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By H. H. Podgurski, H. E. Knechtel

Annealed Fe-Al alloys do not react readily to form AlN when held at 500ºC in NH3-H2 gas mixtures, but do so upon the introduction of dislocatims. Nuclea-tion of the nitride phase occurs on dislocation sites. In turn, the growth of the aluminum nitride particles causes the ferrite phase to yield plastically, generating more dislocations for the nucleation process. The nitride phase extracted from an Fe-2 pct A1 alloy nitrogenated at 500°C was identified as stoichio-metric aluminum nitride with a hexagonal crystal lattice. THIS investigation reveals the role that dislocations play in initiating and sustaining the nitriding reaction in Fe-A1 alloys. As early as 1931 the work of Meyer and Hobrock1 suggested that the initiation of the nitriding reaction could involve a nucleation controlled process. Recently Bohnenka2 depicted the gas-phase nitriding process below 600°C as one of mixed control limited by nitrogen penetration through the surface, by nitrogen diffusion, by aluminum diffusion, and by nucleation of the nitride phase, Fig. l(a). In our research in a comparable alloy (0.57 pct Al) at 575ºC, we have observed a nitrogenation which we feel is better described by Fig. l(b). In the case of a 2 pct-A1 alloy partially nitrided at 500°C we propose the profiles shown in Fig. l(c). For a complete and accurate description of the process, a concentration profile of the dislocation density in the test specimen would be needed. EXPERIMENTAL Nitrogenization was conducted between 500" and 575°C in a variety of NH3-H2 gas mixtures on three Fe-A1 alloys: 1) zone-refined iron + 0.16 i 0.2 pct Al—levita-tion melt, 2) zone-refined iron + 0.57 0.02 pct Al— levitation melt, 3) plastiron + 2 pct Al—melted by induction heating. To demonstrate the effect of dislocations on reactivity, both cold-worked and annealed samples were investigated. All nitrogenation rate studies were conducted gravimetrically with a gold-plated invar balance4 contained in a gas-flow system. To avoid contamination of the specimens in the reaction zone of the system, the reaction chamber was constructed of high-purity dense alumina. The activity of nitrogen was fixed by specific NH3-H2 gas mixtures whose compositions were continually monitored by calibrated thermal conductivity gages and checked by chemical analysis. Variations of ± 0.1 pct NH3 could easily be detected by both methods. Throughout this paper the activity of nitrogen is defined as PN3 /PH23/2 , where PNH3, and Ph2 are partial pressures in atmospheres. Electron transmission, density measurements, and chemical analyses were made on specimens before and after nitrogenating in order to reveal structural and chemical changes. Similar studies as well as X-ray diffraction studies were conducted on nitride extractions from the nitrogenated 2 pct-A1 alloy. These extractions were obtained by the use of an anhydrous bromine-methyl acetate solution which dissolves the iron and leaves the insoluble nitrides as a residue. Hardness profiles were obtained on cross-sections of partially nitrided specimens to demonstrate the extent of nitriding through the thickness of the specimens. RESULTS AND DISCUSSION The nitrogen activity in the NH3-H2, atmospheres was never allowed to reach a level capable of producing iron nitride (Fe4N). Hence, the term nitriding as used in this paper refers only to the formation of aluminum nitride whereas nitrogenation refers to the total uptake of nitrogen regardless of how it is distributed throughout the alloy. The weight increases observed during the initial stage of a nitrogenating treatment are due primarily to the solution of nitrogen in the ferrite phase, particularly when starting with annealed specimens. Because this initial nitrogenation rate in the case of the 0.57 pct A1 alloy, see Figs. 2 and 3(a), was most rapid the weight change that occurred thereafter might be attributed to the nitriding reaction with the exception of a small weight increment due to the irreversible pickup of oxygen by aluminum. The oxygen (<70 ppm) came from traces of H2O and 0, in the hydrogen and ammonia gases. On the basis of discrepancies between total weight increase and the increase in the nitrogen content of the sample as determined by chemical analysis, it was estimated and later established by activation analysis, that as much as 200 ppm of oxygen were taken up by a fully nitrided Fe-0.57 pct A1 specimen at 575°C. Most of the oxygen could have been picked up from the nitriding atmosphere on the surface of the samples during cooling to room temperature. Even 50 ppm of water in the gas phase will become oxidizing to iron before the sample has cooled to room temperature. The lack of reactivity* of these alloys in the annealed

Jan 1, 1970

By L. W. Emery

Undergrorlnd combustion operations were initiated in a 60-acre Bartlesville sand "shoe-string" reservoir in Allen Connty, Kans., in 1956. Tests in separate patterns were conducted using various co~nbinations of air and recycle gas to propagate combustion fronts from the injection toward the producing wells. These patterns were made up of 6 injection and 20 prodrrcing wells Gas and liquid prorluctiorz from each pattern was measured on an individual-well basis, and comparisons were made between the three patterns to ascertain the relative effects of injected gas composition on production behavior. Breakthrough of the combustion front at a well was characterized by an increase in water production from the well followed by an increase in bottomhole temperatrrre to approximately 250" F. After burning fronts had broken through at five producing wells, operations were terminated in 1960. From the total project approximately 79,000 bbl of oil were produced during thermal operations at a cumulative produced GOR of 23 Mcf/bbl. No appreciable change in the character of the produced crude was observed. Combustion in the reservoir was maintained with injected gas compositions ranging fronz 6 per cent oxygen in recycle gas to 100 per cent air. lnjectiotz of large quantities of recycle gas resulted in higher producing GOR&apos;s from offset wells than were measured from a pattern into ~vhich straight air ~vas injected. The air required to move the combustion front through I acre-ft of reservoir was computed to be 20 MMscf. This valrre was found to be relatively independent of the quantities of recycle gas injected. The recovery efficiency from the swept area was esti~izated to be about 59 per cent. Areas swept were similar in shape to tlzose obtained with a laboratory potentiometric model. Samples of sund taken from behind the burning front by coring indicated almost total oil removal from the sand. Petrographic analysis of the core samples indicated that the sand had been heated to peuk temperature of rlbout 1,200" F. No rignificant difference in peak temperature was forrnd in two areas where compositions of injected gas were quite different. Compression costs for thermal recovery were estimated to be $1,20/bhl of produced oil. INTRODUCTION The use of the "forward combustion" process as an oil recovery method has received a great deal of attention. This method involves ignition of the formation in an injection well, followed by propagation of a combustion front through the reservoir. Combustion is maintained by the injection of an oxygen-containing gas to react with reservoir hydrocarbons. As the flame front progresses through the reservoir, oil and formation water are vaporized, driven forward in the gaseous phase and recondensed in the cooler part of the formation. In turn, the condensed fluids push oil into the producing wellbores. Completed field tests of the process were first reported by Kuhn and Koch,&apos; and by Grant and Szasz.&apos; Results from other tests have since been reported by Walter,3 by Moss, White and McNeil,&apos; and by Gates and Ramey." ach of these tests essentially utilized a single injection well surrounded by four or more producing wells. Sinclair Research, Inc., elected to do field experimental work using a number of test patterns in a single field in order that comparisons between various operating schemes could be made. The site selected and purchased in 1955 for this experimental work was a 60-acre Bartlesville sand reservoir located in Allen County, Kans. Combustion operations were initiated in mid-1956. Between that time and termination of the project in mid-1960, combustion fronts were propagated from injection wells to producers in three separate well patterns, using different mixtures of air and recycle gas. The test was terminated before sweep of the three patterns was complete so that information about the effect of combustion on the swept areas could be obtained by coring. Results from the test in the form of injection and producing well performance have been carefully recorded, and these form the general basis for this paper. DESCRIPTION OF RESERVOIR The reservoir in which the combustion tests were conducted is a Bartlesville sand "shoe-string", typical of a number of small reservoirs in Southeastern Kansas. Average reservoir characteristics are shown in Table 1. Fig. 1 is an isopachous map of the producing sand showing the reservoir to be approximately 400-ft wide and 2,500-ft long. Maximum net productive sand thickness is 21 ft. Fig. 2 shows a typical core analysis obtained by coring with water-base mud. The reservoir has no appreciable dip and is closed on the sides by degradation of sand into shale. The main body of sand is heavily laminated with shale stringers, which are not continuous between wells. The main reservoir is overlain by 30 to 40 ft of laminated low-permeability sand and shale streaks. No information is available on the original properties of

By Michael J. Castner

"INTRODUCTIONMultiple-seam mining is an ever growing concern for engineers and mine management in every portion of the mining industry and is especially true for coal mining operations. The goal of this report is to identify the location and severity of multiple-seam interactions, provide AMSS calculations performed on the worst of these locations, and follow up with a visual examination of the underground physical effects on the roof and ribs in the locations identified for analysis. Multiple-seam mining is increasingly being studied because:1. Multiple-seam mining can create a multitude of problems such as roof falls, pillar crushing, pillar failing, rib spalling, floor heave, and inundation of water, gas, or oxygen-deficient air that can disrupt mining operations and threaten the safety of the miners.2. Multiple-seam mining is becoming more prevalent due to the depletion of virgin coal reserves.Currently, coal mining in the United States has progressed to the point that a growing number of mining companies are operating in coal seams located above, below, and/or adjacent to previously mined out coal seams. As a result, the state and federal governments are enacting higher safety standards on mining operations. For example, in years past, pillars may have been properly designed to handle single seam interactions for a particular mine or mines; however, today, where mining is now being considered above or below a previously mined area, these loading conditions may not be adequate to handle the removal of additional seams above or below the previously mined reserve. Studies from 1981 estimated that two-thirds of the mineable coal reserves in the United States would be impacted by multiple-seam implications. Today, over three decades later, it is obvious that most of the remaining mineable coal reserve will be influenced by previously extracted seams. Thus, thefocus on multiple-seam mining interactions on current and future mining operations. In 2012, underground mining in the United States produced 342,287 thousand short tons of coal. Northern Appalachia accounted for over 30% (103,301 thousand short tons) of this total (U.S. Energy Information Administration, 2013). Rosebud Mining Company and Western Allegheny Energy (RMC and WAE) have a combined total of 23 actively producing underground mining operations and at least four new mines under or ready for development. All of these mines are located in coal seams (Upper and Lower Freeport; Upper, Middle, and Lower Kittanning) of northern Appalachia (Pennsylvania and Ohio). Currently, more than half of the RMC and WAE mines are dealing with multiple-seam interactions. Seven mines are undermining previously mined out coal seams, and five mines are overmining previously mined out coal seams. Also, between these companies, five mines have inner-seam sloping possibilities (2 completed, 3 planned), most of which will result in mining over or under previously mined areas."

Jan 1, 2015

By Gerald Edmunds

CASTINGS of pure metals and many alloys usually have a coarse-grained structure characterized by long columnar grains throughout the main body of the casting. Frequently, the surface exhibits finer, some-times nearly equiaxed grains, and such grains may also compose other parts of the casting. This paper deals primarily with determinations of the grain-orientation textures of the columnar and surface grains of polycrystalline zinc castings. It includes some results upon a cadmium casting and a magnesium casting. A hypothesis is devel-oped to account for the observations on columnar grains and to use as a basis for predicting orientations in other cast metals. A general description of the position of the columnar grains in castings is that their long axes are approximately parallel to the direction of the thermal gradient during crystallization. Thus, in cylindrical castings the columnar grain axes tend to be radial, and in large flat castings where most of the cooling is through one or both of the large mold surfaces they tend to be perpendicular to the mold surfaces. At the edges and corners the direction of heat flow and there-fore the position of the grains is more com-plex. Actually observation shows that even in castings made in flat molds the cooling seems to be somewhat irregular, since columnar grains tend to emanate from certain areas of the cooling surface, indicat-ing that thermal contact was better there than in neighboring areas.

Jan 1, 1940

By Victor Maksaev, Marcos Zentilli

"Abstract - The Domeyko Cordillera, the westernmost uplifted crustal block of the composite High Andes of northern Chile (20°S to 28°S) hosts a narrow N-S trending belt of Late Eocene-Oligocene giant porphyry copper deposits, which include Collahuasi, Chuquicamata, El Abra, La Escondida, and El Salvador. These deposits are spatially and genetically associated with the closing igneous activity along this range, prior to a 30 km eastward jump of the magmatic front in response to tectonic plate interaction. The porphyry copper deposits are also spatially associated with a major intraarc strike-slip shear system, the Domeyko Fault System. Although the tectonic uplift of the 3000 m to 5000 m high range has generally been assumed to be mostly Miocene in age, field relationships suggest that the Domeyko Fault System and tectonic uplift were active as early as the Eocene, coinciding with porphyry copper emplacement between 41 Ma and 30 Ma. Apatite fission track (FT) thermochronology provides both age data and a time-temperature history for rocks since they cooled below a temperature of ca. 125°C (equivalent to a depth of 4 km to 5 km under normal geothermal gradients) on their way to the surface during exhumation, or after a heating event. Apatite FT data from the Paleozoic crystalline basement of the Domeyko Cordillera indicate that at least 4 km to 5 km of rocks were eroded during exhumation of this tectonic block between ca. 50 Ma to 30 Ma (Middle Eocene to Early Oligocene), a time that immediately precedes and overlaps with the emplacement of giant porphyry copper deposits. The FT data constrain the age and duration of a period of crustal thickening and extensive erosion known as the Incaic compression, an event recognized in the Andes of Chile and Peru. Assuming that cooling was due to denudation alone, modelling of the FT data allow estimation of denudation rates between 200 and 100 m/My during this period. In contrast, exposures of pre-porphyry Paleocene intrusives on the western edge of the Domeyko Cordillera reveal apatite FT ages that are concordant with biotite 40Ar-39Ar dates, indicating shallow emplacement, fast cooling and negligible exhumation. The apatite FT ages of the Chuquicamata and El Abra porphyry copper deposits are only marginally younger than their 40Ar-39Ar dates, implying fast cooling/exhumation of shallow mineralizing systems (ca. 2 km to 3 km). Their FT time-temperature history is compatible with extremely low rates of exhumation (ca. 50 m/My) since about 30 Ma (Early Oligocene). This limited extent of erosion, due to exceptional aridity, has greatly contributed to the preservation of rich supergene enriched blankets above some of the porphyry copper deposits.A model is proposed, which is consistent with field relationships, geochemical, and geochronological data. High relative velocities and intermediate-angle oblique convergence between the Nazca and South American plates in the Eocene-Early Oligocene led to intra-arc transpression partitioned into reverse faults of opposing vergence and a right-lateral shear system (the Domeyko Shear System) localized along the magmatic front. Crustal shortening and thickening led to uplift within the Domeyko Fault System and to erosion of at least 4 km to 5 km. Crustal thickening deepened the zone of magma generation, and magmas accumulated in the lower crust, allowing small volumes to rise rapidly to shallow levels along transtensional domains of the regional shear system. A similar model of crustal thickening and shortening before and during porphyry copper emplacement in zones of transtension may also apply to the Miocene-Pliocene giant porphyry copper province of central Chile."

Jan 1, 1999

By D. T. Peters

To better understand the Co-Mo interaction in maraging steels, the precipitate reversion behavior of two alloys closely related to the 18 Ni-250 grade has been studied. The reversion experiment is carried out by aging at a low temperature, T1 (preaging temperature), for some period of time and then aging at a higher temperature, T2, called the reversion tetnperature. Aging and reversion tmzperatures used were in the range 679 to 1050°F. Reversion is marked by an increase in resistivity and a decrease in hardness. It teas found that some reversion took place at all cornbinations of T1 and T2 but that pronounced rei3ersion resulfed for an Fe-18 pct Ni-5 pct Mo-8 pcl Co alloy exposed to preagz&apos;ng&apos; temperatures at or below 850°F. A similar alloy not containing cobalt exhibited no such discontinuity in reversion behazior with TI. The results are interpreted in terms of two types of molybdenum-rich precipitates, one nucleated at dislocations and the other in the matrix. The increased supersaturation resulting from the presence oj- cobalt evidently provides sufficient energy to nucleate the matrix phase. Anotnalies in the temperature dependence of the resistivity decrease and peak hurdness in the Fe-18 pct Ni-5 pct Mo-8 pct Co alloy as a junction of aging temperature noted in an earlier study are explained on this basis. SEVERAL investigatorsl-9 have studied the details of the precipitation-hardening reaction of the maraging steels. The great majority of conclusions have been drawn from transmission electron microscopy. Although much has been learned by this method, alternate techniques which will give information earlier in the aging process are needed for a more complete understanding of the series of precipitation steps probably involved in the aging reaction. Peters and cupp&apos;&apos; have recently shown, by measurements of the kinetics of precipitation, that an 18 pct Ni-Co-Mo maraging steel shows a distinct change in precipitation behavior at aging temperatures below 850°F. The results were interpreted in terms of the existence of two types of precipitates at low aging temperatures. Only one precipitate type is present at higher aging temperatures. The low-temperature precipitate was found to be a particularly effective strengthener. No evidence for the additional low-temperature precipitate was found in the 18 pct Ni-5 pct Mo ternary alloy. The object of this investigation was to study further the characteristics of the two types of precipitates and the interaction between cobalt and molybdenum characterizing this system. Some preliminary experiments indicated a difference in reversion behavior in specimens aged above and below 850°F. This suggested that knowledge of the reversion behavior might shed some light on these two questions. Hardy and Heal11 have defined reversion as the loss of hardness, electrical conductivity, or other properties caused by heating for a very short time at temperatures above the aging temperature. The precipitate reversion referred to in this paper is entirely distinct from "austenite reversion" often referred to in maraging steel literature. This latter phenomenon could more accurately be called the diffusion-controlled formation of austenite. Much has been written about reversion in several of the aluminum-base binary and ternary alloys.&apos;2-16 Two explanations for reversion have been advanced. Based on the classical nucleation theory of Volmer-Weber-Becker-Doring,17 Konobeevski18 suggested that reversion was due to the size of the precipitate particles

Jan 1, 1968

By D. Thibault, A. Akhiate, M. Brochu, E. Braud

Cast martensitic stainless steels, 13%Cr-4%Ni, having carbon contents between 0.018 wt% and 0.067 wt% were normalized, air quenched, and tempered at two different temperatures (550°C and 610°C). Their microstructures were characterized by optical microscopy and X-ray diffraction (XRD). Macro and microhardness, tensile strengths, and impact resistance were quantified for each material and condition. Results show that the prior-austenite grain size is constant through the materials but the percentage of reformed austenite, contained in the martensitic matrix, depends strongly on the material chemistry and on the tempering temperature and on its duration. It is observed that, independently of tempering conditions, an increase in carbon content increases the material hardness and tensile strengths, whereas the elongation remains constant. In contrast, the results of Charpy type impact toughness tests show a different trend. The material containing the average carbon content (0.034 wt%) is significantly tougher than the two other alloys. Surprisingly, the toughness of the steel containing 0.034 wt% carbon was found independent of the reformed austenite content. It is thus concluded that carbon and reformed austenite contents are not the only parameters affecting the toughness of these steels.

Jan 1, 2014

By Elmer R. Kaiser

G. A. Vissac (Consulting Engineer, Vancouver, B. C.) —Some of the data presented in this paper, in connection with cost studies of washed coals, should be clarified and qualified. Washing a raw coal down to a low ash content may mean higher losses in refuse, but the cost of the operation may be more than compensated by the increased value of the resultant product. However, careful engineering and accurate machinery are required to insure maximum profits. Washing at a low gravity separation demands a very accurate automatic process, chiefly when the small sizes of coal are being handled. Coal consumers today are buying mostly on a Btu basis, cognizant of the fact that low ash contents result in lower installation costs and in savings in handling and transportation charges. The attached Table X gives the actual balance sheets of the various cleaning operations corresponding to various ash contents for the two coals presented in the paper, using the old technique of a two-products separation. or the new technique, now commonly used in Europe, of a three-way separation made possible by new methods and new equipment. Savings in capital costs, handling, and transportation have been calculated on the basis of a delivered cost f.O.b. plant of $10.00 per ton of coal at 16.5 pct ash (actual 1953 average price reported by Consolidated Edison, N. Y.), and of $3.50 at the mine also for 16.5 pct ash coal. In both cases this corresponds to values of 126 and 4.26 per 1 pct of combustible and per ton, respectively, on delivered and on at the mine prices. As an example, the middle western coal at 16.5 pct ash, raw, washed down to 4 pct ash in a two-way process will give 53.75 pct of clean coal at 4 pct ash and 46.25 pct of refuse at 31 pct ash. The value of the losses will be 0.4625x(100—31)x0.042 = $1.34. Add the cost of washing, capital, and operation, which is $0.35. The total cost will then be $1.69. But with a three-ways separation we will have 53.75 pct of first-grade coal at 4 pct ash, 37.25 pct second-

Jan 1, 1955

By J. R. Elenbaas, J. A. Vary, D. L. Katz

The development of gas fields, oil fields and aquifers for storing natural gas is treated from two main vieu.-points: (I) the volumetric storage capacity for gas in a given situation and (2) the prediction of the number of wells required for the delivery of gas. Other experiences in the design and operation of storagc fields are incluclerl INTRODUC TION Storage of natural gas in underground reservoirs near the terminus of long distance pipelines has been the prime factor in opening the space heating market to the natural gas industry. Storagc has permitted a major. increase in both the load and the load factor of pipe-lines; some are now operating at steady load throughout the year. Thus, underground storage has been responsible for the rapid increase in demand for natural gas in recent years. Three types of reservoirs have been used for gas storage: natural gas reservoirs, oil reservoirs, and waterbearing sands or aquifers. This paper presents the factors to be considered when developing gas storage reservoirs of these three categories. There are two prime considerations tor any storage reservoir: (1) the volume of gas which a given reservoir will store advantageously and (2) the number 01 wells needed to provide the required peak deliverability. These two problems will be considered for the three types of reservoirs just noted STORAGE IN PARTIALLY DEPLETED GAS FIELDS Early storage operations consisted of replenishing the natural gas in a depleted gas field situated adjacent to the market. Today, newly discovered fields near the market may be considered for storage, and this discussion applies equally to both types of reservoirs. For reservoirs originally containing gas or oil, the question of the impermeability of the cap rock nor-mally does not arise. However, such fields are likely to have many wells drilled either to or through the reservoir under consideration. Positive assurance must be obtained that such wells are or can be made mechanically tight. Corroded casings may need to be lined or permanently plugged. Abandoned wells should bc reopened and properly cemented. The volumetric capacity for gas storage depends upon space available in the porous rock as well as pressure and temperature of the gas in the reservoir. The production-pressure decline data on partially depleted gas reservoirs without water drive permit calculation of the reservoir space for gas. Isopachous maps of sand volume and porosity data for the reservoir rock provide an alternate method of calculating the pore volume for water-drive reservoirs. The pressure range selected for the storage cycle depends upon ()) the safe upper limit of pressure. 2) the flow capacity of wells and (3) compression requirements when injecting gas into the reservoir or delivering to market. Normally, gas and oil fields have pressures at discovery in the range of 0.43 to 0.52 psi/ft of depth. Pressures of around 1.0 to 1.2 psi/ft of depth appear to lift the overburden1-3 and invite uncontrolled movement of fluids in the porous rock. Some top pressure is normally selected for a storage reservoir ranging from below discovery pressure for deeper reservoirs to 0.65 psi/ft of depth for shallower reservoirs. Pressures to 0.66 psi/ft have been experienced without difficulty. The lower pressure limit is set by water intrusion accompanying low pressures, reduced flow capacity for wells at lower pressures and compression requirements. Depletion-type gas reservoirs often encounter water problems in the later stages of gas production. Such water intrusion may be due to movement from the surrounding aquifer. Accordingly, displacement of this water back into the aquifer by gas pressure and subsequent surges of water corresponding to the gas storage pressure cycle must be considered. Storage fields often produce in four months a volume of gas equal to its initial content. Rapid decreases in reservoir pressure occur, such as 20 psi/day. Accordingly, closed-in pressure observation wells which reflect the pressure in the bulk of the reservoir are required for following the operation of the reservoir. It has been found that a plot of observation wellhead pressures against gas content, Fig. 1, is very useful in observing operation of the field, checking the inventory and predicting future behavior. The plot is based on a given quantity of base or cushion gas in place. The injection and withdrawal curves may spread depending upon the homogeneity of the reservoir rock. permeability of the rock, well spacing and flow rates.

By G. L. Fisher, R. H. Geils

The effect of small amounts of columbium (<0.01 to 0.10 pct) on the ?-a transformation occurring during the continuous cooling of a low carbon Ni-Cu steel was investigated. Dilatometer specimens were aus-tenitized at 950" and 1068?C and cooled at 17? and 375 C° per min. Columbium caused a marked depression in the ?-a transformation temperature except when cooling at the slower rate from 950°C. The effec of columbium on the transformation temperature was greater the higher the austenitizing temperature and rate of cooling. A maximum depression of 92 C" was observed. Metallographic examination of specimens of <0.01 and 0.07pct Cb steels heated at 1200°C for 1 hr and cooled at various rates showed that columbium had a major effect on the ferrite morphology. The fer rite in the columbium -free steel remained equiaxed at cooling rates as high as 440 C? per min while the columbium-bearing steel exhibited mixed structures o equiaxed and bainitic ferrite at cooling rates as low as 130 C° per min. The ? grain boundaries in the columbium -free steel provided the ferrite nucleation sites in rapidly cooled specimens. There was a complete absence of nucleation at these sites in the colum bium-bearing steel. It is concluded that columbium depresses the transformation temperature by suppressing ferrite nucleation at the austenite grain bound-aries. In this respect the effects of columbium are analogous to those of boron in low C-Mo steels. It is well known that small columbium additions can substantially strengthen plain carbon steels. As little as 0.02 pct Cb can increase the yield strength of mild steels by 10,000 psi.1 A fine precipitate of CbC has been observed in columbium-bearing steels2 and is generally thought to be responsible for the strengthening. Little attention has been devoted to the effect of columbium on the ?-a transformation. Webster and woodhead3 have studied the effect of columbium on the isothermal proeutectoid ferrite reaction in mild steels. They found similar transformation behavior in steels both with and without columbium additions. However, as the austenitizing temperature increased, the incubation time for the start of the ferrite transformation became longer in the columbium-containing steel. Morrison1 found that the addition of 0.03 pct Cb to a C-Mn steel lowered the transformation temperature by 50 C° during cooling from 1200°C at a rate of 80 C" per min. The strengthening effect of columbium has recently been utilized in an age-hardenable, low-alloy steel containing copper and nickel.4 A small amount of columbium has a substantial effect on the as-rolled strength of this steel. By increasing the columbium level from <0.01 to 0.13 pct the as-rolled yield strength is increased by 15,000 psi. Columbium also significantly lowers the ?-to-a transformation temperature of this steel during continuous cooling from the austenitizing temperature. Because of the low carbon level in this steel (0.05 pct max), it is almost entirely ferritic. Thus, it offers the opportunity of studying the effect of small columbium additions on the proeutectoid ferrite reaction. Of particular interest in this study was the reason for the marked lowering of the transformation temperature by columbium during continuous cooling. EXPERIMENTAL PROCEDURE Materials. The compositions of the steels used in this investigation are shown in Table I. The steels were 30-lb air induction melts. They were forged to 4 by 8 by 1 in. plate at 1230°C, air cooled, and then reheated to 1230°C and cross-rolled in two passes to in. plates. Dilatometry. A Leitz Bollenrath dilatometer was used to record the transformation during continuous cooling from two different austenitizing temperatures. The dilatometer specimens were + in. in diam and 2 in. long. Oxidation and decarburization of the specimens was prevented by maintaining a small positive pressure of dry argon in the dilatometer furnace and by plating the specimens with 1 mil of Cu. For the lowest cooling rate, 17 C" per min, the temperature of the specimen was measured with a Pt-Pt 10 pct Rh thermocouple placed in a & in. diam well in the center of the specimen. During air cooling, 375 C° per min, this method of measuring the temperature interfered with the operation of the dilatometer. However, it was found that the temperature of the specimen could be measured accurately by placing a thermocouple in an identical specimen in a holder adjacent to the one being used to operate the dilatometer mechanism. The dilation-temperature curves were recorded on photographic film and then converted to volume percent ferrite-vs-temper-ature curves. The cooling rates obtained with the dilatometer are shown in Table 11. Cooling rates of

Jan 1, 1970

By R. K. Dann, L. W. Roberts, R. B. Benson

The mechanical properties of 300-series stainless steels were investigated in both high-pressure hydrogen and helium environments at ambient temperatures. An auslenitic steel which is unstable with respect to formation of strain-induced a (bee) and € (hcp) mar-tensile is embrittled when plastically strained in a hydrogen environment. A stable austenitic steel is not embriltled when tested under the same conditions. The presence of hydrogen causes embrittlement at the mar-lensitic structure and a definite change in the general fracture mode from a ductile to a quasicleavage type. The embrittled martensitic facets are surrounded by a more ductile type fracture which suggests that the presence of hydrogen initiates microcracks at the martensitic structure. If a steel is unstable with respecl to fortnation of strain induced martensile, plastic deformation in a hydrogen environment will produce rapid embrittlement of a notched specimen in comparison to an unnotched one. FERRITIC and martensitic steels can be embrittled by hydrogen that has been introduced into the alloys, either by thermal or cathodic charging prior to testing.1-5 However, conflicting reports exist as to whether austenitic steels that are stable or unstable with respect to formation of strain-induced martensite can be embrittled by hydrogen.8-12 A recent investigation has shown that cathodically-charged thin foils of a stable austenitic steel can be embrittled.13 An earlier investigation of a thermally charged 18-10 stainless steel revealed a significant decrease in the ductility only at the lowest test temperature of -78°C, although strain-induced bee martensite was shown to be present in one specimen tested at ambient temperatures.&apos; When martensitic steels are tested in a hydrogen atmosphere, they are embrittled.&apos;4-&apos;7 It has been observed in this Laboratory that 304L steel, which is unstable with respect to formation of strain induced martensite, forms surface cracks when plastically strained in a high-pressure hydrogen environment. Work in progress elsewhere concurrent with this investigation has also established that 304L is embrittled when tested in a high-pressure hydrogen atmosphere." The objective of this investigation was to study the effect of a high-pressure hydrogen environment on the tensile properties of a stainless steel that contained strain-induced martensite (304L) and one that did not (310). EXPERIMENTAL TECHNIQUES Notched and unnotched cylindrical specimens were machined from 304L* and 310 rods that were heat- treated at 1000°C in argon for 1 hr followed by a water quench. The chemical analyses of these steels are given in Table I. The unnotched specimens had a reduced section diameter of 0.184 & 0.001 in., a gage length of 0.7 in., and were threaded with a 0.5-in.-diam. thread on each end. The notched specimens had a reduced section diameter of 0.260 * 0.001 in. and a 0.75-in. gage length, with a 30 pct 60 deg v-notch at the center. The notch had a maximum root radius of 0.002 in. The tensile bars were fractured in a hydrogen or helium atmosphere of 104 psi at ambient temperatures. The system used for mechanically testing the specimens is to be described in detail elsewhere.19 Several specimens of each type were tested in air using an Instron testing machine. The same yield strength and ultimate tensile strength were obtained in 104 psi helium with the above system as with the conventional testing machine. Magnetic analysis was employed to determine that there was a (bee) martensite in plastically deformed 304L and that it was not present in plastically deformed 310. The magnetic technique depended on allowing the material being studied to serve as the core between a primary and secondary coil. Thus, any change in the amount of magnetic material present between the annealed and plastically deformed steels will be indicated by corresponding changes in the induced voltage in the secondary circuit." The ratio of the output signal of a nonmagnetic stainless steel to a completely magnetic maraging steel was 2000 to I. Several unnotched 304L bars tested in hydrogen were analyzed for hydrogen by vacuum fusion analysis. There was an increase in the hydrogen content to approximately 2 ppm for the specimens tested in hydrogen, as compared to less than 1 ppm for the as-received material. Several thin sections cut from notched areas of 304L specimens tested in hydrogen and containing the fracture surface contained approximately 1.5 ppm H. The accuracy of these determinations was estimated to be ± 50 pct.

Jan 1, 1969

By P. Shahinian, H. H. Smith, M. R. Achter

Crack growth rates are measured at elevated temperature in a resonant fatigue machine from vibration frequency decreases calibrated in terms of crack depth. Crack growth rates in Type 316 stainless steel at 500º and 800°C show a sharp increase with oxygen pressure in an intermediate pressure range and little or no change at high and low pressures. At 500°c, I torr of oxygen reduces the fatigue life by almost a factor of 100 in comparison to that in vacuum and raises the growth rate of shallow cracks by the same At At 800°C the effects are smaller. Changes in slope in the crack growth rate curves are discussed in terms of a model in which rates of surface production and of surface coverage by gas are compared. The use of a calculation method in which the surface exposure time is equal to X/v, where x is the interatomic spacing and v is the growth rate, makes it possible to obtain order of magnitude agreement at 500°C between the observed pressure and the predicted pressure at these slope changes. At 800°C oxidation becomes a .factor and the data cannot be treated by simple adsorption theory. THE decrease in the fatigue life of metals as a function of gas pressure usually follows a stepped curve with virtually all of the decrease concentrated in a sharp drop in a transition zone at intermediate pressures and little or no change at low and high ranges. A number of models, differing in the details of the mechanism, have been offered to explain the shape of the curve. Measurements of crack growth in aluminum as a function of gas pressure by Bradshaw and Wheeler&apos; and Hordon2 demonstrated opportunities for quantitative comparison to evaluate the proposed models. Since comparable data were lacking at high temperatures, in the present work rates of crack propagation were measured in Type 316 stainless steel at 500" and 800°C as a function of oxygen pressure. Choice of this material was dictated by two considerations; it is stiff enough at these elevated temperatures to resonate with the regenerative drive on our fatigue machine and it is known to display a large effect of environment. A new method of calculation is described to predict the gas pressure at the critical point. EXPERIMENTAL PROCEDURE Because of the difficulty of measuring crack depths directly at high temperatures, an indirect method was developed based on the decrease in the resonant frequency with the growth of a crack. A reversed bending, constant amplitude fatigue machine, described previously,3 vibrates a specimen at its resonant frequency, automatically records any changes in it and shuts itself off after it has reached a preset value of frequency decrease. The record of frequency change is used to determine the rate of crack growth. Sheet type specimens of Type 316 stainless steel, Fig. 1, incorporated a sharp, shallow notch to localize the formation of a single crack. After machining, they were annealed in a vacuum of l0-6 torr either at 1066" (lot A) or 871°C (lot B) and then electropolished in an acetic-chromic acid solution. Bending strains were measured at 500" and 800°C by an optical technique4 and reported as total strain without correction for the notch. At 500°C, the 0.141 pct strain was 0.085 pct elastic and the remainder plastic. At 800°C the 0.062 pct strain was all elastic. To convert frequency decrease to crack length, calibration curves were obtained by interrupting the vibration at stated intervals of frequency decrease. The crack depth was measured microscopically at a magnification of X400 and reported as the average of the measurement on each edge. Some specimens were sectioned for crack measurement while others were returned to the machine and fatigued further. There was good agreement between the two methods. Before beginning the vibration, the vacuum chamber was first evacuated cold to 1 x 1O-6 torr, then heated to the operating temperature and held there until the pressure was again reduced to 1 x10-6 torr at which time oxygen was introduced to the desired pressure. In this investigation the vibration frequency was nominally 10 cps and a decrease of 0.6 cps was taken as the failure point. The choice of the frequency decrease to represent failure has no appreciable effect on the fatigue life because the crack is growing very fast at this point.

Jan 1, 1970

By H. F. Bishop, F. A. Brandt, W. S. Pellini

The solidification mechanism of experimental steel ingots (7x7x20 in.) was studied by thermal analysis. It was determined that solidification proceeds in wave-like fashion at rates which are determined by the carbon level, superheat, and mold thickness. The thermal cycles of the mold walls were related to the course of solidification. ESPITE marked advances in the field of solid state transformation, metallurgical research has contributed comparatively little exact quantitative data on the mechanism of solidification of metals. There is, therefore, a great need for such data in the various metallurgical industries. The mechanics of solidification of ingots have been investigated in the past primarily by studies of the rate of skin formation as indicated by bleeding or "pour out" tests. The "pour out" method, however, is a tool which gives only approximate information. In the case of alloys with wide solidification ranges, such as irons and certain nonferrous alloys, the method will not work at all; in the case of alloys of intermediate solidification ranges, such as commercial steels, the information may be misleading. Thus, the general adoption of this method has resulted in divergent conclusions regarding the solidification process. Chipman and Fondersmith1 by means of bleeding tests have shown that the linear growth of a solidifying ingot wall follows a parabola of the general form, D = K C, with the start of solidification delayed until superheat is exhausted, as indicated by the constant C. These tests were carried only to a wall thickness of about 5 in. using an ingot of approximately 17x39 in. in cross-section; hence the latter stages of solidification were not studied. Matuschka2-3 indicated that linear solidification of ingots is rapid at first, then slow, but toward the end of solidification the rate becomes extremely rapid again. Spretnak&apos;s4 bleeding studies indicated that, wall growth is expressed more rigorously by two parabolas, and that their point of intersection corresponds to a change of solidification mode from columnar to equiaxed. Spretnak also showed that the K values of the first parabola are always the same regardless of superheat. Nelson bled ingots of square cross-section and found that linear wall growth is initially rapid but decreases continually until the end of solidification. He also concluded that rate of solidification in ingots of square cross-section increases 2.15 pct for every 10 pct increase in cross-sectional area of the mold. The mold ratios considered (ratio of cross-sectional area of the mold to cross-sectional area of the ingot) were all less than 2 to 1. The subject of solidification has also been treated mathematically in many cases, but because of the lack of accurate thermal constants and the simplifying assumptions required, as their authors generally acknowledge, they represent only approaches to the actual conditions of ingot solidification. A third method of studying solidification is the electrical analogue method promulgated by Pasch-kis6-7 and by Jackson and coworkers.8 This method treats solidification as a heat transfer problem with the solidification cycle synthesized on an electrical circuit. Paschkis in his treatment of solidification considered the fact, which was generally ignored, that solidification of steel is not simply the growth of a plane solid wall but a more complex process occurring over a temperature range as indicated by the constitution diagram. Undoubtedly, the anomalous results obtained by bleeding tests arise from the inability to measure quantitatively this mushy condition. The shape of Paschkis&apos; solidification curves are more nearly in accord with those of Matuschka, in that they indicate rapid linear solidification at the beginning and end of solidification with intermediate solidification occurring at a slower rate. Paschkis indicates a definite lengthening of solidification time with increasing superheat. Thermal analysis is a direct method providing exact information for all types of metals regardless of solidification range and was thus adopted in the present program to follow the entire course of solidification from the surface to the centerline of the ingots. The method has the added advantage of being adaptable to following the thermal cycle of the ingot mold during the course of solidification. Test Methods The ingots studied were of square cross-section, 20 in. long, tapered from 71/4 in. at the top to 63/4 in. at the bottom, and fed with a hot top 7 in. in diam and 12 in. high. The molds were uniform in wall

Jan 1, 1953

By E. P. Pfleider, Rolland L. Blake

IT is generally believed that the amount of diamond drilling will increase appreciably in the next decade, as the seaarch for minerals throughout the world becomes more difficult and intense. An attendant problem may be one of short diamond supply, resulting in higher bit and drilling cost. With this background, the U. S. Bureau of Mines&apos; and the School of Mines at the University of Minnesota&apos; have established comprehensive research programs in diamond drilling. One of the several aims is the design of a more efficient bit, which would lower diamond consumption and increase rate of advance, both essential in reducing drilling costs. The objective of the specific research problem" discussed in this paper was an investigation of the cutting action of the cliamonds set in a diamond drill bit, cutting action meaning the manner in which the diamonds cut or. loosen the minerals in the rocks being drilled. In the literature on cutting action such descriptive terms are used .as: grinding, wearing, cutting, breaking, shearing, scraping, melting, and chipping. These actions were seldom described or defined. Grodzinski describes the cutting action of a single diamond in the shaping of certain types of material as "breaking out chips of the material." Brittle mate-. rials break as small separate chips, and tough materials, because of heat generated, give a continuous chip. Deeby said about diamond drills: "When diamonds are forced into the formation and rotated, they either break the bond holding the rock particles together, or they cause conchoidal fracture of the rock itself. The former action occurs when drilling in sandstones, siltstones, shales, etc. and the latter action when drilling in chert, flint, or quartz." He said that diamonds cut on the "grinding principle" but he does not define or elaborate on this action. The cutting action of diamonds on glass was first investigated about 1816 by Dr. W. H. Wol-laston, an English physicist. The best glass-cutting diamonds have a natural or artificially rounded cutting edge. This edge first indents the glass and then slightly separates the particles, forming a shallow and nearly invisible fissure. Since none of the material is removed, this action is one of splitting rather than cutting. No other reports of research work on the cutting action of the diamond were found, and further work was considered justified and advisable. It is impractical, even if possible, to observe directly the cutting action of a diamond drill bit in rock; therefore it was necessary to devise an indirect method. It was believed that a study of the following three observations would lead to a better understanding of the cutting action: 1—the appearance of the minerals or rock surface in the bottom of the hole, 2—the size, shape, and other characteristics of the drill cuttings, and 3—the condition of the diamonds in the bit. The cutting action in a particular rock probably varies with bit pressure and speed. If the bit were slowly lifted off the rock, the effect of decreasing pressure might obliterate those bottom hole characteristics that are specific at the test pressure. Likewise, if the drill were stopped with the bit still in contact with the bottom of the hole, then decreasing speed effects would tend to obliterate the characteristics at the set test conditions. Therefore, in order to preserve those cutting effects impressed on the rock at test conditions, it seemed necessary to lift the bit off the bottom of the hole almost instantaneously once drilling conditions, i.e., revolutions per minute, pressure, and water flow became constant. In addition to observing the cuttings, the bit, and the bottom of hole, it seemed desirable to collect some quantitative data for purposes of correlation with the observations and for a record of bit performance. Consequently such data as revolutions per minute, force applied, and rate of advance of the bit were recorded. Six rock types, listed in Table I, were chosen for the tests. It was felt that these rocks had most of the variable characteristics of texture, bonding, and mineral hardness met in the common rocks generally being drilled. The sandstone was so poorly cemented as to be friable, even though most of the cement was silica. The limestone, though well cemented, was quite porous. Originally it was planned to conduct the tesk work with a full-scale drill unit, using EX bits, 7/8-in. core, 11/4-in. OD. The drill worked well, but was too cumbersome for rapid, accurate drilling of many short holes (1 ½-in.) in varied rock types. A new

Jan 1, 1954

By J. B. Clark, A. J. McEvily, R. L. Snyder

The nonuniform distribution of precipitate particles has been recognized as a leading factor contributing to the relatively low fatigue resistance of aluminum alloys. The structure of many of these alloys is characterized by narrow precipitate-free zones adjacent to the grain boundaries. Alloys with such zones exhibit a tendency for brittle inter crystalline fracture. The interrelation between this type of structure and mechanical properties was investigated in an Al-10 wt pct Mg alloy. It was found that deformation during fatigue occurs preferentially along these zones and cracks initiate there. In Al-10wt pct Mg, the zones were found to be supersaturated even after extensive general precipitation and are due to the absence of proper precipitate nuclei in the region near the grain boundaries. Cold working the alloy prior to aging improves the mechanical properties by inducing precipitation within the zones and also by jogging of grain boundaries. The mode of fracture is changed from brittle inter crystalline to more ductile trans granular fracture. THE process of fatigue is highly structure sensitive, with the strength of the whole often dependent upon some localized discontinuity, either geometrical or metallurgical in nature. Much has been learned about the role of geometrical discontinuities, e.g., notches, in fatigue, but with the exception of the effects of inclusions or the shapes of carbides, relatively little is known about the specific effects of discontinuities in metallurgical structure such as nonuniform precipitation. In most age-hardening aluminum alloys, metallo-graphic studies have shown that the extent of precipitation adjacent to grain boundaries is much less than that which occurs in the interior of the grains. The width of these almost precipitate-free regions, which are sometimes called denuded zones, and the extent of solute depletion within them, are dependent upon the particular alloy and its aging treatment. It has been observed1 that these zones are relatively soft with the result that plastic deformation takes place preferentially within them. It has also been shown 2-4 that there exists a tendency for intercrys- talline cracking in fatigue when such zones are present. It is of interest to note that Broom et al.2,3 were able to reduce the incidence of this type of failure in an A1-4 wt pct Cu alloy by stretching the material 10 pct prior to aging. In the present study, the effects of precipitate-free regions on the fatigue properties of an A1-10 wt pct Mg alloy were studied in detail, and the effects of deformation prior to aging on the nature of the precipitation process as well as on fatigue properties were also investigated. MATERIAL AND PROCESSING An A1-10 wt pct Mg alloy was selected for this study, because it was known that well-defined precipitate-free regions along the grain boundaries are readily obtained in this alloy after aging at 200oC.5 The starting materials were 99.998 pct A1 and singly sublimed magnesium of about 99.9 pct purity. The aluminum was induction melted in a graphite crucible, and then the magnesium addition was immersed until dissolved. Chlorine gas was then bubbled through the molten alloy for 4 min to degas the melt, after which the melt was cast at a pouring temperature of 730" to 760°C into a cold, graphite-coated, tapered steel mold. Since A1-Mg alloys are difficult to homogenize,5 special care was taken to obtain a uniform composition. Two-in. cubes were cut from the ingot and heated at 446°C for 30 min. These cubes were then hot forged approximately 35 pct in each of the three cube directions and homogenized for 16 hr at 446°C. Sheet specimens were then obtained by pressing 40 pct and rolling 35 pct per pass with reheating between reduction steps to a final thickness of approximately 0.10 in. The sheet was then solution treated for 16 hr at 446°C and water quenched. The age hardening behavior of this material at 200°C was then determined, and the results are shown in Fig. 1. The age hardening of this alloy when subjected to cold work prior to aging is also shown in this figure. Preliminary work indicated that extensive deformation after quenching was required to affect drastically the precipitate-free regions in this alloy, and a rolling reduction of 50 pct was chosen. For purposes of comparison the following three conditions were studied: a) Solution treated, quenched, and aged 20 hr at 200°C

Jan 1, 1963

By J. M. Woodall

GuAs crystals which have been grown in quartz boats by the horizontal Bridgman method in the pvesence of Ga20 vapov have beetz found to have carrier and donor distributions which do not correspound to those expected from simple dopant seg-vegation during directional freezing; Instead, the carrier distribution is determined by the heat-trentnzent history of the crystal, while the donor distribution, zohiclz is principally due to silicon, is fixed by the pozuth rate, the geo)tlet.ry of the crystal growth vessel, and tlze initial Ga20 pressure. WHEN semiconducting materials are made into doped crystals by the normal freezing method,&apos; they usually exhibit doping variations along the growth axis. If a) there is no dopant diffusion in the solid, b) the dopant is distributed uniformly in the melt, and c) the distribution coefficient, k, does not vary with composition, then the doping variation along the growth axis is represented by the equation: where C is the doping level in the solid at a point where a fraction g of the original liquid has frozen, and Co is the mean concentration. When the dopant is either a singly ionized shallow donor or shallow acceptor, C also represents the carrier concentration. Even though this equation accurately describes the dcping profiles of a large number of normal freeze systems, there are several special systems for which Eq. [I] does not apply. One such system is the horizontal Bridgman method for preparing oxygen-grown GaAs crystals using quartz vessels. Several workers2"* have shown that GaAs crystals grown by the horizontal Bridglnan method using quartz vessels are generally contaminated with silicon in concentrations in excess of 5 < 10lG atoms per cu cm. This contamination is ascribed to a reaction: occurring at the walls of the crystal-growth vessel which liberates silicon into the melt and Ga2O vapor. It has been shown4 that this reaction, and, hence, the silicon contamination, can be suppressed by the addition of oxygen to the crystal-growth apparatus. It is the purpose of this paper to describe a special apparatus capable of yielding single crystals of GaAs grown in the presence of oxygen and to describe both the kinetics of silicon suppression in this system and the relationship between the carrier concentration profile and the silicon concentration profile. EXPERIMENTAL-CRYSTAL GROWTH A schematic diagram of the apparatus used in the oxygen addition experiments is shown in Fig. 1. The most important features of this apparatus are: a) the use of a sand blasted quartz boat, h) a quartz rod of length 1, with a hole of cross section A, that is placed near the boat to limit the free space volume V, over the melt during the growth, and c) the temperature gradient at and near the solid-liquid interface. Sand blasting the boat is necessary to prevent wetting of the melt. The quartz rod retards the diffusion of the GazO vapor away from the melt to the colder portions of the ampoule. A crystal is prepared by first loading a 5.5-in. boat, which has been cleaned in aqua regia, with 40 g of 99.9999 pct Ga along with 1 to 8 mg of Ga203 powder. GazO3 is a convenient source of oxygen since it reacts with gallium at the melt temperature to form Ga20 vapor, the species which apparently controls the suppression of silicon contamination. The loaded boat, the quartz rod, and the 99.9999 pct As are placed in the ampoule as shown in Fig. 1. Generally, GaAs seeds were not used since most of the unseeded growths resulted in monocrys-tals. The ampoule is evacuated to 10-5 Torr and sealed off. The GaAs melt is synthesized by placing the ampoule into a two-zone horizontal Bridgman furnace. The two zones are separated by several sandwiched layers of -in. Fibre-Fax board drilled with holes slightly larger than the OD of the ampoule. This causes a very large temperature gradient between the two zones, which is necessary for single-crystal growth. The two-zone furnace is mounted on a stand fitted with a roller bearing which allows uniform motion of the furnace in a horizontal direction. A uniform velocity of the stand is achieved by the use of a windlass device which winds up a wire attached to the stand. Movement of the solid-liquid interface is accomplished by fixing the position of the ampoule and moving the stand. Growth rates investigated in this experiment were between 0.4 and 1.2 in. per hr. The composition of the melt is fixed by maintaining an arsenic reservoir at 618°C. The stand is moved away

Jan 1, 1968

By Larry Kaufman, Martin Schatz

The effect of pressure on the extension of the ? loop in the FeSi system has been determined by means of metallogvaphic studies and hardness measurements performed on a series of high-purity Fe-Si alloys containing 7.5, 11.0, and 13.9 at. pct Si, respectively. These mensurements, performed at 42 kbar and temperatures up to 1200oC, indicate that the ? loop is expanded to about 10 at. pct Si at 42 kbar as opposed to a maximum extension of 4 at. pct Si at 1 atm. Comparison of the experimental results with thermodynamic predictions of the pressure shifts yields satisfnctory results. DURING the past few years, several studies have been performed in our laboratory1-&apos; in order to determine the effect of high pressure on phase equilibrium in pure iron and iron-base alloys. The purpose of these studies has been to elucidate the effects of high pressure experimentally and to compare the observed results with predicted pressure effects derived on the basis of known thermody-namic and volumetric data at 1 atm. These studies have included work on pure iron2,5,7 as well as Fe-Ni,1,5 Fe-cr,l,5 and Fe-c4-6 alloys. In addition, Tanner and Kulin3 have reported results of pressure studies on two Fe-Si alloys containing 2.0 and 6.25 at. pct Si. At the time of this latter study, no detailed information was available concerning the difference in volume between the a (bcc) and ? (fcc) phases in the Fe-Si system as a function of silicon content. In order to compare their observations with calculated pressure shifts, Tanner and Kulin were forced to assume that silicon had no effect on the difference in volume between a and ? iron. The resulting discrepancy between their calculation of the a/? phase boundary at 42 kbar and the observed results led them to the conclusion that silicon additions probably decrease the difference in volume between a and ? iron. Recently: Cockett and Davis8,9 have reported de- tailed studies of the lattice parameters of a series of Fe-Si alloys at temperatures ranging from 20" to 1150°C. These measurements, performed on alloys in the bcc and fcc range, show that silicon does indeed decrease the difference in volume between a and ? iron. By correcting the calculations of Tanner and Kulin in line with the observed effect of silicon they were able to show improved agreement between computed and observed pressure shifts.&apos; The present measurements were undertaken to provide additional corroboration of this effect, by extending the range of composition, in addition to exploring a situation where large extensions of a ? loop could result in impingement of the ? field with an ordered bcc phase (based on Feo.75Sio.25). I) EXPERIMENTAL PROCEDURES AND RESULTS The alloys investigated were obtained from Dr. F. Kayser of M.I.T. They were prepared at the Ford Scientific Laboratory by vacuum melting electrolytic iron and high-purity silicon. The melts were poured under an argon atmosphere into hot-topped steel molds. Subsequently the ingots were hot-worked down to 1/2-in.-diam rods. Three alloys containing 7.5, 11.0, and 13.9 pct Si were studied. Carbon, regarded as the principal impurity, analyzed at, or below, 0.001 wt pct for all of the alloys. Prior to pressure-temperature treatment, the rod was annealed for 24 hr in vacuum at 1000°C, water-quenched, and subsequently machined into 0.100-in.-diam by 0.100-in.-long specimens. Subsequent to machining, the specimens were again annealed and then examined metallographically. They were found to exhibit a clear coarse-grained ferrite similar to Figs. 10 and 110 of Ref. 1 and Fig. 2 of Ref. 3. Subsequently, specimens of each alloy were equilibrated at 42 kbar at various temperatures in supported piston apparatus.1,3,4,6 Three specimens, one of each alloy, were wrapped in platinum and exposed simultaneously. The pressure-temperature cycle consisted of increasing the pressure from ambient to 42 kbar at 25oC, heating rapidly to the desired temperature, holding for 15 min, and quenching to 100°C, followed by slower cooling to 25°C and pressure release. The temperature was measured with a Pt/Pt-13 pct Rh thermocouple which was not corrected for pressure effects. Subsequently, specimens were examined metallographically and by

Jan 1, 1964

By Charles H. Grant

Some of the limiting factors relative to explosive crushing of rock and ways to overcome a few of these problems are presented. Relationships between borehole diameters, bench heights, and spacings, along with a review of the influence geometry has on energy as these are changed, are discussed. Efficiency in use of explosives and the decay of energy as it moves through rock and is absorbed and dissipated, is described, along with fragmentation as a function of spacings and energy zoning, etc. Communications are one of the major problems encountered. In an effort to provide a better understanding of the use of explosives, it is necessary to take a little different view of what explosives are, how to look at them as tools to fragment rock, and some of the problems encountered in doing so. First, take the explosive: although there are many factors involved, consider these as being reduced to only two — shock-strain imparted to the rock by the high early development of energy, and the gas effect which is a combination of heat, moles of gas formed, rate of formation of these gases which develop pressures, etc. First, consider shock energy by itself and assume there is no gas effect in the reaction. Fig. 1 illustrates a block or cube of rock, in the center of which is detonated an explosive charge which is 100% shock energy. Tensile slabbing would be seen on the surface and probably the cube of rock would generally hang together even though microcracks were formed. If the situation is reversed and an explosive whch has no shock energy and only gas effect (Fig. 2) is considered, the cube of rock would act as a pressure vessel and contain the pressure from the gas effect until it exceeded the rock-vessel strength; then the rock would break in a few large pieces. If these two kinds of energy are put together and the area of shock-strain around the explosive (Fig. 3) is considered, the two energies will be seen working together to furnish broken rock. The gas effect applies pressure to the microcracks formed from the shock energy to weaken the rock-pressure vessel and propagate these cracks to break the rock apart. It not only will be broken more finely, but will break apart at a lower pressure than the gaseffect case, since the shock energy has first weakened the rock vessel. Although tensile spalling from the shock-strain imparts momentum to the rock, the main source of displacement comes from the gas effect. The term "rock" is being used to mean any material to be blasted. These energies are absorbed by the rock in different ways. First, classify rock into two main categories: "elastic" and "plastic-acting." Elastic rock should be thought of as rock which can transmit a shock wave and is high in compressive strength, such as granite or quartzite. Since this elastic rock transmits a shock wave well, it makes good use of the shock energy from the explosive-forming cracks, etc., for the gas effect to work on. Plastic-acting rocks are rock masses which are relatively low in compressive strength and absorb shock energy at a much faster rate, thereby making poor use of the shock energy by not developing as extensive a cracked zone for the gas effect to work on. Rocks of this type are generally softer materials such as some limestones, sandstones, and porphyries. For the most part, the shockenergy part of the explosive reaction is wasted in plastic-acting rock, leaving most of the work to the gas effect. Since the ratio of gas effect to shock energy is different in different explosives, it is easy to understand why some explosives perform well in elastic rock and poorly in plastic-acting rock, and vice versa. Some of the most difficult blasting situations arise when mixtures of plastic-acting and elastic rock are encountered (Fig. 4). Fig. 4 shows an example of granite boulders cemented together with something like a decomposed quartz monzonite which is plastic-acting. The elastic granite boulders will transmit the shock-strain within itself, but when this shock tries to move through the monzonite to the next boulder, its intensity is absorbed by the monzonite and little shock-strain is placed on the adjoining boulder. In addition to this loss by absorbtion, shock reflection at the surface of the boulder will effect tensile spalling. The net effect is poor breakage of the boulders which do not have drillholes in them as they simply will be popped out with the muck. The same is true (Fig. 5) when layers and joints make

Jan 1, 1970

By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates&apos; have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959

By W. Bonfield

A study has been made of the dislocation substructures produced in hot-pressed beryllium specimens strained to various levels in the range from 800 x 10-6 In. pev in. to fracture. A number of distinctive dislocation configurations were observed in this region which had not been noted at lower levels of strain. These included dislocation-dislocation interactions to form networks, dislocation "walls", subgrain boundaries and complex arrays, interactions between dislocations and large beryllium oxide particles, and the generation of dislocations from certain particles. The nature of these differences in substructure and their relation to the stress-strain characteristics of polycrystalline beryllium are discussed. In a previous study1 of the plasticity of commercial-purity, hot-pressed beryllium a transition was found in the deformation characteristics in the mi-crostrain region. The initial plastic deformation could be represented by a parabolic stress-strain equation, but above a critical stress there was a complete departure from this relation and a reduction in the strain-hardening rate. The dislocation configurations produced by various levels of micro-strain in this region were examined by transmission electron microscopy and a general correlation was established between the observed transition in deformation characteristics and the dislocation structure of the material. The two stages in the micro-strain region distinguished in these experiments were designated as Stage A&apos; and Stage B&apos;. Stage A&apos; type deformation generally was noted up to a plastic strain of -80 x 10"6 in. per in. and Stage B&apos; type from -80 x 10-6 to -800 x 10&apos;6 in. per in. The discovery of two stages in the microstrain region naturally posed pertinent questions as to the existence of any further distinct stages in the subsequent plastic deformation. The purpose of this paper is to present a study of the dislocation configurations produced in similar beryllium specimens strained to various levels in the range from -800 x 10 in. per in. to fracture and to discuss the relation between substructure and the stress-strain characteristics. It is concluded that this region of strain can be considered as a distinct stage in the plastic deformation of polycrystalline beryllium. Tensile specimens of gage length 1 in. and cross section 0.18 by 0.06 in. were prepared from commercial-purity, hot-pressed QMV beryllium and then annealed at 1100°C for 2 hr. 2 followed by a careful chemical polishing procedure.3 The specimens were strained at a constant rate to various levels of strain in the range from -800 x 10-6 in. per in. to fracture (at 0.5 to 2 pct elongation), using the Tuckerman strain-gage technique1 to measure plastic and total strain. Thin foils were obtained from the strained and fractured specimens by chemical polishing3 and were examined using an RCA-EMU 3 electron microscope. Considerable care waS taken to avoid both accidental deformation during the preparation of the thin foils and excessive heating during their examination. Selected-area diffraction patterns were determined for each micrograph. Tilting experiments were also performed whenever appropriate to establish the dislocation zero-contrast position and hence determine the Burgers vector. This operation was sometimes not possible due to the rapid contamination of the foils which occurred in the electron microscope. RESULTS AND DISCUSSION To enable the distinctions between the dislocation arrays at high and low strain levels to be adequately made, the main characteristics of Stage A&apos; and Stage B&apos; deformation are briefly reviewed. 1) Stage A&apos;. In the annealed starting condition there was a variable density (5 x 107 to 3 x 10&apos; cm per cu cm) of isolated dislocations within a grain. The initial deformation in a tensile specimen was heterogeneous, with the dislocation density increasing in a few grains to 5 x 10g to 1.5 x 101° cm per cu cm. The deformation occurred exclusively on the basal plane by the movement of one or more 1/3 (1130) type dislocation systems. The dislocations were long and regular in form and nearly all the intersections exhibited a simple four-point node configuration. No interactions between glide dislocations and beryllium oxide particles were observed. 2) Stage B. In Stage B&apos; there was a large increase in the number of grains exhibiting dislocation movement and also a change in the nature of the deformation, in which jogged dislocations and elongated loops became the characteristic feature. The splitting up of the elongated loops into smaller loops and the possibility of source action from the re-

Jan 1, 1965