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By Walter R. Hibbard

THE increased strength of a polycrystal-line metallic aggregate compared with that of its individual crystals generally has been associated with complex stress distributions at the grain boundaries resulting from atomic irregularity between grains. This disregistry, together with the necessity for adjacent crystals to deform 'compatibly regardless of the single crystal crystallographic strain mechanism, complicates this mechanism so as to increase the metal's resistance to deformation. Although Taylor1 has shown from purely mechanical considerations the requirement for at least five active slip systems to absorb the complexities during the homogeneous deformation of polycrystalline face-centered cubic metals, experimental studies by Barrett and Levenson2 indicate that this is feasible only in a qualitative sense because of deviations from homogeneous deformation. Seitz and Read in their review3 state: "Unfortunately . . . present knowledge of the grain boundary influence is not sufficient to complement the work in single crystals and provide us with a good foundation for treating polycrystals." The purpose of this investigation was to attempt to clarify the gap between single crystals and crystalline aggregates by an analysis of the effects of deformational stresses. Some of the results were described by C. H. Mathewson in his 1943 Campbell Memorial Lecture.21 PREVIOUS INVESTIGATIONS Since the performance of single crystals deformed under pure stresses has been relatively thoroughly investigated, the most significant researches are concerned primarily with deviations from single crystal behavior of large grained specimens. Qualitative grain boundary effects involving the observed amount of slip were reported by Carpenter and Elam5 in 1921. Individual crystals in a two or three grained aluminum specimen deformed by tension acted in the normal manner described by Taylor and Elam4 except for marked modifications at the grain boundaries. There the power to withstand deformation was considerably increased, leaving a ridge on the specimen where decreased slip occurred, often noticeable 34 in: from the boundary. Adcock,6 Yamaguchi,7 Seumel,8 Hirst9 and others have also reported this phenomenon as a qualitative trend. Yet attempts by O'Neill10 and Ljunggren11 to measure a difference in hardness at grain boundaries in undeformed specimens were unsuccessful. Miller12 measured quantitatively the reduction in slip near the boundary between the single crystal and polycrystalline areas of zinc specimens. These effects consisted of two parts: I. Next to the polycrystalline interface the distribution of stresses was so altered

Jan 1, 1948

By Shawn T. Sorrell, Carl Hrovatic

Land is a precious resource and should be treated as such by all members of our society. The soil covering this earth is only a very thin outer layer, varying in thickness from a few inches to a few feet and covering the rocks and minerals lying beneath the surface. The wise use of this valuable commodity is the responsibility of everyone. Many everyday activities disturb the earth's surface. Examples are highway construction, housing and commercial developments, agriculture, and surface mining. This chapter discusses the relationships of the environment to land as it applies to surface operations ill the coal industry. Mining by surface methods disturbs, for a brief period of time, thousands of acres of land annually. In addition, refuse piles, slurry ponds. abandoned mine structures, unprotected mine openings, and unsightly cleaning plants can also adversely affect land unless properly handled. ACTIVE SURFACE MINING OPERATIONS Mining by surface methods includes rock quarries; sand and gravel pits; huge open pits to extract iron, copper, phosphate, and other ores: and coal mining. Production of coal by surface methods is now approaching 300 million tons annually, amounting to almost 50% of the total coal output. Surface coal mining can be classified into the following four broad categories: Open pit mining is practised where the coal beds are extremely thick, as in some western states, or where the coal beds are sharply pitching, as in the anthracite region of the eastern United States. A typical open pit mine, with coal beds of 10 to 100 ft or more thickness and a relatively small ratio of overburden, generally employs large scraper-loaders to re-

Jan 1, 1973

By I. Iwasaki, P. L. De Bruyn

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

Jan 1, 1972

By Jun-Yan Chen, Stefan H. Boshkov

Metal mining in the People's Republic of China has shown great growth during the last three decades. Over 150 new iron ore mines and nonferrous base metal mines have been opened since 1949, althouc.11 most of them of medium and small size. Concurrently, many old mines were enlarged and reconstructed. The production of iron ore has grown from less than 1.5 million tons per year in 1949 to almost 76 million tons in 1978. A corresponding increase in the total annual output in the nonferrous metal mineral industry has also been noted. It is well known that the PRC is very rich in metal mineral resources. The reserves of tungsten, tin, antimony, molybdenum and iron ore are ranked in the top three in the world. Recently, some copper porphyry ore deposits were discovered in Jianxi and Anhui provinces. Some large nickel-copper sulfide deposits were discovered and have been developed in North- West China. Huge iron ore deposits have been found in Liaoning, Hebei and Szechwan provinces. However, the bulk of the iron ores are low grade. The growing metal mineral production has met basic domestic needs since 1949; it has also proven China's big resource potential. Mining methods have also undergone development in the past 30 years. About 80% of the annual output of iron ore comes from open pits, whereas about 58% of nonferrous metal ores come from underground mines. Blasthole open stoping, sublevel caving and induced block caving are widely used in Chinese underground metal mines (table 1). This paper summarizes in detail the planning for and application of these three bulk mining methods in the nonferrous and iron ore mines in China. CLASSIFICATION OF UNDERGROUND MINING METHODS The main principle of the classification of underground mining methods in PRC is ground support in the stoping cycles of the mining blocks or stopes. Table 2 lists this classification. It is essentially the same as that given in the SME Mining Engineering Handbook. Be- cause pillar removal is a secondary mining operation, using a variety of methods, they are not included in this classification. As is the case with most classifications in science and technology, there is no precise division between the classes of mining methods. Because of the rapid development of consolidated filling techniques in the past twenty years, some types of open stoping methods use fill in order to improve the ground conditions for the secondary recovery stage. Thus, these mining methods have features of both methods using no artificial support and those using artificial support. In this classification, this type of mining method is placed in the latter category. The shrinkage stoping method has been employed extensively to mine steeply dipping narrow veins of tungsten and tin in the Jiangxi, Hunan, Guangdong and Guangxi provinces. Shrink- age stoping is placed under the class of mining methods without artificial support be- cause this reflects the nature of the Chinese experience. The function of the broken ore serving to support the footwall and/or hanging wall is limited, because the expectation is for the host rocks to remain unsupported until the stope is drawn empty. APPLICATION OF BULK MINING METHODS Bulk mining methods consist of blasthole open stoping, sublevel caving and block caving. These stoping methods have much in common, such as: bulk ore materials blasted by long holes; higher production rates of stopes or blocks and higher production efficiencies of the whole mining systems.

Jan 1, 1981

By H. A. Kendall, W. C. Goins

Several investigations in recent years have shown that drilling rates are increased significantly with increased hydraulic horsepower. But, there has been no over-all method of designing jet-bit programs that efficiently uses the surface power. A study of present practices indicates that frequently as little as 50 per cent of the possible effects at the bit are used. Some observers have indicated that the best utilization of hydraulic horsepower (maximum effect on drilling rate) occurs when the bit hydraulic horsepower is maximum; others have stated that jet impact force is more important, and others have believed that maximum jet velocity is required. Limited efforts to date have shown some optimum conditions for bit hydraulic horsepower and impact, but these conditions cannot exist during drilling of a large part of the hole and do not provide a basis for designing a complete jet-bit program. This paper shows the maximum obtainable bit horsepower, impact force and jet velocity at all depths, taking into account the limitations of the pump, piping, hole and minimum circulating rate for adequate cuttings removal. Ranges of operation are developed; and flow rates, surface pressure and bit pressures are specified for each range to provide a maximum of any one of the desired effects. It also is shown that, by proper selection of nozzle sizes and by following the rules presented, the maximum obtainable quantities can be effectively utilized from surface to total depth. Finally, a simple graphical method of selecting nozzle sizes and flow rates is presented which can be used with familiar bit-company hydraulic tables and calculators to design jet-bit programs for maximum bit hydraulic horsepower, impact or jet velocity, as desired. These programs make most effective use of the pumps. Heretofore, there was no method available for designing field tests which adequately separated the effects of bit horsepower, impact and jet velocity. The programs and procedures developed in the paper are dissimilar and, when used in future field testing, should demonstrate which program is the most important in obtaining the fastest drilling rate. INTRODUCTION During the past decade, rig hydraulics has come into increasing prominence. There has been a definite trend toward providing higher horsepower pumps, jet-type bits have had increased use, numerous investigators"" have reported increased drilling rates as a result of increased hydraulics, and bit manufacturers have provided tablesa-" and calculators that are now commonly used 10 design jet-bit programs. Opinion has varied as to the hydraulic quantity which has the great- est effect on drilling rate. Papers and data have been presented that show pump horsepower,'9 it hydraulic horsepower and jet impact force,' each to be the most significant factor affecting drilling rate. Examinatibn of jet-bit programs of the bit companies indicates emphasis on jet velocity. Only pump horsepower can be eliminated because it can be used to produce any one of the bit effects which, a priori, must be more relevant factors. This contradictory state of opinion and practice regarding the bit effects is unfortunate, but several published references have been concerned with making one or another of the factors maximum; and, because these in each case have given results applicable to only intervals of the hole drilled, there seems to be ample reason to complete the previous efforts. It also is believed that the differences in programs for each effect, where they exist, should be delineated so that future use may determine which hydraulic effect is the more relevant. It is the purpose of this paper to: (1) show the theoretical maximum bit hydraulic horsepower, jet impact force and jet velocity available at all depths, taking into consideration all necessary restrictions on operating conditions; (2) illustrate procedures by which the maximum available horsepower, impact force or veIocity may be obtained; and (3) present a graphical method for rapid selection of jet-nozzle sizes and flow rates to be used with conventional procedures to design jet-bit programs for maximum bit horsepower, impact force or velocity as desired.

By S. K. Tarby, A. E. Rathke

A series of 0.21 pci carbon steel melts was processed under conditions which sinzulated industrial vacuum degassing practices. The results indicated that the efliciency of carbon deoxidation was not significantly increased by vacuunz degassing at chamber pressures below 100 torr. The two common phenomena of vacuu?rz carbon deoxidation, i.e.,an unaccountable carbon loss and nonequilibrium deoxidation, were observed in this study. Oxygen from adsorbed and chenzically combined water of certain refractory structures was probably responsible for the unaccourttable carbon drop. The nonequzlibrium deoxida-tion phenomenon was adequalely correlated by a bubble nucleation )mechanism. Although the major limiting factor in oxygen removal from these melts contained in alumina crucibles could not be eslablished with certainty, there was some evidence that melt-refractory interactions were not the most imp-portant limiting factor. CONSIDERABLE attention has been given to the use of carbon in conjunction with vacuum degassing* as a deoxidation technique. An advantage of utilizing the reaction: for deoxidation purposes is that the reaction product is gaseous and hence can be effectively removed from the melt. The pressure dependency of Eq. [I] is illustrated by the expression for the thermodynamic equilibrium constant, K: where pco is the partial pressure of carbon monoxide, and hc and ho are, respectively, the Henrian activities of carbon and oxygen in molten steel. The thermodynamic aspects of the C-0 reaction in molten Fe-C-0 alloys have been investigated extensively. Theoretical predictions based on Eq. [2] indicate that, at the chamber pressures reached in most vacuum degassing units, carbon is the most effective deoxidizer that can be obtained. ~ornak' has compared industrial values of carbon and oxygen contents with values calculated from theory, and has shown that on a commercial basis vacuum carbon deoxidation has not achieved the degree of success that is predicted from theoretical considerations of the C-0 reaction. The use of industrial units to determine the reason for this deviation is limited by economics and the difficulty in controlling critical process variables. Therefore laboratory-sized experiments in this area should yield valuable information. Investigations on vacuum carbon deoxidation have been made in experiments conducted under vacuum induction melting conditions where pressures in the low micron range, long treatment times, exposure to highly dynamic vacuum conditions, and relatively quiescent bath conditions have been maintained. Inve~ti~ators~~~ utilizing vacuum induction melting for the production of high-purity iron by carbon deoxidation have concluded that, under high vacuum conditions, melt-refractory interactions constantly supply oxygen to the melt. Thus, it has been suggested that refractory dissociation rather than the C-0 reaction establishes the lowest possible oxygen content of a melt. Thomas and Moreau4 and Bennett, Protheroe, and ward5 have studied carbon deoxidation of Fe-C alloys melted in magnesia crucibles under reduced pressures. The results of both studies differed considerably from those predicted by theory, and the limiting factor for lower oxygen contents was attributed to melt-refractory interactions. Because the refractory material used in both investigations was magnesia, no quantitative measure of crucible reaction could be made and the amount of carbon consumed during treatment was utilized as an indirect indication of the extent of crucible reaction. Studies concerned with the determination of the minimum oxygen content attainable in pure iron and Fe-C alloy material vacuum-induction-melted in various crucible materials have also been conducted."' The suitability of a crucible refractory for use under vacuum conditions appears to depend upon the major refractory constituent, the amount and type of impurity oxides, and the composition of the melt. Meadowcroft and Elliott9 have presented a theoretical review of the type and extent of various refractory reactions which should be considered in vacuum refining. ~eadowcroft'~ considered the vacuum degassing process to be dependent upon the "carbon boil" and has proposed that a part of the difference between the experimental and theoretical results for vacuum carbon deoxidation may be explained by the fact that the pco term in Eq. [2] is not the chamber pressure. Instead, the pressure necessary for carbon monoxide

Jan 1, 1970

By B. Kopelman, C. C. Gregg

THE reduction of tungstic oxide to tungsten metal powder by hydrogen is a process by which one might expect the resultant metal powder to he porous. In- deed, sponge iron, prepared by rcduction of the oxide in a reducing gas, is generally accepted as quite porous. with pores large enough to be seen readily under the optical microscope at relatively low magnifications. However, any pores that may exist in tungsten metal powder are not resolved by the optical microscope, and apparently, not even by the electron microscope. Fig r shows commercial tungsten powder magni- fied at I0,000 X by the electron microscope,' both etched and unetched. In an earlier paper by one of the authors,* the existence of ports in tungsten powder was required to explain adequately the particle size changes occurring during the reduction of tungstic oxide. The inability to detect these pores under the electron microscope at 10,000 X implies that these {pores} are of a size of 100 A units or less. (This in itself is by no means proof that pores above 100 A would not exist, since polishing effects on the specimen might smear up holes of such small magnitude). If, then, these pores are less than IOO A. and of the order of molecular size, then the density of the metal powder should be

Jan 1, 1949

By M. B. Ramachandra Roa

This paper records the results of the earth resistivity surveys made in the Godavari River in connection with the Ramapadasagar project. After describing the topographical and geological features of the area, the results of the investigation at the several sites have been mentioned. Further, a detailed account has been given of the resistivity methods adopted, the apparatus used and the interpretation of the curves. The resistivity measurements carried out over the water course have been specially outlined, and a review of the verification of the electrical indications by drilling in a number of cases, has also been presented. Introduction The Government of Madras has under consideration the Ramapadasagar project which is estimated to cost some Rs.660,-000,000 (about two hundred million dollars). The most essential feature of this project is the construction of a high dam across the Godavari near Polavaram for impounding the waters of this great river of South India, whose maximum discharge is 2 million cu secs in flood time. It is estimated that when the proposed reservoir is constructed, about one million tons of rice could be produced annually under irrigation. To those who have had any acquaintance at all with the recent distressing famine conditions which India has passed through and is still undergoing, the Lounteous effects which this project will bring about to the country in the future, are obvious. In the region of the proposed reservoir, the river flows for several miles through a hilly tract, hemmed in between flanks of hard, solid rock; but the river bed is mostly sandy. A few bore holes put down in this sandy bed touched rock at a depth of 180 to 200 ft. The river bed is about jo ft above the mean sea level (m.s.l.) and the bedrock was found at —125 to —160 ft m.s.l. The crest of the dam is proposed at +162 ft m.s.l. The proposed dam mould therefore be about 120 to 130 ft above the river bed, and the foundations would have to reach down nearly zoo ft below the bed at the deepest part. A number of alternative sites were proposed for investigation, and it became necessary to quickly ascertain the bedrock topography at these sites. Dr. M. S. Krishnan,* who was consulted in the matter, furnished a detailed account of the geological features of the region and suggested a geophysical investigation which the writer carried out from February to April 1944, employing solely the electrical resistivity methods. The total length of the survey lines for the electrical measurements amounted to 62,600 ft and the number of resistivity determinations was about 2500. Altogether nine alignments for the dam were inten-

Jan 1, 1949

By Frank M. Monroe, James R. Cost

The solubility of nitrogen in vanadium is determined from 275" to 575°C by measuring the height of the nitrogen internal friction peak of equilibrated V-N alloys. The proportionality constant at 275°C between the internal friction peak height (Q- 1) and the atom percent nitrogen in solution is found to be 0.095 per at. pct for nitrogen concentrations up to 0.8 at. pct. The heat of solution of the nitride in vanadium is 5500 cal per mole. The solubility of nitrogen in the Group V metals is discussed. LITTLE work has been performed on the vanadium-nitrogen terminal solid solution. Hahn1 found the solubility for nitrogen to be very small and reported the existence of a hexagonal phase of composition near that of V2N at the solubility limit. Rostoker and Yamarnoto2 reported the solubility to be at least 3.5 at. pct at the melting point and to be less than this value at 900°C. In addition, they reported from X-ray diffraction studies that nitrogen in solution produces tetragonality in the vanadium lattice. An X-ray study by Schonberg3 has confirmed the results of Hahn but indicated that the tetragonality observed by Rostoker and Yamamoto was due to the presence of oxygen in their specimens. Beatty4 has performed lattice parameter and hardness measurements on terminal solid solutions and found the upper limit of the solubility to be at least 0.66 at. pct N. No measurements have been made of the pressure-temperature-composition relationships (P-T-X) for the terminal solid solution. As a part of a research program on gas-metal equilibrium, an attempt was made to study the P-T-X relationships in the V-N system using both the internal friction and the gas equilibration methods which have been successful with the Nb(Cb)-N and Ta-N systems (see Ref. 5 for a review of this work). Extensive investigation, using the gas equilibration methods, showed this method not to be applicable with vanadium This was presumably due to the gettering action of vanadium sublimed on the walls of the Sieverts apparatus. Thus, the nitrogen pressure relationships with temperature and composition were not obtained. The internal friction methods were, however, found to be applicable, and the temperature-composition relationships are reported in this paper and compared with similar results for the Nb-N6 and Ta-N7 systems. The existence of a Snoek internal friction peak due to nitrogen in solution in vanadium has been clearly demonstrated. 8-10 Powers and Doyle found the peak to be at approximately 275°C for frequencies near 1 cps.8 In a subsequent paper10 they reported the proportionality constant at 275°C between the internal friction peak height (Q-1) and the concentration of ni- trogen in solution (in atom percent) as 0.06 per at. pct. The studies of Stanley and wert9 indicated qualitatively that the height of the Snoek peak decreased with aging at the peak temperature and thus suggested that internal friction methods were suitable for study of the solubility. EXPERIMENTAL METHOD The vanadium for this investigation was of particularly high purity. It was obtained from the Ames Laboratory of the U.S. Atomic Energy Commission, Ames, Iowa in the form of a 1/2-in. diam, three pass zone-refined ingot. The electrical resistivity ratio (p300ºk/p4ºk) was 160. The initial composition was determined as follows: Carbon 200 ppm Oxygen 150 ppm Chromium <50 pprn Iron 125 ppm Silicon <50 ppm Other metallic 100 pprn The initial vanadium ingot was fabricated to 30-mil wire by swaging and wire drawing without the need of intermediate annealing. Lengths of this wire were then further purified (particularly for oxygen) by outgassing at 10-6 torr at 1400°C for 4 hr. The outgassing treatment resulted in specimens with a bamboo grain structure and a lustrous appearance. Desired amounts of nitrogen were added to the outgassed wires in a Sieverts apparatus in which known amounts of nitrogen were equilibrated with the wire at 1300°C. Nitrogen concentrations were produced in the desired range from less than 1 to 10 at. pct N. Monitoring of the partial pressure of nitrogen in the Sieverts apparatus indicated that at 1300°C equilibrium between the nitrogen gas and the vanadium was obtained within 10 min. Relatively rapid cooling from the nitrogen addition temperature was obtained simply by turning off the specimen heating current and cooling to room temperature in the partial pressure of nitrogen. Internal friction measurements of wire specimens were made under forepump vacuum in a torsional pendulum at frequencies near 1 cps. The torsional pendulum was of low thermal inertia and was designed so that specimens could be heated both by a conventional tube furnace and by the joule heating of a separate current through the wire specimen." Use of a static atmosphere of helium gas as a quenching medium made it possible to cut the specimen current, rapidly cool the specimen to the measurement temperature, and make a measurement of the internal friction in less than 1 min. Because of the large solubility of vanadium for nitrogen, the internal friction peak heights were in some cases greater than Q-1 = 0.1. This high damping resulted in an estimated relative uncertainty in the damping measurements of approximately 10 pct. X-ray analyses made to identify the precipitated ni-

Jan 1, 1970

By H. H. Reamer, B. H. Sage

An experimental investigation was conducted upon five different paired samples of oil and gas from a field in Louisiana. The study, with each pair of samples, included the measurement of the formation volume and the volume of the liquid phase for three mixtures of the oil and gas. The gas-oil ratio varied from approximately 200 to over 40,000 cu ft per bbl and measurements were made at temperatures between 40" and 250°F. The gravity of the tank oil for the five samples under investigation varied between 38.0" and 55.8" API. The composition of the oil and gas samples and their mixtures is submitted &apos;References given at end of paper. Manuscript received at the office of the Petroleum Branch February 21, 1950. in tabular form. A number of diagrams depicting the effect of temperature and gas-oil ratio upon retrograde dew-point pressure are presented. INTRODUCTION During the past two decades a fairly large number of investigations were made of the volumetric behavior of naturally occurring hydrocarbon mixtures. The earlier work of Beecher and Park-hurst&apos; and a more recent report on samples from Dominguez Field2 are typical of research of this nature. Such studies have been used in estimating the volumetric behavior of fluids in producing fields other than those from which samples were taken. Progress has been made3.4.5 in correlating the influence of pressure, temperature, and composition upon the specific and formation volume of hydrocarbon mixtures of relatively low gas-oil ratios, but attempts to extend this correlation to higher ratios have not been particularly successful. The influence of composition upon the volumetric behavior of such systems cannot be simply related to a single parameter such as gas-oil ratio. In order to aid in the extension of the correlation of the volumetric behavior of mixtures of oil and gas to higher ratios, a rather complete study was made of five different pairs of samples from a Louisiana field. The complexity of the influence of composition upon the volumetric and phase behavior of such systems in the regions of retrograde condensation was indicated by earlier Work,6,7,8,9,10 and it is doubtful if simple correlations can be established in these regions with the information currently available. The terminology employed in this paper is identical to that utilized earlier."

Jan 1, 1950

KNOWING the endpoint, or the equilibrium state, in steelmaking reactions is only part of the story. The rate at which the reactions proceed can be equally important. But the power of thermodynamics, which enables us to estimate the endpoint, is that a knowledge of the mechanism is not required. The methods of kinetics, however, are step-by-step analysis in which a knowledge of the detailed reaction mechanism is essential. As is evident from Chapter 16, a great deal of thermo- dynamic data for steelmaking are available and the underlying theory rests on a completely sound basis. This is far from the case with kinetic data and even kinetic theory. Nevertheless, it is worthwhile to examine the present state of knowledge, to see how far it may be applied to electric furnace reactions. KINETIC THEORY Heterogeneous Reactions. Classical kinetic theory and experimentation have been mainly concerned with homogeneous reactions taking place between different chemical species in a gas or liquid phase. The species are mixed together and the progress of the reaction can then be observed. This is possible because most experiments have been done at relatively low temperatures where the characteristic time for the mixing process is much shorter than the time for the chemical reaction to be completed. For example, in the homogeneous gas reaction, H2 (g) + I2 (g) 2HI (g) hydrogen and iodine may be added to opposite ends of a tube containing a diaphragm. When this is withdrawn, gaseous diffusion (and convection) mixes the two types of molecule almost completely before any hydrogen iodide molecules begin to appear. Such an experiment is inconceivable at more elevated temperatures, since the rate of the chemical process is so sensitive to temperature that reaction would be completed almost instantaneously wherever hydrogen and iodine came into contact; the rate of the mixing process would then determine the rate at which hydrogen iodide was formed. We should not, therefore, expect to observe many homogeneous reac-

Jan 1, 1964

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days &apos;steel&apos; was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days &apos;steel&apos; was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By Edward Keller

THE ASSAY FOR COPPER. SOMEONE some time ago remarked that some chemists still insist on telling us how to determine copper by the electrolytic method. The. writer must confess that he believes that everything is not known definitely as yet as to how the exact amount of copper is determined in such material as purest commercial electrolytic copper. Some of us are not yet convinced that the pure copper atom is at all times deposited from an acid solution and that no oxygen or hydrogen will, under certain conditions, accompany it. Difficulties with impurer material are frequent, but erroneous results are not always apparent, since these do not speak so readily for themselves as those in the first case. By this is meant that if a chemist finds 100 per cent. of copper in electrolytic copper it is pretty certain that he perceives the result to be wrong, while if he finds 0.1 per cent. of copper too much in a very impure material he is far more likely to be unconscious of his error. These, in a wide experience, are frequent happenings and the writer has always looked with interest to publications on this subject. In turn, he :feels justified in giving to others a few of his own observations. Up to a few years ago there were two methods of electrolytic copper assay in technical use, which had in common, that the amount of copper deposited on the cathode did not exceed 2 g., and they differed in that, for the one a large sample 1 (20 to 80 g.) was taken from the general sample by a splitting device, dissolved, and from the solution a small portion (to contain 1 or 2, g. of copper) measured out for the electrolytic deposition; in the other Method the copper was determined, generally in 1-g. portions of the separated coarse and fine portions of the sample, all of which passed -a 16 or 20-mesh screen, being accomplished by a 40-mesh screen,

Jan 8, 1913

By H. B. Heller, T. J. LaChapelle

Phosphorus nitride has been used as a diffusant for introducing phosphorus into silicon under various conditions. It has a temperature -dependent rate of decomposition beginning in the 500°C range, increasing very rapidly above 1000 C, producing gas -eous phosphorus and nitrogen. Best control was obtained with a two-temperature arrangement, with silicon at the proper higher diffusion temperature. It is an easier compound to use than the usual P2O5 because it is nonhygroscopic and yields temperature-controlled surface concentrations together with excellent final surfaces. Surface doping nearly as high as that produced by phosphorus pentoxide has been observed for sources at 850" to 900°C. Reproducible high sheet resistances were obtained by using slow flow rates (1 linear in. per min) and staggered-baffle gas mixing with the nitride at 550°C. Both inert gas (argon, nitrogen) and oxidizing ambients have been examined. Oxygen reacts to produce anhydrous P2O5, consuming the source at a rapid rate. Nitrogen, except for short diffusion times, suppressed the dissociation reaction and sometimes produced inferior surfaces. Argon appears to be a more useful ambient. PHOSPHORUS is a common impurity atom which may be introduced into a semiconductor lattice to create a p-n junction or an nn contact region. Various investigators1-4 have described techniques which can be used with either elemental phosphorus or certain of its compounds. This paper discusses a newly available compound of phosphorus, phos- some processes silicon wafers are precoated with a phosphate glass which acts as the doping source. Although a nonoxidizing form like elemental phosphorus or a phosphine can be used, most diffusion methods usually involve the use of phosphorus pentoxide. Because of the rapid volatility of this compound, a two-step process is often used, combining a gaseous deposition to introduce a predetermined quantity of phosphorus into the silicon with a later redistribution to obtain the desired distribution and surface concentration. Such a process usually involves predepositing phosphorus at surface concentrations greater than 1020 cm-&apos;. At such doping levels the phosphorus-diffusion coefficient appears to be strongly concentration-dependent.596 Distribution profiles5&apos;9 for these high concentrations of phosphorus do not follow Fick&apos;s laws, having extended subsurface regions which appear electrically to be nearly uniformly doped with ionized impurity atoms. Radioactive-tracer experiments also show near-surface anomalies in the distribution profile. Additionally, it has been shown1&apos; that the introduction of very high surface concentrations of impurity atoms into silicon (a step necessitated by the subsequent lowering of concentration during the redistribution) creates dislocations, even in material having no dislocations originally. For device fabrication the use of oxide masking introduces certain difficulties and limitations.7&apos;8 The standard practice of using phosphorus pentoxide as an impurity source adds other problems to these because of the speed and ease with which this compound reacts with moisture present in any gas in contact with it. In fact, P2O5 is one of the fastest and most effective drying agents for gases. Because it is such an excellent desiccant, completely anhydrous phosphorus pentoxide is difficult to obtain and is even more difficult to keep dry. Adequately dry gloved boxes must be used for storage and transfer of the chemical. The presence of even traces of moisture will cause formation of phosphoric acids which, during the high-temperature diffusion, results in polyphosphoric acids of variable composition. Such reaction by-products end up as gradually accumulating viscous fluids in the cooler parts of the diffusion furnace. The calculation of the final solute distribution for

Jan 1, 1964

By Lester A. Blackner

Discussion of the paper of LESTER A. BLACKNER, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 102, June, 1915, pp. 1249 to 1290. SIDNEY J. JENNINGS, New York, N. Y.-In the historical part of the development of the caving system discussed by Mr. Blackner, I notice the absence of one man&apos;s name, Charles Henroten. Mr. Henroten used the caving system in South Africa in the. Kimberly mines, and realized from his work there that ground would cave when properly prepared. I think it is due him that his name should be mentioned in connection with an exposition of this system in America.

Jan 12, 1915

By M. Garfinkle, W. D. Klopp, W. R. Witzke

The tensile properties of binary W-Re alloys containing up to 33 at. pct Re were determined at temperatures from 78" to 3630°F. Elongations as high as 260 pct were observed in electron-beam-melted tungsten containing 23 at. pct Re when tensile-tested at 3630°F after a 1-hr anneal at 3090°F. All alloys tested under these conditions with rhenium contents between 20 and 28 at. pct exhibited elongations of at least 200 pct. These alloys also showed enhanced grain growth rates. The values of strain-rate sensitivity ranged between 0.2 and 0.3 for the alloys exhibiting high elongations. Houlezler, for swaged alloys tested just above the re-crystallization temperature, strain-rate sensitivities as high as 0.8 were observed. The high-temperature strengths of the high-rhenium-content alloys were also less than those of alloys with intermediate rhenium contents. ALLOYING with rhenium has two distinct effects on the mechanical properties of tungsten. One effect occurs in dilute solid solutions and is most clearly seen in the lowering of the hardness and of the ductile-brittle transition temperature at about 5 at. pct Re.1-3 The second effect occurs in the concentrated solid solution at about 25 at. pct Re, and is characterized by twinning and a larger decrease in the ductile-brittle transition temperature. An aspect of the high-rhenium-content alloy which has received little attention is the higher-than-usual tensile ductility at 3500°F.3 Anomalous high ductility has been observed in several other alloy systems. usually associated with a phase transformation or a solid-solubility limit.4&apos;5 The phenomenon is now commonly termed superplasticity. High-strain-rate sensitivities6 and grain boundary sliding7 have been reported for materials that undergo superplastic deformation. Also, it has been found that superplastic materials usually have a very fine grain structure (less than 10 pm).8 and it has been proposedg that such a structure alone is sufficient for superplasticity. The purpose of the present study was to further characterize the high-temperature tensile properties of W-Re alloys to determine the conditions under which they might be superplastic. Tensile and selected strain-rate sensitivity tests were conducted on alloys containing 0 to 33.3 at. pct Re at temperatures from 78" to 3630°F. Grain-growth rates were also determined on most alloys at 3630°F. Fig. 1 indicates the compositions evaluated and their locations relative to the solvus line in the tungsten-rich end of the W-Re phase diagram. Twelve binary W-Re alloys containing up to 33.3 at pct Re were double electron-beam-melted and subsequently fabricated to 0.3-in. rod by extrusion and swaging. The starting materials were commercial powders of tungsten and rhenium with impurity levels as listed in Table I. The various blended W-Re compositions were hydrostatically pressed at 70 ksi. The pressed bars were drip-melted into 1.5-in.-diam ingots and then remelted into 2-in.-diam ingots at a chamber pressure of 10~5 torr. The ingots were canned in molybdenum and extruded to round bar at a reduction ratio of 6:l. The alloy extrusions were swaged to about an 80 pct reduction at 2100" to 2900°F. Buttonhead tensile specimens with a reduced section diameter of 0.16 in. and a gage length of 1.0 in. were centerless-ground from the swaged bars

Jan 1, 1970

By John B. Hastings

THE reconnaissance of the Goldfield mining-district, described in this paper, was made in May and June, 1905, and, though this time was too short for a complete report, the work accomplished may serve as a basis for more thorough future research. Dr. Berkey has examined the rocks collected by myself, and I am using his classifications. As a result of further field-work, and Dr. Berkey&apos;s examination of the rocks, this paper is an elaboration and correction of my views expressed in the Gold-field Sun, May 12, 1905. The sketch-map, Fig. 1, illustrates the geology of the Goldfield mining-district. Goldfield is an eruptive complex, consisting of alaskite (binary granite), hornblende-andesite, hornblende-dacite, rhyolite, pyroxene-andesite, pyroxene-dacite (sometimes containing, a small quantity of olivine), quartz-felsite, olivine-pyroxene-ande¬site, and basalt. Considering this list to be arranged in the order of eruption, the age-sequence of the rocks conforms to Richthofen&apos;s law, formulated in 1868. From his observations in Europe and America, propylite, andesite, trachyte, rhyolite and basalt, occurring together, succeed one another. In a general way, the medium and more acidic rocks precede the most asic-a result supposed by some to have arisen from their relative position beneath the surface, and due to a rude stratification by gravity in the original cooling magma during the older history of the earth, or to the same differentiation occurring during a quiescent (molten ?) period preceding eruption, being aided by the ease with which acidic rocks, mixed with water vapors, become fusible. In effect, the more basic and less re-

Mar 1, 1906

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

The subjects of this study are two corrosion phenomena familiar to operators of aluminum plants employing Soderberg anodes of the vertical type, namely the sul-fide scale formation observed at the steel contact spikes and the corrosion wear observed at the lower edge of the gas collecting skirts. The causes of these corrosion phenomena are discussed on the basis of observations from practice and measurements on commercial cells as well as on laboratory experiments. It is concluded that the anode spike corrosion is mainly due to the attack by sulfur compounds contained in the anodically evolved gases and that this attack is greatly promoted by cracks and pores in the anode carbon embedding the lower spike ends. The corrosion of the gas collecting skirt is mainly attributed to anodic dissolution of the iron during occasional contacts with the melt. ANODE SPIKE CORROSION The visible result of this corrosion is the formation of a brittle loosely adherent scale on the lower ends of the mild steel spikes maintaining the electric contact to the carbon anode, Fig. 1. The thickness of the scale usually varies from 0.5 to 3 mm, but in some cases scale of about 10 mm thickness has been observed by the writers. During the spike pulling, usually repeated every 3 weeks, part of the scale often loosens and remains in the anode carbon, resulting in contamination of the aluminum with iron. This corrosion has been attributed to reaction of the iron with gaseous sulfur compounds originating from the anode paste materials.&apos;-4 This paste usually consists of 70 pct precalcined petroleum coke with 1.2 to 1.4 pct S and 30 pct coal tar pitch containing 0.5 to 0.7 pct S. During operation the gasification of the anode materials takes place in two ways: First, gases are evolved by the gradual baking of the anode paste added on top of the anode. Due to the sealing effected by the upper semifluid zone of the paste, these gases, containing sulfur compounds from the pitch, are forced downward through pores and cracks in the rigid anode carbon. At the temperatures of the zone of the lower ends of the spikes, 700" to 900°C, the original components of the baking gas must undergo decomposition, similar to that taking place with the production of coal gas, resulting in a gas mixture consisting mainly of H2 and CH4 with small percentages of H2S as the main sulfur compound.5 Second, the anodic reaction results in a mixture of C02 and CO, the total quantity of which is about 15 times that of the baking gas. These anode gases must carry the entire sulfur content of the carbon gasified by the anodic reaction. Henry and Holliday6 have shown that COS is the main sulfurous component of the anode gases from Soderberg cells. Soderberg anodes usually exhibit a network of vertical cracks, frequently traversing from one spike to the next one and to the outside of the block and widening downward to the working face of the anode. In addition the anode carbon, particularly that below the spike ends, is rather porous, as indicated in Fig. 1. It therefore seems probable that the anode gases also may partly penetrate to the spike ends. As the anode is partly immersed in the melt, the static pressure of this must forward this penetration. I) SPIKE SCALE COMPOSITION A great number of freshly extracted spikes from industrial plants were inspected and samples of the scale collected for examination. Before analyzing the samples a thin iron oxide layer, formed by air oxidation of the outside of the red hot scale immediately after spike pulling, was removed. On the average the Fe/S ratio found by these analyses corresponded to I the composition FeSl. oo7. X-ray powder patterns showed no oxide and otherwise agreed with those found by Haraldsen7 for iron sulfide with 50.00 at. Pct

Jan 1, 1970

By Donald W. Scott, Nathaniel Arbiter, A. C. Richardson

THIS paper describes the application of amine flotation to a specific problem-that of increasing the grade of magnetite concentrates derived from an iron ore requiring extremely fine grinding for mineral liberation. Experiments conducted on an iron ore from Wisconsin had shown that concentrates containing 60 to 62 per cent iron and 12 to 14 per cent silica could be produced by magnetic separation. The residual silica occurred as quartz and hornblende, either entrained or locked with magnetite. Most advantageous utilization of the concentrate, however, necessitated that the silica content be reduced to about 5 per cent, equivalent to an iron content of 67.5 per cent. It had been demonstrated that tabling of the magnetic concentrate removed sufficient quartz and hornblende to yield an acceptable concentrate, but disadvantages inherent in tabling dictated that flotation be investigated as a substitute. The goals set for the flotation investigation were: (I) the production of concentrates of about 68 per cent iron content from the magnetic concentrate; (2) an iron recovery of about 85 per cent of that in the feed to flotation; and (3) minimum reagent cost. Both batch and continuous flotation tests were employed; the former, to establish the procedure and the latter to verify it. Although the data were obtained on a specific ore, and with a commercial application in view, it is believed that they have a bearing on other problems where amine flotation is being used or is anticipated. SAMPLES Two samples, designated "minus 100mesh magnetic concentrate" and "minus 150-mesh magnetic concentrate," were used for the batch experimental work. They differed only in the degree to which the crude ore was ground prior to magnetic separation. They were stored moist in steel drums in quantities sufficient for all the experimental work reported. This procedure had the advantage of allowing all tests to be made on common samples, but had the disadvantage that the individual flotation samples, because of the difference in storage time, were subject to various stages of surface alteration. Previous work had indicated that common samples were desirable for the batch studies, and it was decided that if these data appeared sufficiently promising the effect of surface alteration could be checked best by continuous tests. The size distributions and the assays of the samples are given in Table I. The minus 150-mesh magnetic concentrate, on which most of the flotation tests were made, assayed 60.9 per cent iron, 13.3 per cent silica, and 0.016 per cent phosphorus. The minus 325-mesh portion represented 78.1 per cent of the sample by weight, and assayed 67.9 per cent iron. Thus, the insoluble, mainly silica, was concentrated

Jan 1, 1945