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By L. F. Elkins

In 1946 Littlefield, Gray and Godbold published a thorough geologic description of the West Edmond Hunton Lime reservoir, located in Central Oklahoma, and discussion of its early performance.l They stressed implications of the nature of the reservoir rock on performance to be expected with production both by natural means and by pressure maintenance with gas injection. The essence of their analysis was that presence of an extensive interconnected system of fractures and solution channels constituting about 10 percent of the total reservoir void space in otherwise very low permeability reservoir rock would result in severe channeling of naturally encroaching water or injected gas through the fractures with little or no benefit to ultimate recovery of oil. Considerations were in progress to unitize the reservoir for pressure maintenance by gas injection. Some other engineers involved in the project had considerably different opinions at the time regarding continuity of fractures and regarding effects of such fractures on performance. The field was unitized Oct. 1, 1947. Subsequently, pilot gas injection tests were conducted in four areas of the field; large scale waterflooding was conducted in two parts of the field in the Bois d'Arc or Upper Hunton; and pilot waterflooding was conducted in the Chimney Hill or Lower Hunton. Full scale water-flooding is now in progress in the Chimney Hill section where it is oil productive. The primary purpose of this paper is to divine some of the secrets of this reservoir through analysis of all aspects of its performance, with the hope that it will be of help to engineers and operators in developing and operating other low permeability fractured reservoirs. In part, this considers variance of actual performance from some widely used conventional reservoir engineering assumptions. For brevity, other aspects of unit operation and its benefits to the owners are not discussed. Oil and Gas in Place For unit participation, net pay in the Bois #Arc defined by the gross SP anomaly on electric logs totalled 2,100,000 acre-ft in the 30,000-acre reservoir. Development of West Edmond predated modem logging techniques that now would be used to determine "net" or "productive" pay. In Fig. 1 this log pick is compared with detailed core analysis and core descripfion by Littlefield et a1.l for one well identified as A on the index map in Fig. 2. Not all of the gross Bois #Arc section had oil staining, but all cores with measureable intergranular permeability were stained. (The committee selection of the Bois d'Arc SP interval also includes the Frisco section as identified from cores by Littlefield.) The Bois d'Arc is oil productive throughout the entire 600-ft monoclinal accumulation from the eastern upstructure erosional pinchout to the west-side oil-water contact. (See Littlefield et al.l and McGee and Jenkins for geologic detail.)

Jan 1, 1970

By W. T. Bell, M. P. Lebourg

The perforating of multiple tubingless completions, in which two or more strings of 27/8-in. OD casing are installed in the same borehole, presents two basic problems. First, good completion practices require an eficient perforator that leaves no debris to interfere with subsequent completion operations. Second, and of more complicated nature, a system is needed for controlling the direction of fire so that adjacent strings are not damaged. Development of of a 2-in. OD, steel retrievable, shnped-charge gun has solved the first problem. The second was resolved through development of three different devices to provide directional perforating for the two types of completion methods being employed today. These include a mechanical orienting device and two self-orienting radiation devices. Conceivably, the latter methods could be adapted to the directional perforating (of .upper zones) of conventional dual and triple completions without removing production tubing and packers. INTRODUCTION The recent trend to multiple tubingless completions,' wherein two or more strings of 27/8-in. OD casing are installed in the same borehole, has presented two basic perforating problems. The first problem to be overcome was the design of a gun that would result in efficient perforations without causing debris to bridge in these small-diameter casings. The second problem was, of course, to devise a system for controlling the direction of fire such that adjacent strings would not be damaged. The problem of gun debris in slim-casing completions has been well defined in the numerous 27/8-in. single tubingless completions which have been effected during recent years with the expendable-type perforators. Failure of expendable-gun debris to settle out properly, even with good gun break-up, has resulted in bridging inside these small-diameter casings. This, in turn, has interfered with completion and re-conditioning operations. The past two years have clearly shown, in fact, that debris problems are not confined to this small range of casing with most designs of expendable-type guns. A high incidence of bridging has even been reported in 4%-in. OD casing. The perforating of multiple tubingless completions has entailed, therefore, the development of a completely debris-free gun of adequate performance, as well as the necessary devices to provide positive directional perforating in the two completion methods presently being employed. THE GUN —DESIGN CONSIDERATIONS The design of a shaped-charge gun for slim-casing perforating has presented a maze of interrelated prob-lems. Since the primary specification has been leveled at efficient charge performance with complete elimination of gun debris, it has been necessary to develop a retrievable steel-carrier gun of tubular construction to house the charges. The carrier must be retrievable through 2.29-in. API pump-seating nipples which are usually installed in 2 7/8-in. strings. To provide for recovery of the gun from the well, swelling of the carrier on firing must be carefully controlled. Control of swelling automatically means control of explosive weight in the shaped charge which, in turn, influences charge performance. Carrier swelling also depends upon the confinement pressure at the level being perforated, which imposes a hydrostatic pressure-depth limitation. Burr interference on the wall of the carrier, resulting from passage of the jet through the carrier wall, must be eliminated by suitable design. Clearly then, a satisfactory shaped-charge gun design for slim-casing operations represents a fine balance between carrier swelling, hydrostatic pressure, explosive weight and charge performance. Additionally, to lend itself to directional perforating, the gun design must provide a positive locking mechanism for individual charges within the gun carrier. This fixes charge orientation within the carrier and prevents

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'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,' and by Grant and Szasz.' Results from other tests have since been reported by Walter,3 by Moss, White and McNeil,' 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 R. F. Shurtz

The problem of estimating the precision of systematic samples from a mineral deposit is attacked by interpolating the quality, or other attribute measured, by using Fourier approximation. Such approximation using trigonometric functions yields a particularly simple expression for the variance of the mean value of the attribute sampled. The increasing volume of publication in which the science of statistics has been applied to the problem of predicting the quality of an ore deposit from sets of samples taken from it might lead one to believe that engineering judgment can be replaced by statistics. There is, in fact, an implicit application of the principle of indifference or of "no advance knowledge" which has been discredited in modern statistical theory and practice. These pages will show that it is not always advantageous, efficient, or safe to apply this principle. This problem will be dealt with by using series of orthonormal functions to describe the distribution of the quality of ore in space as contrasted with the more commonly used distribution of quality as a frequency function. Mining engineers are rarely well acquainted with the use of such series or of the functions comprising them. These uses are commonplace in the fields of communication and information theory and it is not surprising that applications taken from these fields should be found appropriate for the analysis of the information contained in a set of samples from an ore deposit. It is hoped that presentation of the following basic, but incomplete, results will generate wider interest in this method and a fuller development of it as well as of the necessary computational techniques. FUNDAMENTAL PREMISES Random variables in the strictest sense are not very common in mine sampling. The sets of samples are almost always taken systematically and are, hence, not subject to all the laws governing random events. Therefore, unless there is indeed random experimental error in the determinations of quality, the treatment of systematic samples of n members as though they were random samples of n members often leads to calculation of confidence limits for the mean quality which are larger than they should be with the result that unnecessary additional sampling is done. The reason for this will emerge in the following discussion leading to Eq. 24 and its generalization. In order to inquire into such questions on a rigorous basis and at the same time avoid arithmetic complications that would obscure the concepts involved, a one dimensional distribution of quality will be assumed. The quality, Q, in suitable units is expressed as a function of the distance, x, along some straight traverse of the deposit. Such a function

Jan 1, 1967

By Arthur Glance

MINE safety is of the utmost importance to all operators and most operations have a safety organization, or safety inspector, whose job it is to be continually on the alert to detect and correct the hazards of mine operation. Reports from the Bureau of Mines show that next to roof falls, gas presents the greatest hazard in mining. The Bureau of Mines Information Circular 6680 shows that 162 explosions occurred in the United States during the five-year period ending June 30, 1932. Deaths resulting from these explosions amounted to 984, with a great many disabled and disfigured. A fatality rate of 6.07 persons shows the ex¬treme severity of this hazard to the industry. Various mine appliance companies have put on the market instruments for methane detection, which record in direct percentages the amount of methane present in the atmosphere. Unfortunately, few mining companies are using these instruments, however. Those available include the Burrell methane detector, the Wolf, the Martienssen, the Mine Safety Appliance detector, and the Union Carbide Company methane detector, which last I have used extensively in making mine inspections.

Jan 1, 1936

By R. W. Raymond

ALEXANDER BRINTON COXE was born in Philadelphia, Pa., Jan. 19, 1838, the second of five sons of lion. Charles Sidney Core and Ann Maria Brinton. A more extended history of his family and its important relations to the development of the United States will be found in my Biographical Notice of his younger brother, Eckley B. Coxe, published in 1895. It is therefore sufficient to say here that Dr. Daniel Coxe, a distinguished physician and surgeon of London, and a medical attendant of Charles II and Queen Anne, purchased, in 1684 and 1686, lands in East and West Jersey from grantees of the Duke of York, and became Governor of West Jersey, in which capacity he did much to develop the provincial fisheries, the manufacture of marine salt and pottery, the exportation of tim¬ber and the West India trade. In 1698, having acquired the royal patent of the Province of " Carolana," covering (with some reservations) the territory extending from the Atlantic to the Pacific, between the 31st and 36th parallels of N. latitude, Gov. Cole sent an expedition from Charleston, S. C., to the Mississippi. In 1769, seventy years later, his grandchildren surrendered to the Crown their title under this vast and vague patent, receiving in return a grant of 100,000 acres in the Colony of New York. The line of his descendants, so far as they concern this sketch, is as follows 1. Col. Daniel Core, his son, b. 1673, who came to New Jersey in 1700; resided there until his death (1730); held many high offices; and issued in London (1722) A Description of the Provinces of Carolana, containing probably the earliest published plan of political union for the British Colonies in North America.

Sep 1, 1906

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969

By Thomas T. Read

IN reviewing the field of mineral industry education last year reference was made to recent assertions, mostly emanating from sources not in a position to know the facts, that mining engineers as a class are disappearing. Attention might also then have been called to a statement that appeared in Engineering News, August 11, 1892 (p. 130), ". . . the great absolute decline in number of mining graduates, which last amounts almost to a complete abandonment of mining engineering as a distinct branch of study." Evidently we outrank opera stars in the number of farewell appearances we are able to make; 43

Jan 1, 1936

By T. A. Wilson, S. L. Hoyt

The plastic deformation of slender single crystals of zinc has been described in some detail in the paper by Mark, Polanyi and Schmid,' which has become a classic, and also by one of the present authors in a somewhat shorter account. 2 The study of single-crystal zinc is termed classical because zinc single crystals offer, perhaps, the best material yet available for the study of atomic behavior during deformation and the effect known as "strengthening" in metals. A considerable amount of additional work has also been done on single-crystal zinc, but as it is not closely related to the present paper it will not be considered. Throughout all the former work, the mechanism of plastic deformation first described by Mark, Polanyi and Schmid has been assumed to hold. This may be said to offer the strongest confirmation of its correctness. Even so, the picture of the process has never been as completely portrayed as is desirable. The first object of the present paper is to describe work that has been done in this field, and which is even yet being carried on, in the hope that a more complete picture may be obtained. Mathewson and Phillips3 have recently described a new mechanism of the deformation of zinc based on their study of large rectangular crystals. One of their conclusions was that deformation produced twinning with a rotation of some of the basal planes into positions 94" removed from their original position; a position almost the same as that of the prismatic planes before twinning. A second conclusion was that fracture occurred along these basal planes in their new position, and, therefore that fractures previously regarded as prismatic were in reality basal. Such findings are of great significance and they raise a question as to the generality of such behavior. Professor Mathewson's opinion is that even the slender cylindrical single crystals behave in the same manner as his large rectangular crystals when strained by simple tension.

By M. M. Singh, J. W. Brown

Three rocks of highly varied physical properties are selected for the first reported experimental study concerning microseismic activity of rock under tension to determine the effects of static fatigue, loading rate, repeated loading and rock anistropy compared to compression and bending loads. The microseismic method of detecting rock under deformation may be a great potential tool in surveillance and location in situ of dangerously stressed strata, as well as predicting rock failures. Noises emitted under load or the rate of energy (energy of noise pulses generated per unit time) are computed for varying conditions. The tests are conducted at constant load on a dead weight loading machine to eliminate all possible extraneous noises — an indispensable precaution — at various load levels. Experimental results are reported including the relation of total energy emitted to tensile strength of rock and the possibility of simulating a phenomenological model for microseismic activity. Plots of some of the experiments are included. INTRODUCTION Rock failure, whether on a large scale faulting in the earth's crust and rock bursts in mines, or on small scale ruptures of laboratory test specimens, generates transient vibrations in the rock mass. Mechanisms of intermittent deformation, such as twinning and cracking through and between mineral grains, also produce similar vibrations, but of very small amplitude. Such vibrations from both deformation and failure are referred to as microseismic activity, rock noise, or occasionally seismo-acoustical activity. An individual rock noise is sometimes

Jan 1, 1967

By R. D. Nelson

The purpose of this technical note is to briefly present some data on a phenomenon—recrystallization with concurrent deformation—that has been found to occur in a plutonium. This phenomenon is unusual because a plutonium is considered brittle, not easily deformed, and not easily recrystallized; the a phase is simple monoclinic having 8 atoms per unit cell and it is stable below about 115°C. The properties of the recrystallized metal were different from the as-cast metal. Even though a plutonium is difficult to deform, Ianniello successfully rolled it' and he also observed some recrystallization at 120°C.2 Pavlick and Hanson3 detected some recovery at 109°C but they observed no recrystallization. Gardner4 and Bronisz5 studied the compression properties up to 100°C but they did not report having seen recrystallization. In the present deformation studies of electrorefined plutonium pronounced recrystallization took place concurrently with plastic deformation in compression between 24" and 115°C. The metal contained less than 300 ppm total impurities with the major impurities being 100 ppm Am, 30 ppm C, 40 ppm W, and 25 ppm U; all other impurities totaled less than 100 ppm. The compression specimens were machined to dimensions of 1.2 cm long and 0.8 cm diam from as-cast rods having a density of 19.65 g per cu cm. They were heated to the test temperature in a high-temperature silicone fluid that was evacuated to 10-4 Torr. With this procedure the specimens oxidized a negligible amount, and the temperature was maintained within ±0.2°C for times up to 3 weeks. Deformation and recrystallization

Jan 1, 1969

By M. A. Quader, D. Kuhlmann-Wilsdorf, R. A. Dodd

STACKING fault tetrahedra were first observed in quenched and aged pure gold by Silcox and Hirsch1 and identified as defects originating in the collapse of vacancy discs on {111} planes. It was supposed that sessile loops are the first product of the collapse, and that by a dislocation dissociation/glide sequence these are converted into tetrahedra. Although the tetrahedra can be mechanistically accounted for in this way, recent investigations indicate that their growth occurs by the absorption of individual vacancies on small nuclei involving perhaps as few as six vacancies.2-7 Besides stacking fault tetrahedra, triangular and crystallographic shaped Frank loops, although fewer in number, have always been observed in quenched and aged gold.19798 It is not known definitely whether these loops form from collapsed tetrahedra. The fact that the Frank loops are usually larger than the accompanying tetrahedra might indicate that the loops grow independently by absorbing vacancies, but this does not rule out the possibility of the collapse of tetrahedra into loops under all circumstances. Silcox and Hirsch1 have actually observed under the electron microscope tetrahedra collapsing into loops, probably due to stresses set up by the heating of the specimen by the electron beam. The energy residing in the stacking faults of a tetrahedron is proportional to the square of the edge length, while the energy of a triangular perfect dislocation loop depends on its edge length, L, as const L ln(L/ro). Therefore, beyond some critical size tetrahedra must become unstable with respect to collapse into triangular loops.1,3,8-11 However, it seems that in the absence of strong stresses tetrahedra usually decay by the

Jan 1, 1969

By R. D. Daniels, T. G. Oakwood

A study was made of the effects of small quantities of hydrogen on the mechanical properties of colum-bium. Tensile specimens, hydrogenated to concentrations of 20 to 200 ppm, were tested at temperatures of 300°, 191°, and 77°K. Although hydrogen was found to have little effect on the strength of columbium, the ductility of Cb-H alloys was found to be quite sensitive to both hydrogen concentration and temperature. At 300°K, an abrupt loss in ductility occurred at a critical hydrogen concentration, although some ductility was observed beyond the tolerance limit. A similar result was found at a lower hydrogen concentration at 191°K. At 77°K, however, a more gradual loss in ductility with increasing hydrogen concentration was observed. Hydrogenated columbium was thus observed to undergo a ductile-brittle-ductile transition. Metallographic examination of fractured specimens revealed extensive porosity at both 77° and300°K which was a distinct function of hydrogen content. At 191°K, although some secondary cracking was noted, the amount of observed porosity was minimal. These observations are interpreted in terms of hydrogen solubility and mobility as a function of temperature and in the role of hydrogen in promoting growth of microcracks. lHE effect of hydrogen on the mechanical properties of the refractory metals is not, at present, completely understood. A number of studies have shown these materials to be susceptible to hydrogen embrittlement. Roberts and Rogers1 have found that vanadium can be embrittled by hydrogen. It was further demonstrated that fracture undergoes a ductile-brittle-ductile transition as the temperature is lowered from 150° to -196°C; i.e., there is a ductility minimum observed at a certain temperature. The ductility is increased by either raising or lowering the temperature from this point. A more complete study by Eustice and Carlson2 on vanadium containing 10 to 800 ppm placed the ductility minimum at about -100°C with variations reportedly due to hydrogen content and strain rate. Ductility minima have also been found at certain temperatures for tantalum containing 7 ppm H3 and 140 ppm H.4 At hydrogen concentrations above 270 ppm, however, the ductility return at low temperatures was considerably reduced.4 In the case of columbium, some disagreement exists in the literature. Eustice and Carlson,5 Wilcox et al.,6 and Imgram et al.4 failed to find a ductility minimum although a composition-dependent ductile-brittle transition was observed. Hydrogen concentrations in these investigations were 20 ppm,5 1 to 30 ppm,6 and 200 to 390 ppm.4 However, Wood and Daniels7 observed a rather pronounced ductility minimum at hydrogen contents ranging from 19 to 252 ppm. Those theories of hydrogen embrittlement involving the precipitation of diatomic hydrogen which have been applies to ferrous metals8-12 do not seem to be applicable to the case of columbium and other exothermic occluders. Such theories propose that extensive crack formation and propagation occurs by the precipitation and expansion of diatomic hydrogen at internal voids and microcracks. However, photomicrographs of hydrogenated columbium do not show any evidence of damage introduced by the sorption and precipitation of diatomic hydrogen; rather, at high hydrogen concentrations, a hydrogen-rich second phase is precipitated.13'14 In addition, a number of these theories require the development of high hydrogen pressures at voids in the structure.8'10'12 This does not appear to be feasible in the concentration ranges discussed in the aforementioned paragraphs. The possible interaction of atomic hydrogen with microcracks resulting from dislocation pile-ups15,16 remains in doubt since pile-ups have not been observed in bcc metals17 including columbium.18 Wood and Daniels7 have put forth the possibility that a hydride precipitation could be responsible for crack nucleation in columbium. Work by Longson19 has shown that hydrogen embrittlement of columbium parallels the bulk solubility limit; i.e., as the solubility increases, for instance with temperature, the amount of hydrogen necessary to cause embrittlement also increases. Although a hydride precipitation appears attractive as a means of nucleating microcracks in columbium, what require more intensive study are the low-temperature anomalies which have been observed, i.e., the ductile-brittle-d'ictile transition characteristics. Also, the hydrogen concentrations where embrittlement occurs are often below the bulk solubility limits determined by Albrecht et al.13,14 and Walter and Chandler.20 This work is an attempt to determine more definitively the effects of concentration and temperature on the mechanical properties of dilute Cb-H alloys. EXPERIMENTAL PROCEDURE Ultrahigh-purity columbium rods, obtained from the Wah Chang Corp., were cold-reduced by rotary swaging. A chemical analysis is given in Table I. The material was cut into cylindrical blanks 1.50 ±0.005 in. long. Individual specimens were either given a stress relief anneal at 750°C or recrystal-lized at 1200°C. Resulting microstructures were either a "bamboo" structure characteristic of a wrought material or a recrystallized structure with a grain diameter of approximately 100 n. All heat treatments were carried out in a vacuum of 10-5 Torr or less.

Jan 1, 1969

By K. T. Aust

The occurrence of annealing twins in high-purity aluminum resulted in the formation of grain boundaries having orientation relationships which correspond to a high density of coincidence sites. The results provide support for the coincidence site model and indicate that large-angle coincidence boundaries have lower free energies than large-angle noncoincidence boundaries. Observations are presented concerning the coherent structure of twin interfaces in aluminum and the importance of inter-facial energy in preferred orientation. RECENT experiments1 have shown that when an annealing twin is formed during grain boundary migration in zone-refined lead, a large-angle random boundary is replaced at the growth front by a large-angle coincidence site boundary. The coincidence site orientation relationships obtained by twinning were of the type considered by Kronberg and Wilson,2 Frank,3 and Dunn.4 On the basis of the theory of annealing twins advanced by Fullman and Fisher,5 these observations indicate that the energy of a coincidence site boundary is less than the energy of a random boundary by an amount which exceeds the energy of the coherent twin boundary. This energy difference between the coincidence and random boundaries must be at least about 5 pct since the ratio of twin boundary energy to grain boundary energy in zone-refined lead is 0.05 * .014.6 Fullman7 has found that the twin boundary energy in aluminum is about 21 i 5 pct that of a large-angle grain boundary. A twin boundary energy as large as this would be expected to exclude the formation of many coincidence site grain boundaries, especially those which have a relatively low density of coin- cidence sites. Therefore, if the coincidence site model is a useful interpretation of certain large-angle boundaries, then it would be predicted that only coincidence boundaries which separate adjacent crystals with a relatively high density of coincidence sites may be obtained as a result of twinning in aluminum. The present experiments provided a means of testing this prediction since annealing twins occurred during the growth of recrystallized grains into striated, melt-grown single crystals of zone-refined aluminum. EXPERJMENTAL PROCEDURE A striated single crystal of zone-refined aluminum, about 1 cm sq and 37 cm in length, was obtained during zone melting of aluminum of 99.996 wt pct starting purity in a graphite boat under helium atmosphere.8 A molten zone of 2 to 3 cm in length, which was maintained by induction heating. was passed along the length of the bar for eleven passes at a rate of 0.9 mm per min. An additional final pass was given at a rate of 0.2 mm per min. The center portion of the zone-melted bar was characterized by an electrical resistivity ratio between room temperature and 4.2° K of 8000 to 9000. Single crystals of 1 to 2 cm in length were removed from the center section of the zone-refined bar and electrolytic ally polished in a 2:l solution of methyl alcohol and concentrated nitric acid. The specimens were then chemically polished in Alcoa R-5 solution. X-ray analysis of the single crystals indicated the presence of striations or lineage substructure having misorientations as high as 2 deg. New, recrystallized grains were introduced into each striated crystal by the technique of artificial nucleation and growth, previously described.9 During the growth of the recrystallized grains at 300' to 600°C in argon, it was sometimes found that a

Jan 1, 1962

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By Ralph H. Sweetser

C. H. Herty, Jr.,* Pittsburgh, Pa.—The procedure of the Open-hearth Committee in studying pig iron and its effects in the open hearth has been influenced by the discussions at a number of meetings of the Committee. Those discussions have brought out very clearly that, as far as the pig iron affects the quality, interference with quality should be studied for three definite types of pig iron: (1) low-silicon pig iron; (2) very high-silicon pig iron, and (3) pig iron in which the silicon varies over a wide range in short periods, such as 1 to 3 casts. If a blast furnace is running steadily at 1 per cent. silicon iron, practically no trouble, apparently, can be traced to the pig iron, but if the furnace is running from 0.60 up to 1.50 and then down to 0.60 per cent., trouble in the finished steel is liable to occur, which apparently cannot be corrected by open-hearth practice. The open-hearth discussions have shown fairly definitely that with low-silicon iron, one type of trouble arises on the finished product and with the high-silicon iron, another. Our experience with the high-silicon is that any non-metallic matter that may form, does so when the pig iron is put into the furnace; that is, silicates immediately form which are more liable to be high in silica than would happen with low-silicon iron. I think Mr. Sweetser will agree with mc that if a blast furnace is very irregular, different points in the furnace may be working irregularly, in other words, the temperature gradient all over the furnace is not uniform. We have made many determinations on that point which indicate that a varying blast furnace causes hot spots and cold spots around the periphery. If some of those spots are hot and others are cold, although the analysis of the iron may be constant, then unreduced oxide, going through on one side, and good iron, going through on the other, may mix and the average temperature of the iron is not high enough to get completely rid of the oxides. So our method of attack is directly on that point; it is our first objective. Our procedure is to make a number of consecutive tests at a blast furnace, making a detailed study of the blast-furnace operation. We follow the iron through the open-hearth heat, being sure that we know just how much of each kind of iron gets into the open hearth, and take out specified samples at certain times during the process, working on steel where no finishing additions are made in the furnace. We are following one type of iron through the billet mills and into the finished product and are obtaining complete data on open-hearth operation. Besides the ordinary chemical analyses on the samples of slag and metal, we are running samples of the plg iron, the steel in the open hearth and the finished steel, for oxygen and silicates. We are going to find out whether or not oxygen, as silicates or oxides, has some connection with this trouble. If not, we may be able to locate some other factor. I am inclined to think that the silicates are responsible, judging from the indications in some other work that the Bureau of Mines is doing in Pittsburgh. We have laid out a very definite method of testing to which we will adhere at the different plants where we are now working and at others in the future. Our aim is to

Jan 1, 1927

By E. A. Holbrook

AT the meeting of the Committee on Engineering A Education of the Institute at the New York meeting last February, it was brought out that the number of men graduating in mining engineering from our colleges at the present time is not sufficient to meet the ordinary needs of the mineral industries. Following the meeting, Samuel S. Wyer, consulting engineer of the Fuel-Power Transportation Educational Foundation of Columbus, Ohio, prepared a pamphlet called "Mining Engineering's Appeal to High School Seniors." Under the auspices of this Foundation the pamphlet is being sent to every high school in the United States. The pamphlet does not in any way paint glowing word pictures of the profession; rather it is a statement of the importance of mining engineering in our present-day civilization, together with the requirements in young men who are looking forward to an engineering career.

Jan 1, 1930

By R. Taggart, R. H. Ericksen, D. H. Polonis

MarTENSITIC a has been observed to form spontaneously from the retained ß phase during the preparation of thin foil specimens of metastable Ti-Cr alloys containing from 6.9 to 20 wt pet Cr. Similar spontaneous martensite reactions have been reported in thin foils of 0 brass' and other alloys.2 4 The absence of retained austenite in iron-based alloys has also been attributed to spontaneous decomposition during thinning.5 The present work indicates that a unique situation occurs during which the spontaneous transformation takes place when the transitional ? phase is present in the as-quenched or partially aged ß phase. Alloys containing 6.9, 7.0, 8.0, 12.0, and 20.0 wt pet Cr were prepared by the levitation melting of "io-chrome" chromium and iodide titanium. The 0.5-in.-diam ingots were vacuum-annealed at 1000oC, and wafers 0.020 in. thick were then cut from the ingots. These wafers were wrapped in molybdenum foil, encapsulated in Vycor under a reduced pressure of purified helium, and then held for 30 min at 1000°C. The specimens were quenched in water to retain the metastable high-temperature ß phase. The quenched alloys were thinned by mechanical grinding to about 0.005 in. thick, then electropolished in a solution of 300 ml methyl alcohol, 175 ml n-butyl alcohol, and 30 ml perchloric acid at a temperature of -40°C. Needle specimens 0.005 to 0.010 in. diam were taken from each ingot and heat-treated with the foil specimens. X-ray diffraction patterns indicated the structure of the 6.9, 7.0, and 8 wt pet alloys to be a

Jan 1, 1968

By Reginald S. Dean

THE commercial availability of electrolytic manganese has greatly changed the position of manganese as a nonferrous alloying metal. Manganese metal commercially available up to about ten years ago was reduced with either silicon or aluminum and contained substantial amounts of the oxides of these metals and other impurities. Manganese was accordingly not available as an alloy base and its addition to copper-base and nickel-base alloys was generally limited to a manganese content of a few per cent. Several special alloys like manganin contained up to 12 pct of manganese. A method for the production of electrolytic manganese was developed by the Bureau of Mines in 1936 and commercial production was begun in 1938. At the present time (June 1951), production is about 12 tons per day but appears likely to be substantially increased. Electrolytic manganese is deposited from an aqueous electrolyte containing manganese and ammonium sulphates and is marketed as cathode fragments about 1/8 in. thick. The impurities in its composition are as follows: iron, 0.0015 pct; copper, 0.001; arsenic, 0.0005; cobalt, 0.0025; lead, 0.0025; molybdenum, 0.001; sulfide sulfur, 0.017; sulfate sulfur, 0.014; insoluble, 0.002; carbon, 0.002; hydrogen, 0.015. These figures are from Bulletin 463, U. S. Bureau of Mines. From an alloying standpoint, the most important impurity is hydrogen. This can be removed by heating; 95 pct of the hydrogen can be removed in this way without introducing significant amounts of oxygen or nitrogen. Much of the commercial electrolytic manganese used in alloys is dehydrogenited by the producer, since the amount

Jan 1, 1953

By L. W. Kempf, R. S. Archer

The binary aluminum-silicon alloys have certain characteristic advantages which are now well known, and these alloys have come into considerable use during the past several years.' Their field of application has been limited to a certain extent, however, by their low yield point and hardness, low endurance limit, and relatively poor machining characteristics. These properties are improved by the addition of copper, and the ternary aluminum-silicon-copper alloys constitute an important class. The addition of copper decreases the corrosion resistance of the aluminum-silicon alloys and increases specific gravity. Magnesium is a hardening addition which seems to have relatively little effect on corrosion resistance, and which, of course, reduces specific gravity. The object of the work described in this paper was the development of alloys and heat treatments for the production of sand castings and permanent-mold castings having substantially all the advantages of the binary aluminum-silicon alloys together with mechanical properties improved to a degree permitting wider application. Constitution of Alloys Magnesium and silicon combine in aluminum alloys as the compound Mg2Si, which forms a binary system with aluminum. In alloys containing an excess of silicon over that required to form the compound, solidification ends with the freezing at 1022' F. (550' C.) of a ternary eutectic of aluminum, Mg²Si, and silicon. Judging from the horizontal projection of the liquidus surface as given by Hanson and Gayler,² this ternary eut,ectic contains about 13 per cent. silicon and 6 per cent. magnesium. All of the alloys discussed here contain excess silicon, so it

Jan 1, 1931