way out of their overproduction difficulties and developed the principles followed in later curtailment efforts. Thus it was that only a few days after their oil had been reduced to 60 c. per barrel, the operators of Santa Fe Springs got together and agreed to restrict their current production of more than 270,000 bbl. daily to not more than 150,000 bbl. daily. The operators at Long Beach followed the same course a few clays later and agreed to limit their production to not more than 110,000 bbl. daily. The Santa Fe Springs operators chose H. P. Grimm as umpire and director of their proration program. Neal H. Anderson was chosen umpire for Long Beach. Since that time, as the need for curtailment has increased, practically every field of the state has come under the curtailment of these two umpires. Curtailment of the Elwood and

Jan 1, 1931

By J. W. Freeman, E. E. Reynolds, A. E. White

Fram a study of 63 systematic alloy modifications it was found that molybdenum, tungsten, and columbium, added individually or simultaneously, and increases in chromium cause major improvements in 1200°F rupture strengths of Cr-Ni-Co-Fe base alloys. Rupture strengths were a function of the effect of composition modifications on both the inherent creep resistance and the amount of deformation the alloy would tolerate before fracture. THIS paper describes the results of an investigation of a series of alloys with systematic variations of the chemical composition of the following basic alloy: C, 0.15: Mn, 1.7; Si, 0.5; Cr, 20.0; NI, 20.0: Co, 20.0: Mo, 3.0; W, 2.0; Cb, 1.0; N, 0.12; Fe, 32.0 pct. The 62 modifications of this alloy were produced under conditions which minimized all factors influencing properties at high temperatures except composition. Melting, fabrication, and heat treatment were carefully maintained constant. Stress-rupture properties at 1200°F were used as the primary criteria of evaluation of the alloy. The objective of the study was to obtain data for determining the fundamental role of the influence of alloying elements on properties of heat-resistant alloys at high temperatures. In addition the results should be useful in determining optimum chemical compositions, the sensitivity of properties to variations in composition, and the degree to which alloy content could be reduced while retaining worthwhile properties. It is difficult or impossible to develop correlations between properties at high temperatures and systematic variations in chemical composition from published data for wrought heat-resistant alloys developed for gas turbines.' ' The main reason for this is the extreme dependence of the properties on conditions of treatment of the alloys." In most cases variation in final treatments between alloys so influences the properties that the influence of chemical composition is obscured. In addition it is recognized Table I. Basic Alloy and Some Modifications Used Basic AllOy, Variations in Element Pct Composition, Pct C 0.15 0.08. 0.40. 0.60 Mn 1.1 0.03,0.25.0.50,1.0,2.5 S1 0.50 1.2, 1.6 Cr 20.0 10, 30 Ni 20.0 0, 10,30 Co 20.0 0. 10, 30 MO 3.0 0. 1.2.3, 5, 7 W 2.0 0, 1, 5, 1 Cb 1.0 0.2,4,6 N 0.12 0.004, 0.08, 0.18 Fe 32.0 that variations exist between heats of the same alloy which are related to melting practice and that there is a strong possibility that conditions of hot working influence response to final treatments. The development of heat-resistant alloys has been based on the gradual accumulation of data roughly related to composition from extensive testing programs. There is every reason to believe that in most cases the optimum compositions have been achieved by this procedure in the alloys commercially available. There are, however, very little data showing the influence of systematic variations of composition free from the influence of other factors, particularly for alloys of the type investigated. Several investigators of cast alloys have demonstrated compositional effects, notably Grant,1-6 Epremian,t Guy,8 and Harder and Gow.9 Sykes10 eviewed the work on the wrought alloy Rex 78 and the systematic variations of carbon, copper, molybdenum, and cobalt leading to the development of the stronger Rex 337A alloy. From the papers by Wilson11 and Henry12 it is possible to deduce the beneficial effect of substituting cobalt for iron in 0.45 pct C-20 pct Cr-20 pct Ni-4 pct Mo-4 pct W- 4 pct Cb alloys. Wilson mentioned but did not present the extensive compositional studies involved in developing these alloys. Binder" showed optimum properties for 3, 2, and I pct, respectively, for molybdenum, tungsten, and columbium in 20 pct Cr-20 pct Ni-20 pct Co-30 pct Fe alloys for limited systematic variations of these

Jan 1, 1953

By C. S. Sivil

To modern civilization the platinum metals are of inestimable value. Their distinctive properties, both physical and chemical, render them indispensable in an age in which the processes of the laboratory are becoming an essential part of the daily life of the world. Generally, their function, though vital to particular processes, is not spectacular, and so remains unknown to all except the operators. EARLY METHODS OF MANUFACTURE The properties of platinum were recognized as of prime importance for scientific work at. a very early date, probably between 1750 and 1760. The difficulty of making articles from it seemed almost insurmountable, because no means of attaining the temperature necessary to melt it were known at that time. It is true that solid platinum could be obtained by fusing the metal with a more volatile metal such as arsenic, which was subsequently driven off by baking, but such a method, at its best, would give only a very brittle product, which was totally unsuitable for the purposes for which it was intended. Little, if any, progress could be made until it was discovered that platinum sponge, heated to white heat and hammered in an iron or clay mold, would metallize and retain the shape of the mold. This was a process that could not be wholly satisfactory but from it developed the method of pressing the sponge in a mold and forging it at white heat into wire or sheet. At present a somewhat similar process must be used for fabricating articles of tungsten, molybdenum and other metals of high fusing point, as with these metals we face today the same problems that the scientists of the eighteenth century encountered with platinum, but possibly the next significant advance in the metallurgy of these metals will be the devising of means to melt and cast them.

Jan 1, 1931

By D. T. Goettge, E. L. Robinson

The phase changes occurring in low carbon steel during hot strip mill rolling are shown to be metallurgically significant when related to commonly used temperature control points, particularly finishing and coiling temperatures. In combination, these temperatures are shown to have an important influence on the level and uniformity of hardness, grain size, and carbide characteristics of the finished hot and cold rolled sheets. PRODUCTION of wide flat-rolled products ordinarily requires a number of operations in sequence to prepare the material for shipment to the customer. Most products are tailor-made for specific end uses, with each operation contributing certain properties to the finished material. Since the characteristics imparted to the semifinished product by a given step in processing carry through to the finished product in varying degrees, it is important that the intermediate stages of production of flat-rolled strip be carried out with the same care which characterizes the last or finishing operations. The step of hot strip mill rolling is common to the production of all of the various types of flat-rolled product; therefore, the hot strip rolling is an especially important point at which to recognize and control those variables which have an effect on the surface characteristics and metallurgical properties of the finished product and which influence the ease of conducting subsequent operations. Orders entered at a producing mill usually show an end use or describe an article or part into which the ordered product is to be fabricated. Applying his experience as to the properties necessary in a finished sheet to suit the end use and to perform successfully in the fabrication involved, the metallurgist selects a steel of suitable composition and deoxidation practice, and slabs of appropriate dimensions are produced for rolling on the hot strip mill. At this stage of processing, the metallurgist faces the problem of controlling hot strip mill practice in the light of his diagnosis of the properties necessary to meet the end use, paying due attention to the accompanying problem of producing a strip which can meet processing requirements on subsequent units in the mill. It is the purpose of this paper to describe some of the factors which he must consider in solving these problems and to indicate some of the principles which guide him. Equipment, Physical Requirements of the Strip, and Temperature Measurement The metallurgist must, of course, be familiar with the physical layout of the mill, the temperature-measuring equipment available, and the physical requirements of the hot strip product before he can apply his metallurgical knowledge to the problem; hence, the first section will consist of a brief discussion of these matters. The usual hot strip mill consists of reheating furnaces, five or six roughing stands including a scale-breaker, holding table, and second scalebreaker, six-stand finishing mill, runout table with spray cooling facilities, and coilers. A schematic diagram of a typical layout is shown in Fig. 1. Slab temperatures are primarily a function of heating time and furnace temperatures, while mill speeds, spray practice, drafting practice, available water pressure, temperature of the cooling water, cross sectional dimensions of the strip, coil size, and equipment limitations, either singly or in combination, determine what rolling temperatures are practical on a given hot strip mill unit. Thus, it is possible that a set of temperatures which can be utilized successfully on one mill cannot be used on another. However, adjustments in temperatures and rolling practice can usually be made to develop the desired metallurgical properties. In addition to the metallurgical properties developed through proper temperature control, the hot strip mill must also provide strip with certain physical attributes which may be summarized as follows: Strip Cross Section—The strip contour should conform to a section which will give the best results in the cold reduction operation. This is generally recognized as a strip with 0.001 to 0.003 in. crown or shoulder-to-shoulder convexity depending on width, and freedom from concave, flat, or wedge-shaped cross sections which cause metal buildup in cold reduction. Excessive drop off in thickness at the edges can also be very detrimental in cold reducing to light gages. Gage, Width, and Camber—All of these must be controlled. For example, rundown or increasing thickness from the front to the back of the coil results in nonuniformity in the thickness of hot-rolled sheet product and in added difficulty with gage and welds in cold reduction. Similarly, excessive width variation is the cause of guide trouble and excessive edge scrap at later stages of processing, while excessive camber is the source of a variety of processing troubles. Type of Oxide—Product intended for pickling should have a predominance of the type of oxide most easily removable in sulfuric acid. It is generally recognized that this type is obtained by use of maximum table cooling water and cold coiling

Jan 1, 1957

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By G. R. Speich, D. J. Mack

The transformation of was studied by isothermal methods. At all temperatures, the ß transforms quickly to fine grained ß" which develops silver-rich striations. At higher temperatures the striations disappear, the final structure being Widmanstatten a in ß'. At lower temperatures, the striated ß" is consumed by pearlite nodules of a + ß' which in turn form the Widmanstatten a in ß'. The transformation is unlike any previously reported for a eutectoid. AS part of a general program of study on the eutectoid reaction, the Ag-Cd eutectoid seemed particularly attractive because the ß phase which undergoes the reaction is another of the typical "electron compounds," AgCd, having the disordered body-centered cubic structure. This work deals with the eutectoid which occurs at 50.5 wt pct Ag, and not with the eutectoid which has been reported at 42.9 pct Ag.' There has been no work reported specifically on the Ag-Cd eutectoid which was studied. The only information available on this eutectoid is that work done in the determination of the phase diagram. For the most part, the terminal portions of the diagram, Fig. 1, are well established; however, the region from 40 to 60 pct Cd is still somewhat in doubt. The X-ray evidence'..' in this region is in conflict with the results of thermal analysis. X-ray analysis3 does not show a polymorphic transformation at about 240°C as indicated by thermal analysis.1,5 Even the X-ray evidence, within itself, is confusing in this region of the diagram. One investigator2 reports the ß phase as hexagonal close-packed and has found three phases in the one-phase ß field. Other X-ray investigators"' ' report the ß phase as body-centered cubic. The authors believe that much of the confusion resulted from incomplete homogenization of the alloys. It was found that it takes almost a week to produce a completely homogeneous two-phase structure at 370°C. Another possible source of error is the volatilization of cadmium from the surface and cracks of the specimen during annealing with the possible formation of a cadmium-poor phase. The only metallographic data available on this eutectoid alloy are those of Durrant1 and Fraenkel and Wolff.5 his information is very limited. The phase diagram chosen as most nearly correct is that in the Metals Handbook," which is almost identical with the phase diagram suggested by Durrant.1 Materials and Procedure The alloy was prepared from high purity silver (999.5 plus fine) and high purity cadmium (0.02 Pb, 0.005 Cu, trace Fe). The metals were melted in carbon under a nitrogen atmosphere. Some cadmium was lost by volatilization but by remelting several times and adding cadmium a 200 g ingot of approximately eutectoid composition was obtained. Because the CdO fumes are quite toxic, the exit gas from the furnace was led through a water trap to condense the CdO. The ingot was homogenized at 650°C for 24 hr, no attempt was made to prevent decadmiumization. This resulted in a narrow decadmiumized rim on the ingot which was removed. Filings for analysis were obtained from cross sections of the ingot. Silver was determined by the Volhard thiocyanate method,? cadmium by difference. The ingot analyzed 50.8 pct Ag at the top of the ingot and 50.7 pct at the middle and at the bottom of the ingot. This alloy was only slightly hypo-eutectoid compared to the accepted value of 50.5 pct Ag and was used for the isothermal studies. It was felt that further attempts to adjust the composition might be futile because of the volatility of the cadmium. The ingot was sectioned to specimens approximately 3/4 x 3/4 x 1/8 in. These specimens were "austeni-tized" for 3 hr in air at 650°C to yield homogeneous ß and then quenched into a salt bath held at constant subeutectoid temperatures where the transformation

Jan 1, 1954

By Joseph A. Norden, A. R. Willson

Much has been written concerning the hoisting equipment of various mines throughout the country, but most of the literature on the subject, if not all, describes equipment of extraordinary capacity and the small and medium-sized outfits have been neglected. The hoisting equipment here described is capable of handling about 1200 tons per day. It has not been worked to capacity, but 600 to 700 tons, together with men and materials, have been handled in two shifts without any great effort. Only one shaft extends from the surface to the lowest levels of the mine; see Fig. I. It is composed of three compartments, two of which are used for hoisting, and the third for water, air, and electrical lines, and for sinking purposes. In 1909, this shaft was raised from the 1000-ft. (304-m.) level to the 700-ft. There a station was cut and an air hoist installed. At this time all mining operations were confined to the upper levels of the mine; that is, above the 700-ft. The ore was dropped to this level through chutes from the 300-, 400-, 500-, and 600-ft. levels and then lowered in cars on cages to the 1000-ft., which is the main haulage adit, the mill and railroad bins being about 3000 ft. from the shaft. Orebodies were, in due time, developed on the 1000-ft. level and below. Therefore, in 1913,the shaft was sunk to the 1150-ft. level and thereafter sinking was continued at regular intervals until the 1500-ft. level was reached. But, hoisting from the 1300-ft. level was a difficult and slow process with the antiquated air hoist, so, in 1916, it was decided to raise the shaft to the surface and install a modern, electrically operated hoist. This was completed early in 1917 and the hoist was in operation in March of that year. The Hoist Figs. 2, 3, and 4 show various features of the hoist and electrical equipment. A Nordberg engine of the double-drum, geared type, designed for a 10-ton load, including rope, at a speed of 1500 ft. per min., is used. The drums are 7 ft. (2.1 m.) in diameter, with a 54-in. (137-em.)

Jan 1, 1922

By C. E. Nelson

THE purpose of this discussion is to outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as far as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, the principal aim of this paper will be to deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. TYPES OF MELTING PRACTICE All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux.* The flux provides protection during melting and a molten pool of flux into which the solid magnesium melts. It is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies; then on quiet standing separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is usually desirable. The open-pot method is used generally in the following processes: (I) alloying and secondary smelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings requiring hand ladling, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protec-

Jan 1, 1944

By G. R. Fitterer

By means of the C-Sic thermocouple1, liquid metal temperatures have been found to vary much more than was previously supposed, and fortunately these variations can be directly associated with some of our former knowledge which combined to form the "art" of liquid-metal manipulation. Commercial Development of This Device Several types of installations are operating in different plants. There are so many variables in steel plants in regard to operation, procedure, arrangement of pouring platforms, ladles, etc., that most of the installations now in service in this country are "tailor-made"; nevertheless, it is felt that satisfactory gains have been made, inasmuch as each installation has indicated some effect of temperature upon the metallurgical operation, and has pointed the way toward technical and financial benefits. In most cases, it has been necessary to accumulate the temperature data until sufficient metallurgical information is available for the drawing of conclusions. When mechanical difficulties have been eliminated, a distinct correlation of these factors has been obtained. The installations now in service are used for the determination of temperatures in the basic open-hearth furnace prior to tapping and in ladles from both acid and basic furnaces prior to pouring. Some of the installations are in shops making the higher priced steels; others are in "tonnage shops." The errors of human element, smoke screens and emissivity corrections connected with the use of the optical pyrometer do not affect the C-SiC thermocouple readings. The accuracy of the C-Sic thermocouple and the temperatures measured are discussed later in this paper. Temperature Variations or Liquid Pig Iron One well-known discussion between the blast-furnace and open-hearth (or Bessemer) departments has occurred intermittently for more

Jan 1, 1936

By G. R. Fitterer

By means of the C-Sic thermocouple1, liquid metal temperatures have been found to vary much more than was previously supposed, and fortunately these variations can be directly associated with some of our former knowledge which combined to form the "art" of liquid-metal manipulation. Commercial Development of This Device Several types of installations are operating in different plants. There are so many variables in steel plants in regard to operation, procedure, arrangement of pouring platforms, ladles, etc., that most of the installations now in service in this country are "tailor-made"; nevertheless, it is felt that satisfactory gains have been made, inasmuch as each installation has indicated some effect of temperature upon the metallurgical operation, and has pointed the way toward technical and financial benefits. In most cases, it has been necessary to accumulate the temperature data until sufficient metallurgical information is available for the drawing of conclusions. When mechanical difficulties have been eliminated, a distinct correlation of these factors has been obtained. The installations now in service are used for the determination of temperatures in the basic open-hearth furnace prior to tapping and in ladles from both acid and basic furnaces prior to pouring. Some of the installations are in shops making the higher priced steels; others are in "tonnage shops." The errors of human element, smoke screens and emissivity corrections connected with the use of the optical pyrometer do not affect the C-SiC thermocouple readings. The accuracy of the C-Sic thermocouple and the temperatures measured are discussed later in this paper. Temperature Variations or Liquid Pig Iron One well-known discussion between the blast-furnace and open-hearth (or Bessemer) departments has occurred intermittently for more

Jan 1, 1936

By A. M. Kivari

Operations at the cement plant of the Permanente Corporation, in the hills about 45 miles south of San Francisco and 12 miles west of San Jose, are interesting to the members because of the adoption of modern hydrometallurgical methods for handling and beneficiating raw materials. Closed-circuit grinding, classification, hy-droseparation, flotation, agitation, and thickening are familiar terms at this cement plant. These methods make it possible to process refractory limestone into suitable materials for the mallufacture of modern cements. Construction of the plant, having originally a design capacity of 7000 bbl. of cement per day, was started in June 1939, and the first clinker was ground on the following Christmas Day. At present the capacity is about 12,000 bbl. of finished cement per 24 hr., most of the production being low-heat cement. † About 3I30 tons of limestone, 620 tons of clay and I00 tons of gypsum are required daily for this output. Occasionally iron oxide is added to the clay to obtain the desired composition. This, together with the gypsum, is purchased from outside sources. up to the present time, the ccrporation has produced low-heat, normal, moderate-heat, moderate-sulphate-resisting, high-early-strength, oil-well, modihed-oil-well, and plastic cements. Most of the present production is for Shasta Dam, near Red- ding, Calif., the total demand being 5,800,000 bbl. of cement. Following are some of the cement require ments of the Shasta Dam specifications: Per Cent Chemical composition: Loss in ignition.......... 2.25 Insoluble residue......... 0.75 SO3.................... 2.25 MgO................... 5.'' Uncombined lime in clinker (CaO)......... I.25 Percentage of iron oxide to alumina ratio....... I.5 Compound composition: Tricalcium silicate (3CaO.SiO2)........... Not more than 35 Dicalcium silicate (zCaO.SiO2)........... Not less than 40 and not more than 65 Tricalcium aluminate (3CaO.Al2O3).......... Not more than 7 Tetracalcium aluminofcr- rite (4CaO.Al²O³.Fe²O³) Not more than 20 Fineness: The average specific surface in the bin sampled shall be not less than 1800 sq. cm. per gram and no individual sample less than 1600 sq. centimeters. Compressive strength: The average compressive strength in pounds per square inch of three mortar cubes composed of one part cement and 2.75 parts fine testing sand, by weight, shall be equal to or greater than the following:

Jan 1, 1942

By A. M. Kivari

Operations at the cement plant of the Permanente Corporation, in the hills about 45 miles south of San Francisco and 12 miles west of San Jose, are interesting to the members because of the adoption of modern hydrometallurgical methods for handling and beneficiating raw materials. Closed-circuit grinding, classification, hy-droseparation, flotation, agitation, and thickening are familiar terms at this cement plant. These methods make it possible to process refractory limestone into suitable materials for the mallufacture of modern cements. Construction of the plant, having originally a design capacity of 7000 bbl. of cement per day, was started in June 1939, and the first clinker was ground on the following Christmas Day. At present the capacity is about 12,000 bbl. of finished cement per 24 hr., most of the production being low-heat cement. † About 3I30 tons of limestone, 620 tons of clay and I00 tons of gypsum are required daily for this output. Occasionally iron oxide is added to the clay to obtain the desired composition. This, together with the gypsum, is purchased from outside sources. up to the present time, the ccrporation has produced low-heat, normal, moderate-heat, moderate-sulphate-resisting, high-early-strength, oil-well, modihed-oil-well, and plastic cements. Most of the present production is for Shasta Dam, near Red- ding, Calif., the total demand being 5,800,000 bbl. of cement. Following are some of the cement require ments of the Shasta Dam specifications: Per Cent Chemical composition: Loss in ignition.......... 2.25 Insoluble residue......... 0.75 SO3.................... 2.25 MgO................... 5.'' Uncombined lime in clinker (CaO)......... I.25 Percentage of iron oxide to alumina ratio....... I.5 Compound composition: Tricalcium silicate (3CaO.SiO2)........... Not more than 35 Dicalcium silicate (zCaO.SiO2)........... Not less than 40 and not more than 65 Tricalcium aluminate (3CaO.Al2O3).......... Not more than 7 Tetracalcium aluminofcr- rite (4CaO.Al²O³.Fe²O³) Not more than 20 Fineness: The average specific surface in the bin sampled shall be not less than 1800 sq. cm. per gram and no individual sample less than 1600 sq. centimeters. Compressive strength: The average compressive strength in pounds per square inch of three mortar cubes composed of one part cement and 2.75 parts fine testing sand, by weight, shall be equal to or greater than the following:

Jan 1, 1942

By Frederick Laist, Howard Aldrich

The object of the construction and operation of the 80-ton leaching plant was to test out the leaching of sand tailings on a large scale and, if possible, determine a definite method of operation, and the best construction for the larger unit which is now being built. It was also of importance to obtain some practical data as regards cost items. The 80-ton plant was not expected to be a commercial success. A leaching process on such low-grade material necessitates the treatment of a very large tonnage. Such a cost item as labor, for instance, is entirely out of proportion in such a small plant. The amounts of acid, salt, scrap iron, and fuel for roasting, however, are the same per ton in an 80-ton plant as in a 2,000-ton plant. These costs were definitely established. Also the percentages of extraction and grade of tailings were definitely determined for a large-sized unit. Following will be found the description of the plant, the method of operation and the- results obtained. A general view of the plant is given in Fig. 1. The bins consisted of one coal bin with a capacity of 30 tons, one salt bin with a capacity of 20 tons, and a "mill tailings" or feed bin which held 70 tons. The coal and salt bins were placed with their floor level even with the firing floor of the roasting furnace. The feed bin, to give it greater capacity, discharged about 12 ft. below this point, to a 12-in. conveyor belt, which in turn discharged into a pug mill. This fed another conveyor belt, which discharged into the top hearth of the furnace. The furnace was an ordinary six-hearth MacDougall roaster, 20 ft. in diameter. It was equipped with two fire boxes, on opposite sides, the flames entering on the third hearth. An induced draft was obtained with a Buffalo blower, worked as an exhaust fan. Just above the top hearth was an annular flue around the whole circumference of the furnace. Slots at intervals of about 18 in. led from this flue down into the top hearth. The slots were 2 in. wide by 6 in. long. This annular flue proved rather unsatisfactory, as it tended to fill up with flue dust and choke the dots, thus cutting down the draft. The volume of gas through

Jan 1, 1915

By C. D. Demond

IN reverberatory smelting, fuel is the chief item of expense, as it commonly is in processes using large percentages of it. Hence the most suitable supply is eagerly sought; that is, the supply which, in the end, yields the greatest net profit. The better grades are not infrequently bought, even at an advanced price, because they are apt to be decidedly more economical. High price, of itself, however, is no merit, for freight is generally the largest part of the cost of fuel, and the nearby supply may yield as high efficiency as that from a greater distance. If a poorer grade is reasonably good, and if its cost is low enough to more than offset the decreased technical efficiency, it is of course the more suitable. Any smelting, operation depends for both efficiency and economy on raising the furnace atmosphere considerably above the "critical" temperature; that is, above the temperature at which smelting is completed. If this temperature is not exceeded, smelting stops, no matter how much coal is burned; and the real value of a fuel depends on the number of degrees that the temperature is continuously kept above this point. For example, if one fuel maintains 2,500° F. and another only 2,100° F., while the "critical" temperature is 2,000° F., the first is worth at least five times as much as the second, although the increase above atmospheric temperature is only one-fifth more in one case than in the other. This "margin of temperature" above the smelting point is much more significant than the total number of heat units developed from the fuel. The case is parallel to that of water flowing from a pipe. The reservoir may contain a billion gallons of water; but, even though the fluid has come to the nozzle, not a drop will run out, where it can be of practical use, unless the level in the reservoir is higher than the nozzle; and the speed and volume of flow depend on how much higher the level is in the reservoir than at this point. If the temperature inn a furnace is not above the critical level there will be no slag to flow over the skimming plate, even though there are enough heat units to bring an unlimited quantity of charge up to the point of slag formation; and just as the value of a water supply for the purpose of putting out a fire depends largely on the effective head, so the difficulties of furnace management

Jan 8, 1914

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

By G. T. Davis, C. C. Mattax, M. O. Denekas

The effects of crude oil cornponents on the wellabil-ities of sandstone and limestone were investigated. Fractions containing cornponents differing in molecular weight and molecular structure were obtained from crude oils by distillation, extration and chromatography. Individual fractions were then tested for their effects on rock wettability. Tests indicate that sundstone wetta-bility may he changed by a complex variety of surfactants varying both in molecular structure and molecular weight. Limestone appears to be particularly sensitive to basic, nitrogenous surfactants. INTRODUCTION Investigations in recent years have shown that petroleum reservoir rock wettability can exert a significant influence on the efficiency with which oil can be produced by water flooding. While most reservoirs are presumably water-wet, they niay range in their degree of water-wettability from near-neutral to strongly water-wet.'" Reservoir wettabilities other than strongly water-wet are likely to be induced by adsorption of surface-active components froni the crude oil on the pore walls of reservoir rock.:' Little is known, however, about the nature of the surface-active materials which are likely to be adsorbed by the reservoir rock. Due to the complexity of crude oils. attempts made in the past90 isolate these surface-active components have met with only limited success. It is probable that many different types of surface-active materials arc indigenous to crude oils and that many of these may be adsorbed to varying degrees by reservoir rock. This was cxolored in the studies discussed in this paper. The over-all objective in these studies is to ascertain whether the wettability of a given reservoir can be determined by examining the surfactant content of the reservoir crude. To this end, crude oils were examined to determine the variability of indigeneous surfactants with regard to chemical type and molecular weight. Crude oils were separated by distillation into fractions differing principally in molecular weight, by chroma-tography into fractions containing compounds differing in polarity, and by solvent extraction into nitrogenous and non-nitrogenous fractions. Individual fractions were then tested for their effects on the wettabilities of sandstone or limestone rock samples. EXPERIMENTAL PROCEDURES Fractionation of the Crude Oils Samples of Miocene, Eocene and Jurassic crudes were distilled at temperatures not exceeding 200°C. The final stages of distillation were completed in a molecular still at pressures down to three microns of mercury. Fifteen to 30 fractions were obtained from each crude oil. These cuts were sufficiently broad that separation can be considered to have been effected principally on the basis of the molecular weights of the constituents of the crude oil. A considerable portion (20 to 40 per cent) of the crudes would not distill under these conditions. The residues were recovered and tested with the other fractions. Fractions differing in polarity were separated from a crude of Pennsylvanian age and an extracted sample of Miocene oil by chromatography, using a solid adsorbent. Since surfactants are, for the most part, polar compounds, chromatography should separate many of the surfactants from the crude oil. Such a separation should provide fractions containing compounds differing in molecular structure. Nitrogeneous compounds were extracted from Miocene crude oil with a solution of sulfuric acid in meth-anol. The residual oil was further processed by chonia-tography. Each of the fractions obtained by thesc procedures was dissolved in a non-polar solvent (xylene) and diluted to its original concentration in the crude oil. No attempt was made to maintain an anaerobic atmosphere above the samples while they were being dissolved. These solutions of the fractions were then tested for their effects on the wettability of sandstone and limcstone as discussed in the next section. Measurement of the Effects of Crude Oil Fractions on Rock Wettability No entirely satisfactory method for measuring rock wettability has yet been developed. All methods used are empirical. The imbibition test was used in these studies. This test is based on the tendency of a rock to imbibe the wetting phase spontaneously. For example, if a strongly water-wet rock is first saturated with oil and then placed in water, the water will quickly invade the rock by capillarity and much of the oil will be displaced. If the rock is slightly water-wet, water irnbibition will proceed more slowly and, in many instances, considerably less oil will be displaced. A water-saturated, oil-wet rock will imbibe oil. The initial rate with which water (or oil) imbibition takes place indicates, qualitatively, the degree of water (or oil) wettability of the rock.