Search Documents

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. T. Tye

REGARDING the results of preferential flotation at Cananea, Weinig has stated that "The concentrating mill of the Cananea Consolidated Copper Company at Cananea, Mexico, furnishes an excellent example of modern flotation practice. The complete figures are given because they present so forcibly the advantages of modern selective flotation."' L. 0. Howard notes that "Perhaps the outstanding example so far published of improvements in results through the use of selective flotation is that at Cananea, Mexico."2 The following notes indicate the conditions under which the results were obtained at Cananea; also the effect of preferential flotation at the concentrator and at the smelter. In the majority of cases the full benefit of selective flotation is not fully realized, as the concentrates are shipped from the mill to smelters owned by other companies. The saving made at a certain concentrator by this method of flotation may be well understood but the saving resulting at the smelter from the results of preferential flotation at the mill is not so apparent, as the data are contained in the smelting records of some other company. Even at the smelter the great gains following preferential flotation may not be noted, as a variety of ores and concentrates from various sources are received and the difference from the changed concentrator operations of a certain mill may be obscured. As noted by Professor Weinig and Professor Howard, the results obtained at Cananea brought about a veritable metallurgical revolution at the smelter.

Jan 1, 1927

By Eugene Guccione

Before answering the question raised in the title, let's briefly consider how East-West trade is viewed within the entire US political spectrum. Essentially, there are four major schools of thought: (1) The Peaceful-Coexistence School. Advocates of this school call themselves free-traders and hold to the premise that: (a) trade benefits all parties involved, hence it is the best tool to achieve peace; (b) US trade barriers should be removed, and the quicker the better; and (c) negotiations, cultural exchanges, and political compromise should be used extensively.

Jan 9, 1974

By S. Senderoff, D. E. Couch

A PROCESS for the electrolytic preparation of molybdenum from molten salts has been described previously. This previous work centered on electrowinning and electroplating characteristics of the process. In this paper the properties of the process as a refining medium are discussed. In producing metals from ores, it frequently has proven most economical to obtain a comparatively impure metal by smelting, and to purify the product by electro refining. Direct electrowinning from molten salts is rather difficult when a porous diaphragm is required in the process, as in the case of molybdenum, since satisfactory refractory materials for such a diaphragm in molten salts have not yet been developed. In electrorefining, however, a soluble anode is used. By suitable control of anode and cathode current densities, the lower-valent molybdenum compound used in the electrolyte is not oxidized, and a diaphragm is not needed, thus avoiding difficulties which are encountered with other electrowinning processes. Electrorefining may result from two different processes in the cell: Dissolution of the molybdenum and the less noble impurities with a separation of the more noble impurities as an anode sludge; the electrodeposition of molybdenum and the more noble metals at the cathode, leaving the less noble metals in the electrolyte. The amount of separation which occurs in each process is determined by the potential of the operating electrode and the relative concentration of the various species at (or in) that electrode. Since molybdenum has a comparatively noble position in the EMF series in molten alkali halides,2 most refining would be expected to occur at the cathode. In this work only the cathodic process was studied. The objective was to determine to what extent various metallic ions, if they dissolve from the anode or are otherwise introduced, were concentrated in the electrolyte. The necessary conditions for the separation of each and the limiting concentration which may be tolerated in the electrolyte for effective refining were studied. The deposits were chipped from the cathode and analyzed spectrochemically for metallic impurities. Besides determining the major contaminant, a general qualitative analysis was obtained to be sure that other metallic ions were kept at a very low level during each series of runs and to be sure that the baths were not being contaminated accidentally. Samples of the bath, for analysis, were taken at the temperature of operation so there was no chance of selective crystallization during cooling. In this way the ratio of molybdenum in the bath to the other metal could be determined readily. These data permitted a check on the anode efficiency and any volatilization that took place during the electrolysis. Experimental Apparatus—The apparatus as shown in Fig. 1 was used to determine the effect of the various foreign ions upon electrodeposited molybdenum. The entry chamber A allowed the cathodes to be removed without cooling the bath and without allowing oxygen or moisture to enter." The cathodes were made Prom 0.25-in. tungsten rods and were rotated during the electrolysis. The balloon in the lower arm B was inflated with helium after the cathode was drawn up into the upper section for removal. A new cathode was then placed into the entrance chamber A after which the chamber was flushed

Jan 1, 1959

By Chas. Y. Clayton, Francis B. Foley, W. E. Remmers

DuRing the summer of 1919, the late Dr. Henry M. Howe, then Chairman of the Division of Engineering of the National Research Council, organized a committee to obtain a better insight into the behavior of carbon steels under the influence of various treatments by a proper control of the time and temperature factors. During part of 1919 and 1920, work in connection with this investigation was carried on at Dr. Howe's laboratory at Bedford Hills, N. Y. During 1921 there was an enforced hiatus in the work, occasioned by the illness which resulted in Dr. Howe's death in 1922. At that time one of the present authors compiled the results of the work which had been done and this was published in 1923.' Following the publication of this work, it seemed desirable to carry on in the same manner an investigation of steel of C 0.75 per cent., which steel had not been as fully treated as had the other steels of C 0.34 and 0.52 per cent., used in the published work. Furthermore, certain unusual results have been obtained in the treatment of C 0.52 per cent. steel by quenching and drawing, and repetition of this part of the work seemed advisable. This has been done during the past year at the School of Mines and Metallurgy of the University of Missouri at Rolla, Mo., by a cooperative undertaking of the School and the Bureau of Mines, working in conjunction with the Committee on Heat Treatment of Carbon Steels of the National Research Council. The present paper is a report of the results obtained in this work.

Jan 1, 1926

By Cyril Stanley Smith

THE art of metallography is mature and the forms in which various micro-constituents appear are well known. Investigations almost without end have disclosed the importance of the exact manner of distribution of phases on the physical properties and usefulness of an alloy. Surprisingly, however, relatively little attention has been paid to the forces that are responsible for the particular and varied spatial arrangements of grains and phases that are observed. Like the anatomist, the metallurgist has been more concerned with form and function than with origins. In this paper it is proposed to develop the simple concept that many microstructures result from an attempted approach to equilibrium between phase and grain interfaces whose surface tensions geometrically balance each other at the points and along the lines where they meet. From this follows a number of principles which may prove to be of interest to the metallographer and of practical use in explaining failures and in designing alloys for particular service. In general, the discussion will be limited to structures obtained after full annealing. The simple principles do not apply to structures resulting from Widmanstatten mechanisms in precipitation, or to other structures not in local equilibrium and in which lattice coherency is a determining factor. INTERFACIAL TENSION Much has been written by physical chemists about the free energy of surfaces, which manifests itself as a measurable surface tension. Two- and three-phase interfaces in fluids seek a condition of minimum energy and approach a geometrical configuration in which the various forces are in vectorial balance.* Measurement of the angles established between the interfaces when in equilibrium provides a quantitative value for the relative value of the surface forces involved. The case of two fluids meeting at the surface of a solid (of great importance in connection with the flotation of minerals) has often been studied, but there have been few investigations of the equally definite interface between two or more crystals of a single solid phase, or the more complex cases where crystal grains of more than one phase are involved. The principles are best illustrated by considering first the case of two and three immiscible liquids. If, as in Fig I, a liquid, 2, is dropped into a less dense liquid, I, it will form a sphere-if gravity and viscosity can be ignored-for in this shape the interface has the smallest possible area. If these two phases should together encounter a third phase in which they are both immiscible, the geometry will change to become that which gives the lowest total energy for all three interfaces. Thus, if the spherical drop of liquid, falling through r, eventually reaches the interface between liquids 3 and I (we are assuming that the density of 3 is greater than 2, and 2 than I), it will assume the shape of a lens, the angle

Jan 1, 1948

By Otto H. Henry, J. J. Cordiano

THOUGH powder metallurgy is one of the oldest of metallurgical processes, it is in its infancy as a branch of the modern field of metallurgy. As early as 3000 B.C., the ancients produced implements and weapons of iron by reducing iron ore in a charcoal fire and forging the resultant sponge while still hot into the desired shape. Melting and casting soon superseded the powder metallurgy practice, and it was not until the turn of the twentieth century that powder metallurgy was applied to the commercial manufacture of tungsten lamp filaments. From this beginning, the use of the powder metallurgy process spread to the manufacture of porous oil-impregnated bearings, cemented carbide tools, contact points, diamond grinding wheels, clutch facings, starter brushes, resin-bonded radio cores, magnets, metallic filters, and other parts. More recently, and particularly during the present war, there has been a definite trend toward the manufacture of machine parts by this process in competition with the more conventional fabricating methods. Notwithstanding these many developments, scientific progress has been slow. While many articles on powder metallurgy have appeared in the press and various publications, there have been too few contributions to our technical societies, with the result that there is a dearth of the type of information necessary for the full development of this science. It is of primary importance that the results of research and development be freely disseminated if powder metallurgy is to realize its fullest potentialities. PURPOSE OF INVESTIGATION Excluding the refractory metal field, all commercial powder metallurgical products made by a cold compressing and sintering operation contain voids. These voids can be substantially eliminated by subsequent severe working and heat-treatment, but such practice has not proved economical in most applications. By applying heat during the compressing operation, plastic deformation of the powder particles is substantially increased, and the resultant compact or briquette is practically free of voids. However, hot-pressing has many attendant problems, which at present preclude its use in the manufacture of precision parts. The more important of these are to devise: I. A die steel capable of withstanding high pressures at elevated temperatures. 2. A high-temperature lubricant capable of preventing excessive die wear and welding of the compact to the die walls. 3. A method of retaining a neutral or reducing atmosphere in the compacting zone of the die assembly. 4. A means of ejecting the hot-pressed specimen into a neutral atmosphere until reasonably cold.

Jan 1, 1945

By R. F. Lynch, J. D. Wood

The Al-1.0 pct Mg alloy 565 7 was studied using optical microscopy and electron microprobe X-ray analysis. Constituent particles were found to exist inter-dendritically in the as-cast material in a region of precipitate free a -aluminum. Five phases besides a fine precipitate and a-Al were identified in the cast structure: Fel3, Fe2Al7, Mg2Al3, CUMgAl2, and Cu2FeAl7. Thermal treatments conducted for 100 hr at 1180°, 1130°, 1080°, 1030°, 980°, and 880° F revealed a general dissolution and spheroidization of the in-terdendritic constituent network observed in the cast structure. The principal constituents present in the thermally treated structures were FeAl3 and Fe2Al7 with the relative amount of Fe2A17 to FeAl3 increasing with a decrease in the treatment temperature. The phases Present in the wrought structure were identical to those observed after the thermal treatments, with the constituent particles strung out in the direction of rolling. ALLOY 5657 is a nonheat-treatable commercial purity Al-1.0 pct Mg alloy utilized extensively because of its bright finishing characteristics. This investigation was conducted to determine the constituents present in 5657 alloy, and to study the effect of extended thermal treatments on morphology. Numerous studies have been carried out to establish the equilibrium diagrams for various aluminum systems,1-3 with phase identification based on X-ray analysis, morphology, and the etching response of relatively large particles. Phragmen4 conducted a study of the phases in aluminum eutectic systems and compiled a "corrected" table of etching responses, drawing on his work plus that of Schrader,5 Keller and Wilcox,6 and Mondolfo.7 A review of the original work of Keller and Wilcox, and Mondolfo, which was concerned with the constituents found in commercial alloys, reveals that in numerous cases their etching responses differ from those reported by Phragmen and from each other. These inconsistencies may occur because a specific constituent will react to a given etch in a varying manner depending upon its size, the elements dissolved in the phase, the other constituents surrounding a phase, and the solute content of the matrix. Work with a commercial orientation was conducted on alloys 2024 and 3003 by Sperry8,9 and on alloy 3003 by Barker,10 where the relationship between the phase diagram and the nonequilibrium structure of an alloy was examined. Backerud11 investigated the A1-Fe binary system and found that at high cooling rates the equilibrium eutectic reaction forming a-A1 and FeA13 is replaced by another lower temperature eutectic reaction forming a-A1 and metastable FeAl6, a constituent first identified by Hollingsworth et al.12 Most of the above mentioned studies were conducted on materials having a significantly greater alloy content than 5657 alloy, where the relatively small size and sparse distribution of second phase particles hinders the process of identifying constituents. EXPERIMENTAL PROCEDURE Material with a composition as given in Table I was examined in the as-direct chill cast, hot rolled and cold rolled conditions, and after thermal treatment of the cast structure. Thermal treatments were terminated by a water quench. Microscopic examination was conducted under various lighting conditions following the application of standard etchants as specified in Table 11. A semi-quantitative electron microprobe X-ray analysis was conducted for Al, Mg, Fe, Cu, Si, Zn, and Ti. RESULTS AND DISCUSSION Microstructure of the As-Cast Material. Particles of second phase material were found to exist inter-dendritically, principally in regions of precipitate free a-Al, as illustrated in Fig. 1. Adjacent to the ingot edge was a region of inverse segregation, resulting in an increased amount of second phase material containing large sized particles which aided in phase identification. Phase Identification. Cast Structure. Five phases besides a-Al and a fine precipitate were identified using optical microscopy and electron microprobe X-ray analysis, as presented in Tables II and III, respectively. FeA13 and Fe2A17 are often found with Fe2A17 forming a sheath around the core of FeAl3, resulting from an incomplete peritectoid reaction. These phases have a nearly identical appearance under white light, although they are easily differentiated under crossed polarizers, as characteristically illustrated in Figs. 2(a) and 2(b), respectively. Microprobe analysis con-

Jan 1, 1970

By Fulton B. Flick

The micrography and macrography of aluminum and its alloys present certain difficulties. Many of the difficulties attendant on the micrography have been removed by methods developed during the past few years, notably those of E. H. Dix, Jr.1 The development of grain size in aluminum and its alloys may be equally troublesome, yet comparatively little detailed attention appears to have been given to it. Satisfactory reagents are available for the development of such structurcs in ferrous and most non-ferrous metals, but those applied to aluminum and its alloys, i. e., alcoholic or aqueous solutions of sodium hydroxide or hydrofluoric acid are not entirely satisfactory. Hanson and Arch-butt,2 in speaking of these two reagents, state that "These two reagents give fairly satisfactory results, but they sometimes produce badly tarnished surfaces from which the surface deposit is difficult to remove." It has been our experience that neither of these reagents is to be entirely relied on for developing structures suitable for study or photography. This means that when the etch fails to produce satisfactory results the specimen must be repolished, through the 000-paper at least, and then etched with another reagent. This procedure entails a considerable loss of time, and the final results may not be all that might be desired. However, the reagent to be described, although not a panacea for all etching troubles, has improved results so markedly that it is felt that it & worth offering as a grain-size etch generally applicable to aluminum and aluminum alloys. Czochralski3 in 1915 mentioned the application of a solution of 10 to 20 c. c. concentrated hydrofluoric acid in 100 c. c. absolute alcohol, etching in this reagent being followed by dipping in concentrated hydrochloric acid soliltion.

Jan 1, 1925

By C. E. Mills

STUDIES of ground movement and subsidence resulting from mining operations cover a broad field. It is also a very important consideration and one that eventually affects nearly every mining operation of any extent. The damage to surface buildings, removal of mine surface plants and replacements of main hoisting shafts must reach an astounding expenditure were these cost figures available over a period of years. Were the subject one of mathematical formula and dependent only on the angle of draw of the walls or country rocks, the problem would be relatively simple. Consideration must be given to depth and extent of workings; structural conditions of the orebodies and enclosing country rock; physical properties of these same rocks, including schistosity, bedding, jointing, slips, dikes, faults, and other structural weaknesses. The method of mining, extent of openings, supporting pillars, and amount of moisture or water underground are other pertinent factors. With such a large number of variable factors, it is apparent that the subject of subsidence is one that must be based largely on experience and results at other mines where conditions are somewhat comparable. In presenting this paper, it is the intent to describe the progressive results of past ground movements at the United Verde, to bring out physical conditions largely responsible for this movement, but to refrain from theorizing on the ultimate extent of subsidence resulting from future mining operations.

Jan 1, 1934

By F. George, W. Tice, M. Salkind

It was found that Al-A13Ni could be readily cold rolled perpendicular to but not parallel to the whiskers. Reductions of more than 98 pct were achieved without cracking by rolling perpendicular to the whiskers, whereas extensive edge cracking was noted after only 15 pct reduction when rolling parallel to the whiskers. The longitudinal and transverse tensile strengths were nearly doubled, and the longitudinal yield strength more than tripled by cold rolling 50 pct in a direction perpendicular to the whiskers. The whiskers exhibited some waviness (elastic bending) as a result of cold rolling, but at very high reductions (greater than 75 pct) whisker fracture and misalignment became significant. A fine dislocation substructure in the matrix consisting of cells attached to the whiskers was pro -duced by cold rolling. Most of- the substructure was readily removed by a 1-hr anneal at 500°C. Cold rolling was found to substantially reduce the thermal stability of the microstructure at 610°C but did not affect the stability at 500°C. FIBER and whisker reinforced composite materials promise significant improvements in properties over conventional materials. Before they find wide use, however, it will be necessary to understand the response of these highly anisotropic materials to common metalworking processes. Most of the nonmetal-lic fiber reinforced materials have very low elongations (a few pct or less) in the direction of fiber alignment. Thus, metalworking techniques such as rolling and forging would not be as broadly applicable to these materials. This investigation was initiated to determine how a composite system consisting of Al3Ni whisker reinforced aluminum responded to rolling, what changes in the microstructure occurred, and the effect of deformation on the mechanical properties. The composite material studied was produced by unidirectional solidification of the A1-Al3Ni eutectic alloy'-7 and consisted of 10 pct by volume of aligned whiskers of Alai in a matrix of aluminum. It should be pointed out that this system is not representative of all composite materials, and the results will therefore not be universally applicable. The A1-Al3Ni system is characterized by: 1) A strong fiber-matrix interfacial bond 2) A ductile matrix 3) A sufficiently low fiber content to allow significant plastic flow between fibers 4) Strong, completely elastic whiskers (tensile strength 400,000 psi, elastic modulus = 20 X 106 psi.1 These factors allow the material to be readily rolled perpendicular to the fibers. If the fiber-matrix bond were not strong, such a weak interface could fail during rolling. A measure of the ability of a composite to be rolled in the transverse direction can be obtained from noting the transverse tensile behavior. In the case of Al-Al3Ni,2 there is considerable ductility (15 to 30 pct). In the case of boron filament reinforced aluminum, for example, the transverse elongation is less than 1 pct,8 and the material could probably not be cold rolled as readily in that direction. EXPERIMENTAL PROCEDURE 3-in. diam ingots of A1-A13Ni eutectic were unidi-rectionally solidified in graphite crucibles. The starting materials consisted of 99.99+ pct pure nickel and aluminum, and the pure eutectic ingots were made with 6.2 wt pct Ni. The unidirectional solidification process (described in detail elsewhere1-3) consists of preparing a master heat of eutectic composition, remelting, and withdrawing the ingot vertically downward through the heat source at a controlled rate so that plane front solidification proceeds upward at a constant velocity. The resulting microstructure consists of 10 pct by volume of whiskers of very high aspect (length to diameter) ratio. The fiber lengths have not been measured because of the difficulty of detecting fiber ends9 but exceeds 104. There is some possibility that the fibers may be continuous within one grain. Flat sheet specimens 2¾ in. sq and approximately 0.2 in. thick containing whiskers parallel to the plane of the sheet and to one edge were used for this study. A1-A13Ni exhibits either a rod-like (high solidification rates) or a blade-like (low solidification rates) whisker morphology,1,3 and both types were studied. Rolling was accomplished using a two-high rolling mill at a speed of approximately 10 fpm. The rolling direction was either parallel to or perpendicular to the direction of growth (direction of whisker alignment). Reductions of from 0.002 to 0.03 in. per pass were used with the most common value being 0.005 in. per pass. Cold rolling of Al-Al3Ni to more than 98 pct reduction in thickness was accomplished with no intermediate anneals. In addition. a series of speci-mens was cold rolled 97 pct with a 1-hr, 500°C anneal in air after each 50 pet reduction. Tensile testing was accomplished using a Tinius-lsen four screw testing machine. Flat sheet specimens + in. wide and between 2 and 2; in. long with the thickness dependent upon rolling reduction, were used. The gage section was in. wide and 1 in. long. Strain was measured using a clip-on LVDT extensome-

Jan 1, 1970

By A. G. Weber, R. L. Ledbetter, A. L. Hicks

A procedure which makes use of both analog and digital computers has been developed for predicting the pressure-production behavior. of water-drive reservoirs. The electric analyzer is used for matching the past pressure and production history of the reservoir and inferring the physical characteristies of the aquifer. When the history has been matched, a .set of base curves called influence functionce" are derived and the future behavior of the reservoir is calculated from these curves. INTRODUCTION Electric analog methods are particularly well-suited for complex water-drive problems. Like all other methods of analyzing water-drive reservoirs, however, analog methods are subject to certain limitations. One of the more obvious and serious of these results from inaccurate or insufficient knowledge about physical characteristics of the reservoir and aquifer. However, it is not insurmountable because the unknown characteristics can usually be inferred from the reservoir's previous behavior. Simons and Spain have shown that even with scant reservoir data and limited production history, electric analyzer studies can provide useful and reliable results. Aside from this limitation on analyzer predictions, the main disadvantage has been lack of a technique for keeping predictions abreast of latest production forecasts. Pressure behavior of a reservoir depends on the rate at which fluid is withdrawn; it is therefore necessary to specify the future withdrawal schedule before the future pressure behavior can be calculated. Conventionally, the electric analyzer predicts pressure behavior for a specific production schedule. If this schedule is abandoned in favor of some new one, as is frequently the case, either the study must be rerun or results adjusted in some manner. The usual procedure is to predict pressures for several different forecasts covering a wide range of production rates. Pressures for specific rates other than those studied can then be approximated by interpolating between the analyzer predicted curves. However, reliability of this type of prediction is doubtful. This paper describes a technique for predicting future behavior of water-drive reservoirs that retains all advantages of electric analyzer analysis and eliminates the main disadvantage. That is, the analyzer is used conventionally to infer unknown reservoir parameters from the pressure history, but not to predict the future behavior directly. Instead, a derived set of base curves, called influence l'unctions, can be used to calculate future behavior for any production schedule.

By D. J. MacKinnon, J. M. Brannen

Smooth, compact, dendrite free 24-h zinc deposits have been electrowon from zinc chloride electrolyte using a diaphragm cell. The cell consisted of sealed anode compartments containing DSA anodes separated from an open cathode compartment by Dynel cloth membranes. Fresh electrolyte was fed to the cathode compartment where zinc deposition onto an aluminum cathode was aided by air sparging. The catholyte passed through the diaphragms into the anode compartments from which chlorine gas and spent anolyte were withdrawn. Standard electrolysis conditions were: 15 g/L Zn, 0.12 M HCI, I5 mg/L tetrabutylammonium chloride (TBACI) as the addition agent, 35°C, and 323 A/m2 (30 ASF) current density. The effect of variations in these conditions on the morpohology orientation, current efficiency, and energy requirement for 24-h zinc deposits was determined. The effect of total chloride ion concentration on the zinc deposit was studied by adding various amounts of NaCl to the electrolyte.

Jan 1, 1983

By F. T. Selleck, H. H. Reamer, B. H. Sage

An experimental investigation was made of the effect of temperature upon the three-phase pressure associated with the propane-water and propene-water systems when hydrates were present. In addition, the characteristics of the propane-propene-water system were established over a limited range of ternperatureo under conditions such that hydrate was formed. The hydrate phase for this system may he a solid solution and the distribution of propane and propene in it is similar to that found in the coexisting hvdrocarhon liquid phase. INTRODUCTION A knowledge of the characteristics of hydrates of the hydrocarborrs encountered in industrial practice is of importance in connection with the design of process equipment. Villardl.1,2 carried out early studies of hydrates, and de Forcrand1 con-sidered the more probable compositions of the hydrates of hydrocarbons. Hammerschnid1 presented information about the propane-water and the isobutane-water systems. Scheffer5 studied the hydrate of hydrogen sulfide in detail, and de For-crand reported on the hydrates of krypton, argon, and xenon.1 Roberts and co-workers1,2 determined the nature of the hydrates formed in the methane-water and ethane-water systems. Carson and Katz10 studied the methane-propane-water, methane-pentane-water, and the methane-hexane-water systems in the four-phase region. The results of this rather extensive investigation indicated that the paraffinic hydrates formed solid solutions. The experimental evidence now available does not Support the existence of hydrates of the pentanes-antl-heavier hydrocarhons but it cannot be stated with certainty that such hydrates are not formed. Stackelherg. 11,12,13 made extensive studies of the crystal structure of paraffinic hydrate; by means of x-ray techniques and found that hydrates poses; a definite structure and composition. The existence of such a Structure does not preclude the firmation of Solid solutions of hydrates in aqueous systems containing two or more hydro-carbon~. Wilcox, Carson and Katz" reviewrd the information on the hydrates of importance in the processing of natural gas and presented data concerning their formation from natural gas. Kobayashi and Katz1' made studies at high pressure of the Hydrate of methane. and Unruh and Katz"' investigated hy-drates in mixtures of carbon rlioxide and methane. Frost and Deaton contributed to the knowledge of the composition of the paraffinic hydrates The irregularities in the experimental results were several times the expected uncertainties. This experience confirms the behavior encountered by other investigators indicating that hydrates tend to occlude water during their formation, thus rendering difficult the direct measoremeut of their composition. Miller and Strong2 investigated a number. of paraffinic hydrates from the standpoint of their possible application to (, the industrial storage of gas. Powel1 studied the effect of solutes upon the decomposition temperature of paraffin hydrates. Marked lowering of the decomposition temperature at a given pressure may he obtained by the use of such additive agents as ethylene glycol, urea. and sodium chloride. APPARATUS AND METHODS Two method* were here employed to study the behavior of hydrates. The first involved a glass capillary within which the hydrocarbons and water were confined over mercury. The second made use of a double-ended weighing bomb technique." The glass capillary equipment has been described elsewhere.'" A schematic drawing of it is presented in Fig. 1, where the arrangement of the agitator and mercury reservoir is shown in some detail. The lower part of the glass capillary, D, was enlarged to afford space within which the fluids used in the investigation could he stored at low pressures after their introduction through the valve. G. The temperature of the capillary was controlled by the circulation of a hydrocarbon oil of low viscosity from the agitated bath, B, through the vacuum jacketed column. C. The pump, A, was employed for the circulation of this oil. A relatively clear view of the capillary tube, D, was obtained through the vacuum jacket. Mercury was introduced into the lower part of the vessel, E, from

Jan 1, 1952

By D. J. Weintritt, R. G. Hughes

Statistics show arz increase in the average depth of wells drilled in recent years. As a corollary to this trend, drilling fluids have been improved in an effort to meet the problems inherent at temperatures approaching 500°F. Of importance are (1) deterioration of mud components and (2) the effect of solids on filtration and rheological properties. High-temperature, stable water-base and oil-bare muds are discussed. Those areas in which differences exist are pointed out. Results are based on data taken from the Fann consistotneter, rheometer and shear-strength measurements, static and dynamic filtration tests, methy-lene blue test for bentonite solids and specific heat measLrrenlents of muds. INTRODUCTION Higher well temperatures go along with the fact that the average depth of wells continues to increase. Recent data by Gardner' lists 137 completions deeper than 15,000 ft for the first half of 1964 with a record second-half total of 167 wells drilling or proposed. In addition, there has been an increase in drilling for steam for power production or mineral recovery. In this application the depths are modest, but the mud may approach the critical pressure and temperature of water. Scearce and Magnon' report drilling mud used at temperatures of about 700°F in the Salton Sea area of California. Most deep wells have been drilled with water-base muds. In recent years, however, there has been a substantial increase in the use of oil-base muds because of technological advances in effective additives. The significance of this development was dealt with in considerable detail by Simpson and his co-workers.3 Additiona1 field data have now been obtained to indicate that oil muds are competitive in control, performance and cost with the best types of water muds for use at high temperaturc. This parallel offer of two very different fluid systems, each offering a similar variability in performance, cost and convenience, has created the need to evaluate the merits of these fluids under specified conditions so that the advantages and disadvantages of each can be weighed in relation to the over-all drilling program. This paper is not intended as a review of all the factors. Rather, it attempts to emphasize: (1) important condltions and facts peculiar to high-temperature drilling muds, (2) that more than one imposed test condition or testing method is necessary to describe the quality of a mud at high temperature and (3) that elaborate experimental precautions are necessary whenever laboratory data are used in selection of a mud for field use. WHAT IS A HIGH-TEMPERATURE DRILLING FLUID? For the purpose of this discussion, a high-temperature drilling fluid is any system so formulated or treated to economically minimize the effects of temperature on the properties of the fluid. Our experience in drilling fluids suggests that these effects become obvious for many mud materials at temperatures of 300F or higher. It is understood that hydrolysis of starches, depoly-merization of certain organic thinners, or irreversible chemical reactions (such as that of clay and lime) can affect filtration, viscosity and shear strength at less than 300F. However, the temperature level is not a serious point and in no way affects the precautions and techniques used in this study. An up-to-date review of the literature on high-temperature drilling fluids and the many variations was treated by Rogers'in 1963. EXPERIMENTAL REQUIREMENTS TESTING EQUIPMENT AND PROCEDURES With the advent of deeper drilling and increased demand for temperature-stable drilling fluids, new testing equipment and laboratory techniques were devised for the evaluation of drilling fluids subjected to elevated temperature and pressure. While the equipment has not been standardized, it is in widespread use. Milligan et al. Qescribe a filtration cell for determining the filtration properties of drilling fluids at temperatures in excess of 300F. They showed the effect of variations in temperature and pressure on oil and water muds filtered in the 300 to 400F range. The dynamic filtration apparatus described by Simpson6 permits the study of the filtration properties to temperatures of 350F for drilling fluids circulated over sandstone cores. Watkins et al.' describe the use of pressure bombs for studying the effect of prolonged periods of elevated temperature upon the gelation or solidification of drilling fluids. Chisholm et a1.' describe the use of a modified cement consistometer adapted for use in drilling fluid evaluations. A similar consistometer is used in this study, although the application and data-recording method have been changed. The consistency of a mud sample is measured by timing the movement of a soft iron bob which is magnetically moved up and down in the sample container.* Changer in the time of travel and the temperature of the mud at that moment are plotted with a two-point Brown Elec-tronik Recorder. A 10-in. chart with a speed of 4-in./hr is used. Fia.- 1 is a generalized internretation of the data ob-

Jan 1, 1966

By Hsun Hu, R. S. Cline

The effect of rate of deformation on texture formatiotz has been studied with cube-oriented single crystals of 3 pct Si-Fe, compressed 80 pct at two widely different rates. Compression at a low rate (crosshead speed, 0.1 ipm) produces large orienta-tional changes and coarse deformation bands, whereas little change in orientation is observed, particularly at the surface of the crystal, when compressed at a high rate (impact velocity, -500 ips). Thin plates of mechanical twins are produced at the high rate, but their contribution to the deformation texture is practically negligible. The crystal deformed at a high rate has a lower hardness and a more uniform dislocation structure and is morc resistant to recrystallization. There is also a dilference in the recrystallization texture between the slowly and rapidly compressed crystals. These results indicate that plastic flow is less "turbulent" at high strain rates than at low strain ratcs. THE behavior of metals under high-speed deformation has been the subject of wide study in the past decade. Most of these works were concerned with mechanical properties during testing at high rates of loading, the resulting structures, and the theoretical aspects of the observed phenomena. The present status of knowledge and research activities in this field has been documented in recent publications.17' There is, however, very little information available in the literature concerning the effect of high-speed deformation on the texture formation in metals. The possibility of an effect of rate of deformation on texture is suggested by the microstructural differences observed between normally and very rapidly deformed samples. Aside from the strong tendency for twinning (and phase transformation in certain metals) in high-speed deformation, the slip-line patterns and the dislocation configurations show marked differences as a result of large differences in the strain rates. For instance, in mild steel in static and dynamic compression, Campbell and co-worker3,4 observed that coarse slip occurred on several systems in specimens deformed at normal strain rates, whereas specimens deformed rapidly showed only fine slip on fewer systems, the slip-line pattern being very similar to that in specimens deformed at low temperatures and at normal strain rates. The absence of multiple slip was also noticed by Dieter5 in shock-loaded nickel. The dislocation configuration in an iron shock loaded at 70 kbar pressure was shown by Leslie et al.6 to be similar to that produced by light rolling at low temperature—the dislocation lines were mostly straight and uniformly distributed. These observations suggest that the mode of deformation at high strain rates is notably different from that at low strain rates. Consequently, the nature and the extent of lattice reori-entation during deformation should also be different. This investigation was undertaken to test this idea. MATERIAL AND METHOD The remaining part of a single-crystal ingot of a 3 pct Si-Fe alloy,* prepared for an earlier investi- gation,1 was used in the present studies. Specimens 9/16 in. square and 0.365 in. thick were cut from this ingot with (001) planes parallel to the square surfaces, and the [loo] and 1010] directions parallel to the edges of the specimen, within ±1 deg. These machined crystals were etched to remove distorted metal, and annealed at 1300°C for 24 hr in a purified helium atmosphere. The annealed crystals had a hardness of 161 Dph. The crystal orientation was rechecked with X-ray back-reflection techniques. In high-strain rate experiments the crystal was compressed in a Dynapak machine to approximately 80 pct reduction in thickness (from 0.360 to 0.070 in. with an impact velocity of -500 ips). Thus, the duration of loading was approximately 6x 10-4 sec, and the average strain rate was about 103 sec-1. As a result of this rapid, severe deformation, the specimen became a roughly circular thin disc. The original shape of the crystal, however, could still be recognized by a diffusely outlined square area in the center of the disc. For compression at a low speed, the crystal was deformed in a universal testing machine at a rate of crosshead movement of 0.1 ipm. Compared with

Jan 1, 1965

By H. J. Struth

In these trying times of proration and low oil prices, it is decidedly necessary for all branches of the petroleum industry to accord full recognition to the economic phenomena that contribute to its varying state of welfare. Perhaps no other single factor has a more important bearing upon the general oil situation than the supply and demand of gasoline. Year after year, the records have shown that the degree of prosperity or depression accompanying the industry's developments has been to a large extent influenced by the degree of balance maintamed between the supply and demand of gasoline. More and more it is being realized within the industry that equilibrium between the supply and demand of gasoline forms the basic structure of crude and product market values and, consequently, the deciding factor in the financial results of the industry as a whole. The influence of the gasoline situation upon the market and financial structure of the petroleum industry was effectively demonstrated during 1930, when excess accumulation of gasoline undermined not only the refined oil market but the crude market as well. In fact, it was a top-heavy gasoline situation that defeated the realization of benefits that might have accrued from an otherwise favorable statistical position in the producing branch of the industry. Indicative of this is the fact that crude oil production was curtailed to the extent of 98,323,000 bbl. last year, while refinery runs to stills were maintained at an excessive rate until late in the year, creating an excess gasoline production of 6,663,000 bbl. above actual requirements. Nevertheless, the movement to curtail refinery operations during the closing months of the year prevented a far worse situation, although it came too late to turn the ebbing momentum of the general oil market. Despite the severe depression of the market values that accompanied 1930 developments, it can be said that the results attained during the closing months of the year, in the direction of production control, marked a decisive turn in the industry's economic affairs. In fact, a review of the oil situation from every angle points definitely to a better general understanding and recognition of the workings of the economic law of supply and demand. As a result, the year closed with crude production in

Jan 1, 1931

By A. A. Dor

Out of nine new major iron ore concentrators put in operation during the last three years, or expected to be commissioned in 1968, seven incorporate primary grinding mills and have a total design capacity of 13,150,000 ltpy of pellets, while only two include conventional rod and ball mill grinding circuits for a total design capacity of about 6,100,000 ltpy (Table I). This evolution in the application of primary grinding to hard, fine grained magnetite ores represents an important development in the technology of mineral processing. It has been the outcome of comprehensive testwork in the laboratory and in pilot plants.

Jan 11, 1968

By Albert F. J. Bordeaux

The immediate vicinity of the sea-shore, affording special facility for the exportation of ores, makes it possible to work certain mines in the Vladivostok district, which, in more remote places of Siberia., would remain unproductive. Outside of the city of Vladivostok the population is small and the country is very little prospected. Additional discoveries of valuable deposits like the large body of calamine which has recently been opened in the neighborhood of earlier worked lead-silver ores, in the Tetiuhe valley, are still in the field of possibilities. For many years gold alone was produced, in part from the coastal rivers and in part from a quartz-vein on Askold island near Vladivostok. But the production is diminishing, and prospectors are looking for other rivers in the interior, such as the tributaries of the Ussuri. These rivers are now more accessible than formerly, due to the slow but gradual development of colonization by the Russian peasants. The few natives of the country, called Orodjones, are of the Chinese race. They resemble the North American Indian and are hardy fur-hunters. They have given some attention to placers and have already shown good specimens of gold-dust from the rivers Iman, Bikin, Noto, etc. Coal-mining was begun in the Vladivostok region more than 20 years ago, but in a somewhat irregular way. The industry is not as yet important and the best coal-seams are badly prospected, or are even neglected. Copper, lead, and iron exist in several places. The amounts give some encouragement to the anticipation that the discoveries will give rise to important metallurgical works. I here present a review of the various deposits, based upon such safe information as is in hand, when I have not drawn upon my personal observations. Fig. 1 is a map of Eastern Siberia, showing the mineral deposits.

Jan 1, 1913

By J. J. Crowe, G. K. Burgess

PAGE, Theories of Allotropy of Iron........... 667 Previous Determinations of A2 and A3 in Iron........ 668 Critical Ranges as Determined by Expansion........ 669 Critical Ranges by Thermoelectric Observations........ Critical Ranges in Terms of Crystalline Structure....... 670 Critical Ranges as Detected by Mechanical Methods...... 670 Critical Ranges as Given by Electrical Resistance....... 670 Critical Ranges as Determined Magnetically........ 671 Critical Ranges as Determined Calorimetrically....... 673 Critical Ranges from Heating and Cooling Curves....... 673 Summary of Previous Determinations of A3 and A2 in Pure Iron.... 675 The Present Investigation............ 678 The Experimental Method........... 678 Arrangement of the Apparatus.......... 679 The Measurements of Temperaturc.......... 679 The Measurement of Time........... 679 The Thermocouples............ 681 Temperature Scale and Calibration of Thermocouples...... 681 Mounting of Thermocouples........... 682 The Differential Measurements.......... 682 The Furnace and Accessories........... 682 The Vacuum Pump............ 683 The Energy Supply............683 The Rheostat.............. 683 The Materials Investigated............ 685 Sources of Iron............. 685 Preparation and Description of Samples......... 685 Chemical Analyses............. 687 The Experimental Data............. 688 The Preliminary Observations.......... 688 The Definite Series............691 Description of the Plotted Curves........... 694 The Effect of Plotting at Different Intervals........ 694 The Curves of the Definite Series.......... 695 . The Curves of the Preliminary Series......... The Existence of Other Critical Ranges......... 696 The Microscopical Examination........... 697 Summary and Conclusions............ 698 Bibliography............... 701 Plates................ 704

Jan 1, 1914