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By L. D. Jaffe

IT is now well established that quenched and tempered titanium alloys have much better ductility when the quenching is from a two phase a-B structure, rather than from an all B structure. The corresponding microstructural differences, however, have not been shown in previous publications. Accordingly, specimens were cut from a % in. rod of commercial RC-130A, containing 7.9 pct Mn and 0.12 pct C, which had been previously hot rolled, heated 1 hr at 1100°F, and air cooled. (The same heat has been studied by others." 7 Samples about 1/4 in. cube were heated in helium 1/2 hr at 1450' or 1700°F, quenched in brine, tempered in helium 1 hr at various temperatures up to 1250°F, and quenched in brine. They were then sectioned and metallo-graphically examined, using an etchant of HF-HNO, in glycerine. As quenched from 1700°F, the microstructure observed was clear /3. (Probably also present was U, as the hardness was 400 Vhn, but w is not yet reliably revealed by any metallographic technique.) When the /3 quenched alloy was tempered at a high temperature, a precipitated as a grain boundary film

Jan 1, 1957

By Thomas R. Smith

This paper covers oil shale resources in those countries that border the Pacific Rim. The major known resources around the Pacific Rim occur in the Western United States, Australia, the People's Republic of China, (PRC) and the Thailand/Burma region. The location of these deposits is shown in Figure 1. In 1965, the U.S. Geological Survey estimated world oil shale deposits of over 4 quadrillion tons having a potential oil yield of over 2 quadrillion barrels. If all this were extracted, it could meet the world's entire energy needs far into the future. However, the Survey also estimated the spent shale waste could cover all of the surface of the world to a depth of about 10 feet. Thus, for this and many other technical and economic reasons, it does not appear to be feasible to develop a large portion of the world's oil shale resources in this century; nor will shale in itself solve our energy problems. Nevertheless, shale oil and other ' synthetic fuels are expected to play an important role in new energy supplies in the longer term. WHAT IS OIL SHALE OR SHALE OIL? The term "oil shale" is sometimes a misnomer, in that the rock is often more of a limestone or siltstone than a shale. The common link between resources termed “oil shale" is that they all contain an insoluble substance cal led kerogen (which is from the Greek words for waxmaking). Kerogen is a form of organic carbon derived from a variety of plants ranging from algae to higher plants. When heated sufficiently, the kerogen generates hydrocarbons called shale oil, a form of synthetic crude oil that in most cases is lower in hydrogen content than conventional crude oil. The amount of oil in oil shale is relatively small --roughly 10 percent (by weight) in the richer shales. To upgrade this synthetic oil to usable products, additional processing is necessary. This brief sketch gives an idea of what this different, but significant, form of hydrocarbon is like. ENVIRONMENTS OF DEPOSITION Most oil shale deposits fall into three environments of sediment deposition: 1ake (called lacustrine), sea (marine) and river (fluvial-deltaic). In each case, the deposition of oil shales took place in quiet water environments where plant life, particularly algal plants, could flourish and, after dying, be deposited in unoxygenated water where the kerogen precursors would be safe from destruction by oxidation. The oil shales that were deposited in large lake basins (lacustrine) have attracted the most attention for development over the years. They often have multiple seams, deposited in a cyclic nature with extensive areal distribution and rapid vertical changes in kerogen content. Grades are moderate to high, ranging from 80 to 200 liters per tonne. Rundle in Australia and the Piceance Creek Basin in Colorado are examples of this type. Both deposits represent large volumes of oil shale in small areas which could provide the large volume of feedstock needed for future commercial operations. The stratigraphic sections of these two deposits feature thick oil shale seams with average grades of 80 - 125 liters/tonne conducive to both open pit, and underground operations. However, the rock strength of the Rundle shale is not sufficient to - support underground mining. On the other hand, the Colorado deposits, being more carbonate in nature, are sufficiently strong to support either type of mining depending on the overburden to ore ratio. These latter types of deposits will likely provide the first target for development of a commercial industry. The marine type is characterized by extensive areal distribution with relatively thin seams. The grades are generally low to moderate, ranging from 50 to 120 liters per tonne. The marine oil shales are common worldwide, and their attractiveness for mining is dependent on the overburden to ore ratio. Because of their widespread areal distribution, their in situ resources can be quite large. The Toolebuc Formation in Central , Queensland, Australia is a good example of this type of deposit being 7-10 meters thick over an extensive area. The Julia Creek deposit with its favorable overburden-to-ore ratio is being studied for possible development. In a fluvial-deltaic environment, there are many small lakes or bogs associated with rivers in which a very pure type of oil shale called torbanite could form. Torbanites are very high grade containing up to 75 percent hydrocarbons. The known occurrences are generally small lenticular deposits associated with coal seams. Even with the high grades, it is not likely that any of the known deposits would warrant commercial development because of their small size. The torbanite deposits in New South Wales, Australia were processed prior to World War I1 near the town of Glen Davis. However, today's known resources of this type are not large enough to warrant a commercial plant.

Jan 1, 1982

E. T. Dumble, Houston, Texas (communication to the Sec-retary?):—In addition to the list of publications mentioned by Mr. Schorr and those by Prof. Hofman, I call attention to the following references:— Sludi sulle Lignite, by Capacci. Turin (1890). (An excellent work.) Report of Brown Coal Industry in Germany. J. Cosmo New-berry. Department of Mines, Victoria (1892).

Jan 1, 1905

By Carl R. Christiansen

Since the first pay hole in Missouri's "New Lead Belt" was drilled in 1955, this district has become one of the world's leading sources of lead. The belt extends from north of Viburnum in a southerly direction to near Eminence, a distance of about 35 miles. The St. Joseph Lead Company was the discoverer and first to develop new mines in the Viburnum area. Since the discovery of the New Lead Belt, many companies have engaged in exploration programs and several major companies have become active in development of new mines. These include Cominco American, Inc., which operates a joint venture with Dresser Industries; Ozark Lead Company, a subsidiary of Kennecott Copper Company; and Missouri Lead Operating Company, a joint venture of Arnax and Homestake. St. Joseph Lead Company, with over 100 years of experience in the Old Lead Belt, has served as a leader in development of equipment and mining techniques, making its properties some of the most efficient mining operations in the world. The new producers give the district the benefit of fresh viewpoints, as their engineers are mostly from outside of Missouri and their previous experience has been considerably different from conventional lead belt practices. While all operations are similar in that they are room-and-pillar, the diverse experience of the operators has produced a group of mines that employ a variety of equipment and mining techniques to give increased efficiency

Jan 1, 1970

By Tell Ertl

An annual invitational address by an outstanding man in mining, geology, or geophysics who has contributed significantly to the progress of technology in these fields. IN 1954, the first year the award was conferred, Fred Searles, Jr., remarked, "The earlier years are the easiest." In this, the second year, it was easy to choose the outstanding mining engineer. Our conferee this year has been destined to mine. He comes from pioneer stock, and though a son of the American Revolution he is most proud that all four of his grandparents came to the Jordan River Valley of Utah the "first summer," which all Utahns will recognize as 1847. At the time of discovery of high-grade ore in Bingham, his grandfather, Archibald Gardner, had a crew of men getting out saw timber in the area. The first claim staked in Bingham Canyon was named the Jordan, and Bishop Gardner was the colocator of the claim as well as the man to record it. E. D. Gardner was born in West Jordan, Utah, in view of Little Cottonwood Canyon, the site of the Emma Mine. Park City in the Wasatch Mountains a few dozen miles to the east, and Tintic, not much further to the south, were developing their vast ore-bodies throughout his youth. As a boy he was near the present Midvale metallurgical area and could see the Lark and Bingham Canyon mine dumps and imagine the mining activities at Tooele, Ophir, and Mercur just over the nearby Oquirrh Range. He was 11 years old when the first car of copper ore was shipped from Bingham Canyon. It was not surprising that he attended the University of Utah and graduated with an engineer of mines degree. Five years with the Utah Apex in Bingham Canyon as chief engineer and assistant superintendent completed his training for the 44 years of unselfish and lightly rewarded service he was to give the mining industry as a Government engineer. All of us in mining are familiar with the great work he carried on and directed during the genera- tion he supervised the Southwest Experimental Station at Tucson. He has written scores of papers and books. His observations and experiments on drilling and blasting have led to the important improvements in this field during the past quarter century. Whereas those of us who consider ourselves widely informed about underground metal mining methods make hasty trips through a half dozen or dozen mines a year, our conferee has visited them all—not only the metal mines, but also coal and hundreds of nonmetallic mines, in the United States, Canada, Latin America, and overseas. His keen observations and analytical mind have resulted in an encyclopedic knowledge of mining and mines. His improvements in mining technology have been steady and predictable. His elucidation of mining problems to the many young engineers that have come under his guidance have made them grow strong and useful to his industry. When he chooses to stop, his influence will continue to expand and prosper because of the inspiration and dedication he instilled in so many of us. The profits from his ideas have been distributed throughout the mining industry. He has remained a technical man who felt that he could serve the mining industry best as a Government engineer. But he is the staunchest advocate of the belief that the public should gain from his work through private industry. This is not the first recognition E. D. Gardner has received. The Department of the Interior awarded him the coveted Medal for Distinguished Service in October 1949, and he received the Engineering & Mining Journal's Salute in March 1951. His friends who are presenting him the Daniel C. Jackling Award today know this great mining engineer simply as "Ed" Gardner.

Jan 1, 1956

By M. A. Roche

AST fall over half a million tons of ore and rock were broken in one blast at the open pit of the Hudson Bay Mining & Smelting Company's operation, at Flin Flon, Manitoba. The following particulars of the blast, and details of the preparatory work, indicate how an operation of this scope is carried out. The data given, in essentially the present form, were first published by The Canadian Mining Journal. The area blasted was 150 ft. wide and about 700 ft. long. A total of 123 tons of 50 per cent forcite gelatin, in 5 by 16-in. cartridges, was used for the charge. Drilling for the blast was started on May 29, and was completed late in August, requiring 1297 machine shifts for drilling only. Total footage drilled for the shot was over 5 miles of 6-in. hole. The main blast consisted of 232 holes spaced on 17.5-ft.

Jan 1, 1934

By J. Handin, S. J. Bauer, M. Friedman

Deformation mechanisms in room-dry and water-saturated specimens of Charcoal Granodiorite, shortened at 10-4s-1, at effective pressures (Pe) to 100 MPa and temperatures to partial melting (?1050°C) are documented with a view toward providing criteria to recognize and characterize the deformation for geological and engineering applications. Above 800°C strength decreases dramatically at effective pressures ? 50 MPa and water-weakening reduces strength an additional 30 to 40% at Pe = 100 MPa. Strains at failure are only 0.1 to 2.2 percent with macroscopic ductility (within this range) increasing as the effective pressures are increased and in wet versus dry tests. Shattering (multiple faulting) gives way to faulting along a single zone to failure without macroscopic faulting as ductility increases. Microscopically, cataclasis (extension microfracturing and thermal cracking with rigid-body motions) predominates at all conditions. Dislocation gliding contributes little to the strain. Precursive extension microfractures coalesce to produce the throughgoing faults with gouge zones exhibiting possible Riedel shears. Incipient melting, particularly in wet tests, produces a distinctive texture along feldspar grain boundaries that suggests a grain-boundary-softening effect contributes to the weakening. In addition, it is demonstrated that the presence of water does not lead to more microfractures, but to a reduction in the stresses required to initiate and propagate them.

Jan 1, 1982

By AIME AIME

AT the meeting on Engineering Education on Mon- A day afternoon E. A. Holbrook, of the University of Pittsburgh and chairman of the Committee, presided as chairman with W. B. Plank acting as vice- chairman. About sixty members of the educational fraternity were present. Dean Holbrook, after a few introductory remarks, introduced the first speaker of the afternoon, Charles Y. Clayton, who then presented his paper, "Why Do So Few Elect Metallurgy?" in which he stressed the fact that ,one of the things the study of metallurgy ,now needs is publicity and public education on what metallurgy is and 'does. Another thing he brought out is that the study of metallurgy has been looked on for many years merely as a branch of other departments. He gave tables showing past and present enrollment in the course of metallurgy in various schools.

Jan 1, 1930

Jan 1, 1923

Jan 1, 1923

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of gas-solid reactions with special attention given to the hydrogen reduction oj dense spheres of hematite. This reduction process must pvoceed through a sequence of transport and chemical .reaction steps acting in series. Under typical experimental conditions, none oj the individual transport and reaction resistances may be neglected in the development of a physically significant model. A linear vate of thickening oj the product layer, usually taken as evidence of interface-controlled .reuction, may be observed even though transport resistances play a dominant role in the over-all kinetics. The temperature and pressure dependencies of all terms have been carefully evaluated in order to .make fill use oj arailable expe-inzental data in evaluation oj the model. FOR obvious technological reasons, the kinetics of reduction of iron oxides has become the subject of intensive experimental and theoretical investigation during recent years. Continuing efforts to construct mathematical models to describe the kinetics of reaction between a gas stream and a granular bed of solid particles have demonstrated the necessity of a thorough understanding of the reaction kinetics of a single particle within the system as a prerequisite to the construction of physically significant models of complex, reacting systems. This paper presents a critical examination of the transport and chemical-reaction processes involved in single-particle oxide reduction and develops the mathematical expressions necessary to evaluate their importance. Comparison of theoretical predictions with experimental results contributes important new understanding of the complex nature of this process. The reduction process has been studied under a wide range of experimental variables, and it is not surprising that apparent conflicts in observation and interpretation appear in the literature. The interested reader is referred to the reviews of Themelis and auvin"? and Manning and philbrook3 for a description of much of this work. The course of reaction commonly has been followed by measuring the oxygen weight loss from the particle as a function of time. A number of authors have suc- cessfully correlated their data in terms of a model which assumes that the reduction process is controlled by the rate of reaction at a single, sharply defined, advancing interface. According to this model, the interface will advance linearly with time. A mathematical model for gaseous reduction in a packed bed developed by the present authors in an earlier paper4 recognized that reduction must proceed through the series hematite (Fe203), magnetite (Fe30,), wiistite (Fe,O), and finally metallic iron. The reduction scheme permitted a stepwise topochemical reduction of the individual particles to metal or to the lowest oxide thermodynamically possible for the local gas composition in the bed. The limiting situations of theoretically dense and very porous oxide structures were considered. On the basis of available experimental evidence, the simplifying assumption was made in each case that all product layers would thicken linearly with time. A generalized single-particle model has now been developed to determine the significance of transport resistances in the product layers and in the gas film surrounding the particle. The analysis shows that the interplay of transport and chemical resistances is such that an apparently linearly advancing interface may be observed despite the fact that the reaction may be under significant transport control. Attention thus far has been focused on the development of a model for the topochemical behavior of dense spheres of hematite in atmospheres capable of reducing them completely to metal. The formation of successive product layers of iron, Fe,O, and Fe304 is assumed to follow the mechanism originally described by dstrijm.' All oxygen removal from the core occurs at the iron/Fe,O interface, intermediate oxide layers being propagated by sol id-state diffusion without change in the oxygen density of the core. Since fractional reduction is operationally defined in terms of oxygen weight loss, the kinetics of the over-all reduction of FeZ03 to iron is properly studied in terms of the gas-solid reaction occurring at the iron-wiistite interface. The fractional reduction of a partially reduced oxide sphere is given by: here refers to the radial position of the iron/Fe,O interface. This model is not universally applicable because, as explained in the earlier paper,4 a consideration of porous particles or of dense particles in atmospheres not capable of reducing wiistite must allow for the possibility of gaseous reduction at interfaces other than the one between iron and Fe,O. However, evidence that certain hematite specimens actually do follow the dense-pellet mechanism developed here is provided by the data of cewan' and of Bogdandy and

Jan 1, 1967

By Henry Louis

IN the discussion on the paper on subsidence by R. V. Norris and H. W. Montz (Teohnical Publication No. 153), H. N. Eavenson has been good enough to quote some of my views regarding the phenomena of subsidence; he has, of course, only mentioned these briefly, and as he has not represented them quite correctly, it is evident that I have failed to make them clear. Seeing that he, and apparently some of the others who took part in the discussion, appear to hold views different from my own, I think it advisable to put my opinions down as definitely and as clearly as possible, because it appears to me at least possible that some of the differences above referred to may be differences of language and definition rather than of fact. The statements I propose to submit refer to the simplest cases, namely where an area in a practically horizontal bed has been entirely worked out. My experience has been confined to beds of bituminous coal and of ironstone, but D I do not at the moment see why there should be any difference in principle between the working of a bed of anthracite and one of bituminous coal, provided that the other conditions are the same. I wish to emphasize that I am considering the conditions of complete working out of the mineral bed with the roof allowed to come down and form goaf in accordance with the general British practice; 1 am excluding, therefore, methods of hydraulic, pneumatic, and hand stowage where extraneous material is brought in to hold up the roof. I am also excluding the case of bord and pillar working where pillars of small size are deliberately left in, apparently with the idea that these will subsequently crush and let the roof down gradually. Such a method of mining has long been discontinued in this country, indeed in Europe generally, and I venture to predict that the time will come when such a recklessly wasteful method will no longer be tolerated even in the United States. Further, I am referring entirely td static conditions after the mineral bed has been worked out and the ground has come to rest; the phenomena that occur during the course of extraction are much more complicated, and these I am not discussing here. Under these conditions, I have

Jan 1, 1929

By AIME AIME

THE iron and steel activities of this meeting opened on Monday morning with the steel melting session," with G. B. Waterhouse in the chair and A. L. Feild as vice-chairman. N. A. Zeigler's paper, on "Gases Extracted From Iron Carbon Alloys by Vacuum Melbing," created considerable interest and the discussion in general was most favorable. H. W. Gillett and Louis Jordan of the Bureau questioned the method of analysis for oxygen and C. H. Herty, Jr., and J. M. Gaines, Jr., I , expressed their surprise at the large amount of oxygen with the high ,carbon alloys. Whether the gases found existed as gas in blowholes or as oxide inclusions was also a moot point. A paper by C. D. King, on "Basic Open-Hearth Yields," was an extremely interesting and valuable contribution. It was discussed by C. E.Kinney and A. L. Feild and numerous questions were asked throughout the presentation. Mr. King then presented a critical analysis of the losses together with novel methods of calculating them. A paper by C. H. Herty, Jr., and J. M. Gaines, Jr., on "Unreduced Oxides in Pig Iron and Their Elimination in the Basic Open-Hearth Furnace," followed. The question of silicates and oxides in pig iron created much discussion, notably by Henry Hanson and W. J. MacKenzie, who gave figures on chipping cost as a function of blast-furnace practice.

Jan 1, 1929

By Henry A. Wriedt, John Chipman

Equilibrium in the reaction of hydrogen gas with oxygen in liquid nickel, iron, and their alloys has been studied at temperatures of 1500° to 1700°C. The equilibrium con^stant, 0/p, [% O], is greater in nickel then in iron by a factor of 45 at 1594 C. In the alloy steel range, the activity coefficient of oxygen is slightly increased by the presence of nickel. NICKEL is more resistant to oxidation than is iron, in both the solid and the liquid state. The solubility of oxygen,' however, is greater in nickel than in iron. The two metals and their liquid alloys constitute an interesting series of solvents in which the chemical behavior of oxygen can be studied by methods similar to those used for liquid iron.' Experimental Method The furnace assembly, including the tube for preheating the entrant gas, was the same as that described by Gokcen and Chipman. " controlled mixture of water vapor, hydrogen, and argon preheated to approximately the melt temperature impinged upon the surface of the liquid metal. The charge, weighing about 35 g, was held in an alumina crucible at constant temperature in the gas stream for a prolonged period, then quenched in a stream of cold helium, sampled, and analyzed for oxygen by the vacuum fusion method. The temperature of the liquid metal was measured by a Leeds and Northrup optical pyrometer which had been checked against a similar instrument certified by the National Bureau of Standards. The freezing point of electrolytic iron in hydrogen, taken as 153j°C, was used for frequent checks. This point and the emissivity determined by Dastur and Gokcen" established the transmissivity of the optical system. The emissivities of Fe-Ni alloys at 1535" are known from the experiments of Smith and Chipman,h nd it was assumed that the variation with temperature is parallel with that of iron. Recorded temperatures are probably accurate within k5"C. Preparation of Gas Mixtures—Since the ratio H,O:H, had to be much higher for nickel than for iron, it was found convenient to construct two separate systems for gas preparation. In both cases, the ratio of argon to the sum of the other two gases was at least 4, the proportion of hydrogen and water vapor being varied to produce H,O:H, ratios from 0.2 to 70. The primary purpose of the argon was to diminish the errors caused by thermal separation' in the gas phase. In addition, its presence lowered the saturation temperature required for a given H,O:H, ratio and minimized the difficulty of preventing condensation. Both systems were modifications of the one used by Dastur and Chipman.' For H,O:HI ratios greater than 2, welding-grade argon purified by passage over magnesium chips at 620°C was mixed with hydrogen produced in the electrolytic cell shown in Fig. 1. The design was based on a cell used by Bodenstein and Pohl," the important features of which area nickel wire cathode and sodium hydroxide solution as the electrolyte. The rate of hydrogen evolution was controlled by a calibrated ammeter and a rheostat in the circuit, the current efficiency being taken as 100 pct. Precise control of the argon flow rate at about 300 ml per min was achieved by means of a capillary flowmeter having a controlled pressure drop. The molar flow rate was measured volumetrically before each run, and a constant flowmeter setting was maintained thereafter. The A-H, mixture passed through a water saturator of the type previously described," the saturation temperature being maintained automatically with a fluctuation of k0.04"C. The tube between saturator and furnace was heated by a resistance winding. The system was of all Pyrex construction with the exception of the stainless steel tube containing magnesium chips. This was connected with the glass tubing at the upstream end by

Jan 1, 1957

By N. L. Carwile, G. W. Geil

A metallographic study was made of deformation twinning (Neumann lamellae) in ingot iron slowly deformed in tension at —196O and —150°C. The results showed that twinning is initiated mainly during the initial stages of plastic deformation. However, the breadth of the twins generally increases with increase in strain up to fracture of the specimen. HE results of an investigation of the effect of low I temperatures on the flow, fracture, strain hardening, and strain aging characteristics, and the true stress-strain relationship for specimens of ingot iron deformed in tension were reported recently.1,2 In that study specimens of ingot iron, in different initial conditions, were slowly deformed in tension at various temperatures between —196" and +100°C. A phenomenon observed, but only briefly reported, was the formation of deformation twins (Neumann lamellae) in the specimens deformed at the lower temperatures. Preliminary metallographic examination of these specimens indicated that there was apparently some correlation between the deformation twinning and the strain of the specimen and that this factor merited further investigation. Some recent investigations have indicated a direct association of Neumann lamellae and the fracture of the metal. Bruckner".' * postulated that the twinning immediately precedes the fracture and the latter is initiated by the stopping of the propagation of twins, either at subgrain boundaries or at other structural features. Tipper and Sullivan5 postulated that Neumann lamellae are initiated by the shock or a shock wave set up at fracture in the still highly stressed unbroken metal, and that a high rate of deformation is a necessary condition for their formation. An extensive metallographic examination, therefore, was made of many of the specimens used in the study of ingot iron at this Bureau and of additional specimens deformed to selected strains under various conditions. The present paper summarizes the effects of deformation under these conditions upon the breadth and scope of the deformation twins. Other features of twinning will be discussed in another paper. Material and Testing Procedure All of the specimens were prepared from one lot of ingot iron, as hot-rolled, of chemical composition other than iron as follows: C, 0.02 pct; Mn, 0.02; P, 0.005; S, 0.018; Si, 0.002; Cu, 0.10; 0, 0.058; and N, 0.002. Cylindrical tensile specimens with a 2 in. gage length were used. The reduced section was slightly tapered from each end; the diameter (0.438 in.) at the midsection of the gage length was about 0.003 in. less than at the ends. The specimens were finished to the final dimensions by grinding and polishing in the axial direction. The ends of the specimens were machined with 3/4 in. x 10 threads and the shoulder fillets were machined to a radius of 0.75 in. The specimens were extended slowly in tension (deformation rate less than 0.5 pct reduction in area per minute) while immersed in an appropriate cryogenic liquid maintained at the desired temperature. The minimum diameter of the specimen was measured during the test by means of a specially designed reduction of area gage accurate to 0.0001 in." A detailed description of the testing equipment and the method of maintaining the desired temperature is given in a previous paper.' Each specimen, after deformation to a specified strain at a selected temperature, was sectioned longitudinally and examined metallographically. The preparation of specimens for metallographic examination was carried out in the usual manner by mechanical polishing and etching. Results and Discussion Deformation twins in specimens of ingot iron extended slowly in tension at —196" and —150°C are shown by the representative micrographs of Figs. 1

Jan 1, 1954

By J. Nutting, D. H. Kirkwood

The oxidation of lead sulfide in air between 200° and 350°C has been investigated by electron diffraction from thick sulfide films and from galena surfnces. It has been demonstrated that sulfate is the stable reaction product up to 570°C. Sulfate is HAGIHARA has investigated' single crystals of galena roasted in air by the reflection electron-diffraction technique, which owing to the very limited penetration of the beam into the crystal gives information of the nature of the surface only. He has shown that up to 280°C the first oxidation product is lead sulfate, followed by lead mono-oxysulfate (PbO . PbS04). At longer times and higher temperatures more complex patterns appeared which could not be analyzed. All of these patterns were of streaks or spots arising from crystals oriented on the galena surface, and it is probable that these crystals are lead compounds whose structures have not been determined, such as the other oxysulfates (2Pb0 • PbS04 and 4Pb0 . PbS04) or a number of oxides. Certain lead sulfide films, formed chemically, give ring patterns in transmission electron diffraction2 because they are polycrystalline, and should also give ring patterns of the products after oxidation. It was thought that a diffraction study would reveal the sequence of phases produced in the reactions at different temperatures, since X-ray powder patterns are available for many lead compounds. PREPARATION OF FILMS The films were prepared by passing H2S over a saturated solution of lead nitrate in water. Once a silvery film had formed on the solution surface, no further thickening was apparent. The films were transferred by a gauze to a bath of distilled water for washing and pieces of film were caught on small discs on which they were dried. The discs were formed initially on galena up to temperatures of 300°C, followed by oxide and oxysulfates in turn at longer times. The appearance of- these phases is believed to result from an inadequate rate of supply of sulfur to the top surface 01. the crystal. standard Siemens mounts, made of platinum alloy, and had seven 20-p apertures drilled through them. The parts of the film which had dried onto the disc surface were light blue in color, which is the interference color of a film about 600A in thickness. A strong pattern of lead sulfide was obtained in transmission electron diffraction through the apertures but slight broadening indicated a crystallite size of around 200A. Tilting a sulfide film in the beam produced arcing of the rings, increasing the intensities of the (Ill), (3111, and (222) rings and reducing (200) and (220). This arises from preferred orientation in the film, a [loo] direction of the crystallites being normal to the plane of the film. These specimens were oxidized in an oven maintained at the required temperature. The reported times include that taken to heat the film to the reaction temperature. STABLE PHASES FORMED IN OXIDATION The conditions in which various oxidation products of lead sulfide are stable have been considered by the authors in a previous paper.3 It was shown that in a normal atmosphere, taken as containing lo-' atm of SOs, lead sulfate would be stable up lo about 570°C. This was confirmed by oxidizing thin films of sulfide for several days, and the analysis of the transmission-diffraction pattern is given in Table 1. The fit with the patt$rn from X-rays is good, except for the missing 3.62A ring. Some disagreement in intensities of reflections given by X-rays and electrons is to be expected. Up to 570°C a spotty pattern of sulfate was still obtained, indicating grain growth, but above this temperature the film disintegrated. Probably this is associated with the decomposition to PbO . PbS04. It needs to be emphasized that the atmosphere

Jan 1, 1965

By J. J. Gilman

Zinc monocrystals, when compressed nearly parallel to their basal planes (within 20), deform in a new way; and certain deformation markings, called "-bands," are typical of this new mode. Characteristics of these bands are described. Mechanical behavior of low angle zinc monocrystals was investigated in some detail. Recrystallization did not occur upon annealing of banded specimens that were free of deformation twins. -Bands do not seem to be the result of nonbasal slip, but rather, a result of a microbuckling mechanism. u-Bands differ qualitatively and quantitatively from ortho kink bands. A dislocation model, consistent with some of the features of u-bands, is described. THE plastic deformation of zinc monocrystals with slip planes (0001) nearly parallel to the stress axis was studied in this investigation. In a previous investigation, it was shown that some low angle zinc crystals (those with slip planes making angles of more than about 2.5+1° with the compression axis), deform by ortho kinking while others (those with slip planes making angles of less than 2.5+1° with the compression axis) deform in a new way.' This new mode of deformation will be described in some detail here. Some of its striking features are: 1—it operates only for compressive stresses, 2—its temperature dependence is anomalous, and 3—it exhibits a new type of "yield-point" behavior. The mode of deformation to be discussed is not new in the sense that no previous evidence of its existence had been reported. The markings that it creates on the cleavage surfaces of zinc crystals have been described by several investigators.'" However, this is the first time that it has been made to operate under controlled conditions so that its response to mechanical variables, temperature, and aging treatments could be investigated and its geometry completely described. Apparently. Jillson' as well as Holden3 and Pratt" believed that the small bands they observed were simply small versions of ortho kink bands. In fact, two of these authors3,6 "alled the markings "micro kink bands." In spite of the precedence, it is felt that this term is not entirely suitable because these bands do not have the same genesis as kink bands, and they are qualitatively different in structure. As will be indicated by later discussion, the bands seem to be related to the tensile deformation bands observed in aluminum. The present author has chosen to call the bands "micro deformation bands," or simply ",ubands," and the deformation process, ''p-banding." Experimental Methods Crystals were grown from 99.999+ pct Zn obtained from the New Jersey Zinc Co. The details of the technique are given elsewhere." It should suffice to say that the crystals were seeded for orientation control, and precision pyrex tubes were used for molding them. About 40 crystals were used, yielding some 130 specimens. Fig. 1 illustrates the typical form of the specimens and shows how the orientation angles are defined. The crystal specimens were usually 1 3/4 in. long and about 150 mil in diameter. The angle between the slip or cleavage plane (0001) and the specimen axis is designated by xo, while a is the angle between the maximum slope of the (0001) plane and the nearest close-packed direction [1210], vary ing from 0°to 30°. The crystals were cut into specimens with a jeweler's saw and the ends were squared by filing (specimens held in V-block). Crystals of this orientation are stiff toward bending, so this procedure introduced only deformation localized at the ends. Then the specimens were polished either chemically in 50 pct HNO³ or electrolytically in 20 pct chromic acid. The mechanical tests were made with an Instron testing machine. This machine weighs by means of electric strain gages on elastic bars and is quite stiff, since the full-load deflection of its load cells is at most 0.002 in. Most of the testing was done at a

Jan 1, 1956

By O. P. Dolph

SPANIARDS were probably the first to mine the rich surface ore in the veins cutting the rhyolite capping that outcrops on the hills of La Mazata, oil the Allyones side of the Magdalena valley in Jalisco, Mexico, although the name comes from a word of Indian origin meaning "deer". The camp is about 12 km. west of Magdalena, a town on the Southern Pacific Railroad, and about 17 km. north of Etzatlán, on the Mexican National Railroad, at an elevation of 4500 ft. The climate is subtropical with no extremes of heat or cold, the rainy season beginning in June and ending in October.

Jan 1, 1938

By Edmond S. Miksch

The morphology and growth rate of ice grown in supercooled water are markedly affected by convection of the water. A dendritic ice sheet with water flowing past the dendrite tip exhibits deflection of the dendrite spine toward the upstream direction, accelerated growth of secondary spines on the upstream side, and suppression 01" secondaries on the downstream side. Flow causes a thin disk to become corrugated, the corrugations being parallel to the flow. Flow causes an increase in the growth rate of the ice. IF a small seed of ice is placed in slightly supercooled water, it grows initially as a disk with the axis of the disk parallel to the c axis of the ice crystal.' It appears that growth in the c direction is inhibited, while growth occurs with equal facility in all directions in the basal plane. It appears that growth rate as a function of interface temperature is very nearly equal for all directions similarly oriented relative to the c axis. Subsequent to the discoid growth, branching occurs and dendrites develop. The primary dendrite spines grow parallel to the six equivalent a axes of the crystal. Secondary, and in some cases, tertiary spines also grow in these directions. The highly anisotropic: dendritic growth indicates that there must be some finite difference of growth rate for different directions in the basal plane. These differences must be quite small, however, since if they were large, the discoid mode would not occur. Hence, it was expected that the dendrite growth direction could be deflected from the crystallographic direction by perturbation of the thermal field at the dendrite tip. Experiments were done in which perturbation of the thermal field was accomplished by causing the supercooled water to flow past the dendrite tip. The flow direction was perpendicular to the c axis of the crystal, and was perpendicular to the primary spine of the unperturbed crystal. Supercooled water was supplied by a 15 cm cubical copper box, which was refrigerated and insulated so it could cool water to temperatures down to —2oC, and maintain the temperature constant to O.l°C for the duration of a run. A lucite channel of rectangular cross-section, 12 by 24 mm, was mounted horizontally in the box, with one end open so water could flow into it, and the other end leading out through the wall of the box to a length of tubing leading: to an orifice plate 123 cm below. cnunMn s MIKSCH, MemberAiMe, formerly Research Associate, Research Associate, Fig. l(b)—Vertical section of apparatus A horizontal cross-section is shown in Fig. l(a), and a vertical section is shown in Fig. l(b). Means for observing the ice are shown in Fig. l(a). Collimated light passes through the ice sheet and forms an image on the ground glass screen. A lucite box containing dry air was employed to prevent condensation. Ice of the desired orientation was provided by the seed holder shown in Fig. l(b). This device was made of lucite, and had a reservoir in which ice could be frozen by placing it in a freezer. This reservoir com-unicated with the outside only through a narrow gap between two sheets of lucite. The seed holder (after ice had been washed off its exterior) was immersed in the tank of supercooled water, the narrow gap terminating in a slot in the top of the flow channel. Ice growing through a thin water layer in the gap between the two sheets of lucite was oriented so its c axis was perpendicular to the sheets. This orientation is an application of a growth phenomenon2 which causes ice growing along a smooth solid surface in supercooled water to orient itself so its c axis is normal to the surface. After the ice grew into the channel, further orientation was necessary, since the direction of the a axis

Jan 1, 1970

By A. Gittens

In two recent papers stevens13,14 has compared the methods used by various investigators to calculate the contribution of grain boundary sliding to the total creep strain. In previous work Gittins15 has shown that the strain due to grain boundary sliding Egb may be estimated from the lateral, d, and vertical, v, displacements of a longitudinal marker line as it crosses a grain boundary. He obtained the formula, where nL is the number of grains per unit length measured on the specimens before creep, and \p and ?2 are, respectively, the angle between the grain boundary and the stress axis in the plane of the surface and normal to the surface (see Ref. 13, Fig. 1). The subscript L indicates that observations are made in a longitudinal direction parallel to the stress axis. It was generally found more convenient to measure the grain size of a specimen before creep; this was necessary to characterize the specimen. Stevens13,14 however prefers to define Egb in terms of NL, the number of grains per unit length after creep. Since nL - NL(l + €1) where cr is the total strain, Eq. 1 11 becomes The quantities d and ?, can be determined directly from the marker lines, while v and ?2 are found by sectioning normal to the surface. In the interior when symmetry considerations suggest that v = d and ?1 - ?2 the strain due to grain boundary sliding may be estimated from a suitable internal longitudinal marker line by the equation To determine cgb at the surface using either Eqs. |1| or [2] requires a large number of observations, particularly if many estimates of cgb are required, and also it is impossible to determine the variation of cgh with creep strain on the same specimen because the specimen must be sectioned to determine ?2. Gittins15 found that for a number of materials the sliding vectors d and v were related to each other so that provided one was measured the other could be estimated. Also during creep, grain boundaries tend to migrate to meet the surface at angles close to 90 deg,16 so that the term nL(v/tan?2)L was comparatively small when 4,- 90 deg. By determining the frequency distributions of ?2 on control specimens this term can be estimated without sectioning the creep specimen. In this way an empirical equation based on Eqs. |1| and |2| enables cgb to be determined with reasonable accuracy with fewer observations of the angles and sliding components. For B brass, the relationship between the sliding vectors indicated that ceb = 0.85nLVL . In Table I of Stevens paper this equation is stated to be incorrectly derived. However it should be pointed out that this is an empirical equation derived from Eq. |1|, based on a knowledge of the relationship between d and v and on the frequency distributions of ?1 and ?2 for a particular material under given experimental conditions. It was used only when these relationships were known, to reduce the number of observations required to estimate cb. Therefore the comment "derivation incorrect does not apply. Gittins did in fact make use of Eqs. |1| and 131. Author's Reply I must apologize to Dr. Gittins for the inadvertent misrepresentation of his work. Other slight errors in Table I have been pointed out to me. Langdon (No. 12 Table I), Gifkins (No. 7, Table I), and possibly other workers did not measure the number of boundaries per unit length after creep (A') but the corresponding quantity bejove creep (n). As Dr. Gittins points out, a completely analogous set of equations to those given in the paper can be derived by the same method: using the number of boundaries per unit length before instead of after creep. The basic equations corresponding to Eqs. [2] and 171 of the paper, from which all the others can be derived, are

Jan 1, 1968