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By Harry R. Johnson

Domestic expenditures by the U.S. petroleum industry have exhibited distinctive shifts in emphasis over the past 20 years. From the end of World War II to 1955, expenditures for all phases of the industry expanded. Although over one-half of all expenditures were for production, the relative emphasis was changed after 1956-58 from production toward processing and marketing. The period 1967-69 marked the beginning of a return to emphasis on exploration and production. These trends in expenditure patterns are logical and rational when related to domestic and international economic conditions and to the widespread application of improved production technology. As the immense job of developing the oil resources of Alaska and other regions begins, the petroleum industry will continue to turn to external sources for working capital. Long-term debt will probably be the principal method of external financing through 1970, but a definite shift toward new common and preferred stocks will be made. Higher product prices may be sought by the petroleum industry, but the economics of crude-oil production, changes in the tax structure, and possible changes in the oil imports control program make the price structure of crude oil and crude-oil products unpredictable at the present time.

Jan 1, 1970

By R. G. Davies, P. Beardmore, T. L. Johnston

The flow stress of a series of Ni-Cr-A1 alloys consisting of a dispersion of y' (based on Ni3Al) in a rnatrix of nickel-base solid solution y has been measured at temperatures up to 950°C as a fwzction of the volume fraction of y'. At high temperatures the flow stress is controlled by the amount of Y' in the alloy, i.e., the higher the volume fraction of y', the greater is the flow stress. This simple relationship is not obeyed at low temperatures in so far as a peak in the flow stress-volume fraction relation occurs at about 25 pct y'. The variation in the mechanical properlies of these alloys as a function of both temperature and volume fraction of y' has been correlated with changes in distribution of both the dislocations and y'. The results are interpreted on the basis that at low temperatures the y matrix is strengthened significantly bv the presence of a hyperfine y' precipitate due to decomposition on cooling; at high temperatures the y matrix is a single phase of low strength. It is clearly recognized that the high temperature strength of most nickel-base superalloys depends upon a dispersion of the ordered fcc phase y', based on Ni3A1, in a fcc solid solution matrix y based on nickel. Although the volume fraction of y' varies widely from about 0.2 in Nimonic 80A to about 0.6 in Mar-M200, all such nickel-base alloys manifest an unusual insensi-tivity of the flow stress with respect to temperature. In Mar-M200 for example, the 0.2 pct flow stress remains essentially constant from room temperature to 750°C. The conclusion has been drawn1 that the characteristically low temperature dependence of the flow stress of y-y' nickel-base alloys is obtained when the state of dispersion of y' is such that dislocations are forced to cut through the y' particles at the onset of yielding. When the spacing between the y' particles is so large that the flow stress is controlled by dislocation bowing between particles, then the initial flow stress decreases progressively with an increase in temperature at a rate determined by changes in elastic properties. The same conclusion is inherent in the detailed, mechanistic model of the deformation process in commercial superalloys which has been developed by Copley and ear' in which the temperature independent flow stress is attributed primarily to the contribution of the antiphase boundary energy created in the y' particles during deformation. In this theory the temperature insensitivity of the flow stress is a reflection of the constant antiphase boundary energy as a function of temperature. An important microstructural parameter that is relevant to the explanations that have been suggested' to account for the temperature insensitivity of the flow stress is the volume fraction of y'. To vary the latter to any significant extent in a given commercial alloy is clearly difficult. However, it is possible in a relatively simple Ni-Al-Cr ternary system which manifests analogous microstructures in terms of the distribution of y' in y and contains specific alloys which have flow properties that depend on temperature in a manner quite similar to their more complex commercial counterparts. Hornbogen et . have studied precipitation phenomena and deformation mechanisms in such alloys but only where the y' volume fraction was small (less than 0.2) and the y' particle size varied from less than 100A up to a maximum of -1000A. In the present study, a series of alloys was prepared in which the volume percent of y' at 900°C was varied from 0 to 100 pct with the y' particle size (of the order 0.5 p) comparable to the sizes obtained in commercial superalloys. Particular attention has been given to the relationship between variations in the volume fraction and distribution of y' and the temperature dependence of the flow stress EXPERIMENTAL TECHNIQUES The Ni-Cr-Al system was selected because it is well characterized, bears a close relationship to commercial alloys, and offers the advantage of an extra degree of freedom over a binary system. In the present investigation, a series of alloys across the tie line between NisA1 and Ni3Cr (Ni3Cr is not an in-termetallic compound, the nomenclature is only used to designate the composition) were vacuum cast. The pseudobinary6 and the composition of the alloys used are shown in Fig. 1. It is important to note that the compositions of the y phase and the y' phase in the two-phase alloys was always the same. Alloy compositions were selected from the binary diagram, Fig. 1, in order that aging at 900°C would produce from 0 (100 pct y) to 100 pct y' by volume percent. (The size of the y' particles produced during the equilibrium aging treatment increased as the volume fraction of y' increased, ranging from about 0.2 p at low volume fractions up to about 0.8 p at the highest volume fraction.) The y' phase is based on the inter-metallic compound Ni,A1 which has the fcc LIZ type superlattice structure, and chromium substitutes for aluminum in the structure. The y phase is a disordered fcc solid solution. The alloys were heat treated at 1150°C for 2 hr, air cooled to room temperature, and finally annealed for 16 hr at 900°C. The rods were then centerless ground to 0.25 in. diam and cut into compression samples 0.5 in. long. The compression tests were made on an In-stron machine at a strain rate of 7 x 10"4 sec-'. A rapid heating radiant heat furnace was used which minimized the heating and temperature stabilization time to 10 min for the highest testing temperature. All the tests were stopped after 5 pct plastic strain.

Jan 1, 1970

By J. Szekely, G. P. Martins

A formulation is given for describing the rate of expansion of spherical bubbles rising in liquids the freeboard of which is evacuated. The computer solution of the resultant differential equations has shown that, for low freeboard pressures (less than about 5 mm Hg), on approaching the free surface the bubbles expand much less rapidly than predictable from equilibrium considerations. In other words, in this region the pressure inside the bubbles will be significantly larger than the static pressure in the liquid corresponding to the position of the bubble. These theoretical predictions were confirmed by experimental work, using two-dimensional air bubbles rising in mercury. The important consequence of these findings is that the expansion of gas bubbles in vacuum degassing operations will be a great deal less than expected from hydrostatic considerations. This would lead to a significant reduction in the available interfacial area and may explain the apparent poor efficiency of many vacuum degassing units. VACUUM degassing as a treatment for liquid steel has gained widespread popularity in recent years; the number of known installations exceeds several hundred at the present time.' Although much information is available on both the thermodynamics of the system and the overall performance of various industrial units, much less is known about the fundamental aspects of the process kinetics.2-4 The basic physical situation common to virtually all vacuum degassing operations is the interaction between gas bubbles (swarms of bubbles) and the surrounding molten metal, held in a container, the freeborad of which is at a low absolute pressure. Once formed (or introduced from an external source) the bubbles will ascend, due to the buoyancy forces, and, during this ascent, a significant increase in their volume will occur. This progressive increase in the bubble volume is due to two factors: a) the continuous reduction in the static pressure acting on the bubble during its rise; and b) mass transfer into the bubble from the surrounding molten steel. In a recent paper Richardson and Bradshaw developed equations5 for describing mass transfer into gas bubbles from molten metals at reduced pressures. However, in deriving these expressions it was assumed that the pressure inside the bubble was identical to the static pressure in the adjacent liquid. In other words, the volume of the bubble was considered to be in equilibrium with the pressure of the fluid adjacent to it. This assumption, thus their analysis presented, was thought to be reasonably accurate for most of the bubble's ascent; however, it was unlikely to be valid in the immediate vicinity of the free surface, held at a low pressure. It was pointed out in the discussion6 that the region close to the surface may be of considerable importance as both the driving force and the interfacial area available for mass transfer are at their highest value here. The ' 'anomalous" behavior of gas bubbles when approaching a free surface at low pressures was recently confirmed in a preliminary investigation by Szekely and Martins. ?1 Here high-speed motion photography was used to study air bubbles rising in a column of n-tetradecane with a freeboard pressure of 0.1 mm Hg. It was found that significant distortion of the bubbles occurred on approaching the free surface; furthermore, the expansion observed was much less than what one could expect from hydrostatic considerations, i.e., factor a previously discussed. It follows from the foregoing that a detailed study of these phenomena would be justified both from fundamental considerations and because of their potential relevance to technology. The purpose of the paper is to present a more realistic formulation for the expansion of a gas bubble approaching a low-pressure region, together with a comparison of the theoretical prediction with experimental measurement. An inert bubble will be considered in the first instance; it is thought that the understanding of the fluid mechanics is an essential first step toward the realistic formulation of the mass transfer process. This latter problem will be the subject of a subsequent publication. FORMULATION The Physical Model. Consider a spherical bubble, of initial radius Ro, rising in a fluid, having a density pL. Initially let the bubble be at a distance H from the free surface, and at a pressure Pgo, as illustrated in Fig. 1. Pgo, the initial pressure in the bubble, is given by the following equation: pgo = Po = Ptp +pLgH [ la] where Po is the pressure in the liquid corresponding to the initial position of the bubble and Ptp is the pressure at the free surface. The fluid pressure at

Jan 1, 1970

By S. Nenno, T. Saburi, Y. Mizutani, M. Yomarnoto, K. Komatsu

In the equilibrium phase diagram of the Ni-Mo sys-tem1,2 available at present, intermetallic compounds (or ordered phases)ß(Ni4Mo) and ?(Ni3Mo) are known to exist to the nickel rich side. In our recent investigations on Ni-Mo alloys, however, it has been found that the quenched alloys from the high temperature region containing more molybdenum than the Ni4Mo do not decompose directly into 0 and when annealed isothermally below the peritectoid temperature, i.e., 865°C. This note is to report the existence of Pt2Mo type superlattice (possibly ordered Ni2Mo) as a metastable phase in the early stage of decomposition. Alloys containing 20.1, 22.7, and 24.4 at. pct Mo were prepared by vacuum-melting electrolytic nickel of 99.9 pct purity and molybdenum powder of 99.9 pct purity in an alumina crucible. From the resulting ingots, sheets 0.3 mm thick were obtained by forging, hot-, and cold-rolling. The sheet specimens were water-quenched from ! region and subsequently annealed for various periods of time at temperatures below the peritectoid temperature. On these specimens were made optical-microscopic and transmis-sion-electron-microscopic observations. Fig. 1- Optical micrograph of the 22.7 at. pct Mo specimen annealed for 100 hr at 700°C after quenching. (ß + ?) region, B, nucleated along a grain boundaries are invading the preexisting (ß + Ni2Mo) region, A. Details of A are observable only by electron microscopy. Etchant: 60 pct HNO3-40 pct CH3COOH.

Jan 1, 1970

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970

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 R. A. Burmeister, G. P. Pighini, P. E. Greene

An open tube vapor phase epitaxial growth system has been used for large area (multiple substrate) growth of GaAs1-xPx on GaAs substrates. The GaCl-GaCl transport reaction is used with either a GaAs or Ga (nonsaturated) source. Selenium and tellurium have been used for donor impurities, and zinc as an acceptor. The useable substrate area in this system is approximately 20 sq cm. The uniformity of thick-ness of the epitaxial layers are typically better than ±5 pct across a given wafer. Electrical and optical measurerments indicute comparable uniformity in electrical and luminescent properties within a wufer. The application of this system to the large scale pro-duction of GaAs1-x Px for display devices, both discrete and arrays, is discussed. Typical electrical and luminescent properties of light emitting diodes fabricated front material produced by this technique are presented. THE most promising materials currently being utilized for visible injection electroluminescence are GaAs1-xPx, Ga1-xAlxAs, and Gap. All have reasonably efficient emissions in the red portion of the visible spectrum at room temperature; Gap also has an efficient green emission.&apos; At present, GaAs1-xPx has a technological advantage over Ga1-xAlxAs and Gap for display applications, since relatively large (several sq cm) areas of GaAs1-xPx suitable for use in electroluminescent devices may be readily grown by vapor phase growth techniques. In contrast, the preparation of Gap and Ga1-xAlxAs for electroluminescent device applications generally employs solution growth techniques which are at present not well suited for the growth of large areas of uniform thickness and doping level. The capability of uniform growth over large substrate areas and the use of multiple substrates is necessary for the practical utilization of electroluminescent devices. This is particularly important when quantity production or monolithic devices are required. Furthermore, in many display applications arrays of light emitting devices are used, the individual elements of which are of a size resolvable by the unaided eye. Thus the overall dimensions of display are substantially larger than those of most semiconductor devices. It is also necessary to achieve a high degree of control over the growth parameters to attain the required degree of reproducibility of materials properties for electroluminescent devices. In the case of GaAs1-xPx it is necessary to accurately and precisely control the phosphorus content of the alloy, both on a macroscopic and microscopic scale, in addition to the parameters generally associated with epitaxial growth such as thickness and doping level. This value is critical, as it has a major effect on the performance of electroluminescent devices. This paper describes the epitaxial growth of GaAsl-xPx suitable for electroluminescent display devices using a system developed specifically for this purpose, and which contains several novel features. The results of studies of selected physical properties of the epitaxial layers are also discussed. Finally, a brief summary is given of the characteristics of display devices fabricated from GaAsl-xPx grown in this system. EXPERIMENTAL A) Reactants. A number of techniques suitable for the vapor phase epitaxial growth of GaAs1-xPx have been reported in the literature.&apos;-&apos; The method selected for this investigation is that in which the Ga is transported by the GaC1-GaCI3 reaction in an open tube process. The results reported here were obtained using either the combination of GaAs, AsC13, and pH3, or Ga, AsH3, pH3, and HC1 as the initial re-actants.* The ASH3 and pH3 were obtained as dilute *Several different sources of supply were used for these reactants, y~elding comparable results._____________________________________________________ mixtures in HZ; the HC1 was obtained from the reduction of AsC13 by Hz at elevated temperatures. Both selenium and tellurium were employed as donor impurities, and zinc as an acceptor impurity. Selenium was introduced in the form of H2Se, tellurium in the form of tellurium-doped GaAs, and zinc in the form of diethy1 zinc. B) Apparatus. The prinicipal difference between the apparatus used in the present study and that of Tietjen and Amick,8 in addition to size and other related design features, is that RE induction heating is utilized in place of resistance heated furnaces. Induction heating was selected for this application because it appears to have several advantages, including: 1) It is possible to keep all fused silica portions of the apparatus at temperatures well below those of the reaction zone, thus minimizing a possible source of contamination. 2) The thermal mass of an induction heated system can be made small, thus reducing the total time required for the growth process. 3) Sharp temperature profiles (desirable for high deposition efficiency) are easily achieved. 4) The volume of the system for a given substrate area can generally be made smaller than a comparable resistance heated unit. This results in shorter time

Jan 1, 1970

The Bureau of Mines performed cratering experiments in a homogeneous granite to test scaling laws for charge weights of 0.00476, 0.0220, 0.0900, 0.304, and 1.03 lb. Agreement among the data was best when empirical scaling exponents greater than one-third were assumed. Although the analysis showed that the best empirical scaling exponents were 0.37 for crater volume, 0.38 for crater radius, and 0.39 scaling for crater depth, all three crater dimensions could be scaled with a 0.38 scaling exponent.

Jan 1, 1970

By C. F. Weinaug, R. W. Farley, J. F. Wolfe

A rapid, accurate method for predicting the dew points of gas condensate systems and their subsequent normal and retrograde phase behavior with pressure decline has been developed. The method predicts dewpoint pressure, volume percent liquid, condensate content of produced gas, and the liquid and gas compositions at pressures below the dewpoint pressure. Use of a modified form of the BWR equation of state, which was established by regression calculations on experimental data from several gas condensates, provides depletion behavior predictions that are significantly improved over predictions using K-values based on convergence pressures and Standing&apos;s correlation for density. INTRODUCTION Prediction of complex hydrocarbon-mixture thermodynamics is fundamental to reservoir and gas process engineering. In particular, accurate descriptions of phase behavior are needed to plan production operations for gas-condensate reservoirs. Although analysis of reservoir behavior during producing and cycling operations can be made for simple reservoir models, extensions of these studies to more complex reservoir systems are still difficult, both with regard to numerical techniques and the phase behavior of the fluids. This report presents a mathematical method for handling the complex phase relationships encountered in retrograde condensates; it represents an advance in reservoir behavior technology in that it will aid the development of closed-form mathematical representations of total production systems. A typical phase diagram for a complex hydrocarbon mixture is shown in Fig. 1. When the reservoir temperature T, is higher than the critical temperature Tc, and lower than the critical-condensation temperature Tct&apos; the mixture is a gas condensate. Decreasing the pressure on a condensate while maintaining nearly constant temperature will result in two phases forming at the dew point. Further decrease in pressure will cause additional liquids to be formed. This phenomenon is called retrograde condensation. As pressure continues to decrease, normal phase behavior regions are encountered (liquid vaporizes as the pressure decreases) until the low-pressure dew point is encountered. When a gas-condensate reservoir is produced, gas is withdrawn and the volume of fluids in the reservoir remains nearly constant as the pressure declines. Heavier components tend to accumulate in the liquid phase as a result of retrograde condensation, while lighter components tend to concentrate in the vapor phase. Thus, as the gas is produced the composition of the gas and the condensate

Jan 1, 1970

By Donald Bishko

Zoning is the legal means by which land use can be controlled. Although zoning laws have historically been quick to prevent quarrying, one is hard pressed to find zoning ordinances which specifically state that land should be used (or held in reserve) for quarrying and prevent other uses such as recreation, housing, etc. This situation is especially true when the mineral to be quarried has a low intrinsic value such as sand, gravel, and crushed stone. The chance of a gold mine surviving urban sprawl is probably considerably greater than that of a sand and gravel pit, even though it is possible that the dollar value of the sand and gravel&apos; would exceed that of the gold mine. The research reported herein was concerned with two major topics: to delineate the real costs associated with the non-protection of our construction aggregate resources (growth minerals) and to develop a computer simulation model which would aid planners in making economically sound decisions. This paper describes the problems faced by the mineral aggregate industry and discusses the role of computer simulation in planning problems. It briefly describes a simulation model which has been developed and previously reported12 and discusses the results of a pilot study conducted on the Tri-City area (Albany, Schenectady, and Troy, New York). 3

Jan 1, 1970

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

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

Jan 1, 1970

By Karl C. Dean

The current emphasis on environmental problems has focused attention on the massive nationwide accumulations of mine, mill, and smelter wastes that represent potential air and water pollution hazards. The pollution hazards can be reduced or eliminated by utilization or stabilization of these wastes. The U.S. Bureau of Mines, since the inception of the Solid Waste Disposal Act of 1965, has been conducting research to determine the practicality of various utilization and stabilization procedures. Investigations include partial extractions of desirable waste components and full utilization of the wastes as simulated soils or in ceramic or other structural products. Chemical, vegetative, and combined chemical-vegetative methods of stabilization have been actively studied. This report updates information previously developed by the Salt Lake City Metallurgy Research Center and presents the current status of antipollution solid waste work 1/,2/.

Jan 1, 1970

By S. Kobayashi, A. E. Armenákas, C. Mylonas

Earlier work1-4 has shown that commercial mild steels under static loading at the lowest natural operating temperatures fracture in a brittle manner only when damaged by a suitable history of straining. Notched and then compressed plates have fractured in subsequent tension at loads as low as 10 pct of the limit load and precompressed smooth bars at a subsequent extensional strain as low as 0.01. The comparison of the average net fracture stress with the flow limit stress was shown to be an excellent criterion of brittle or ductile behavior of mild steel structures when only loads and general stress levels are known. The present investigation shows that the deformation at fracture is a far more sensitive measure of brittleness than the fracture stress. Both criteria, deformation and stress, are used to determine the amount of uniform precompression of two mild steels, ABS-B and Project E-steel, resulting in brittle fracture under the strong constraint of a subsequently machined severe circumferential groove. The fracture stress equaled or exceeded the theoretical flow limit Ól = 2.680., (&apos;based on the elevated yield stress at each prestrain) up to prestrains of about 0.20 and then fell off to about 1 at prestrains of 0.60. Yet a prestrain of only 0.05 reduced the elongation at the shoulders by a factor of about 4. The total plastic elongation of a region surrounding a sharp notch in prestrained steel deternines whether or not fracture will be initiated in large structures, hence is a direct and realistic measure of the remaining ductility and provides an excellent test of the material&apos;s resistance to embrittlement. ALMOST all engineering structures of mild steel which failed in service in a so-called "brittle" manner exhibited appreciable local plastic deformation (more than 1 pct) and a mixture of "cleavage" and "shear" fracture surfaces. Furthermore, the peak local stress in an advancing crack is always high. Such simple criteria as pure cleavage, absence of plasticity, or fracture stress, so useful in other fields, are insufficient to characterize brittleness in engineering structures at ordnary temperatures. The "brittle)&apos; behavior of engineering structures is caused by the limited ductility at cracks or notch regions, as shown by recent work at Brown University summarized and extended in Refs. 1 to 4. It was also shown that the local ductility of mild steel may be catastrophically reduced by a suitable strain and temperature history similar to those which may occur in real structures. Localized yielding begins at the notch roots at low loads but is contained by surrounding elastic regions. The plastic strains are hence small. They increase slowly with the load up to the flow limit or limit load for an ideally plastic material. Unrestricted plastic flow then occurs. At such strains the real material locally st rain-hardens and fractures. With work-hardening materials no flow limit exists, and the transition from low to high plastic strains is gradual but increases more rapidly at loads close to the flow limit of an equivalent perfectly plastic material. When the available ductility is sufficient for reaching the limit load, the behavior is normal or "ductile". With insufficient ductility, fracture will occur at a low load and will be defined as "brittle". Accordingly the sufficiency or not of the ductility at a notch is reflected in the magnitude of the fracture load or average net stress as compared with the limit load or flow limit. The application of this criterion gave surprising results. Service failures under semistatic loading occurred mostly below the limit load, hence were "brittle". On the contrary all static tests with undamaged commercial mild steels reached the limit load in spite of the deepest notches and temperatures below Charpy impact transition (say about -30°F or higher). Notched bars showed no brittleness even under fully dynamic axial loading up to 1.5 x107 psi per sec at -23°F and about 2.5 x l06 psi per sec at -ll0°F, but broke in a brittle manner at -200°F and l03 psi per sec.&apos; To propagate a fracture at low load, experimenters had to trigger it by superimposing a strong dynamic impact at a notch cooled by liquid nitrogen as in the Robertson5 or Esso tests.&apos; Once started the cracks would run through warmer regions of smaller stress. Obviously the ductility of the apparently undamaged commercial steels was "sufficient" in the laboratory tests but not in the service fracture, where it must have been reduced by some embrittling procedure of fabrication or service. These conclusions were confirmed by the achievement of low static stress (brittle) fracture initiation in unwelded steel after a local reduction of ductility by simple prestraining. Symmetrically notched plates of undamaged mild steel cooled below the Charpy V-notch transition range were tested in central static tension: Undamaged plates withstood loads of limit intensity, but when subjected to prior in-plane com-pressive prestraining perpendicular to the notch axis and to accelerated aging, the plates fractured completely or partially at very low static loads, as low as one-tenth of the flow limit.2-4 However, damage could not be easily related to the strongly variable prestrain around a sharp notch. To obtain easier strain measurements, it was decided to use axially precom-pressed bars and bent bars. Final testing was done by

Jan 1, 1970

By Alexander May

This report describes a new method of weighing based upon observing the apparent weight of an object ill two separate pure gases. The method is presented in terms of experimental data which prove its soundness, but does not attempt to show the maximum accuracy possible with this technique. The new method incorporates the underlying principle that the apparent weight of an object is a linear function of the density of the atmosphere in which the object is weighed. The coefficients of this linear function are the true mass and volume of the object. From this functional relationship the true mass and volume of the object may be determined.

Jan 1, 1970

By Frank Littlewood

Research over a period of ten years resulted in the development of an efficient automatic ore feed regulator for mill grinding circuits. The facilities that a large mining company gave the inventor made it possible to develop the control apparatus under actual mill operating conditions. The Littlewood Regulator automatically determines the optimum power input at which a mill should operate, and controls the rate of ore feed to maintain this optimum power for any predetermined operating conditions. It is to be noted that the optimum power varies with many factors such as ball, rod, and mill liner wear, therefore the regulator is designed to automaticall keep itself properly calibrated. To efficiently control the rate of ore feed of a mill grinding circuit the regulator analyzes and interprets all power changes of the mill motor. The critical electrical measurements for this type of control are made possible by a patented device that has the ability to detect and integrate minute changes in power. In ball mill operation the small but significant changes in power serve to select the rate of ore feed in accordance with the rate at which ore accumulation takes place within the mill, and in rod mill operation they serve to select the rate of ore feed in accordance with the degree of rod spread.

Jan 1, 1970

By W. A. Zingg

Impervious zones in copper waste heaps create a problem in contacting the rock with leaching solutions. These zones are normally associated with compacted layers .formed on the surface of each lift by dump truck traffic and by disintegration of the rock exposed to atmospheric conditions. These layers are usually only a few feet in depth--but, nevertheless, act as barriers to vertical flow causing the leach solution to perch in the heap, Consequently, much of the rock remains untouched and the leach solution breaks out the side of the heap instead of continuing downward to bedrock. One solution to this problem is breaking the hard pans with explosive charges. However, to use explosives means adopting new explosive materials and methods. To use this process successfully requires finding answers to operating conditions inherent to waste heaps. Foremost among these are: (1) type and size of casing that can be used because of limitations brought about by drilling problems, caving and, corrosive conditions; (2) perforating the casing at required levels; (3) an explosive capable of being pumped; (4) obtaining detonation of the, main charges through, the wail of the casing; (5) an explosive with the ability to propagate through the voids of the rubble and one which is not affected by water, acidic solutions, or back pressure conditions from hydrostatic heads; (6) to heave and rupture the compacted zones without chambering or recompressing the waste material.

Jan 1, 1970

By Michael Tenenbaum

Selected characteristics of nonmetallic phases were determined in low-carbon sheet steels which had been produced by various refining; deoxidizing, and casting procedures. The results showed little influence of the refining process on the quantity, distribution, size, and character of the nonmetallic phases. The quantity of inclusions was governed by the deoxidation procedures. While the mode of casting influenced the internal structure and the pattern of inclusion distribution, it had little effect on the quantity of nonmetallics. The vast majority of inclusions were under 30 µ in diam, and there was little change in size distribution during hot and cold rolling. The composition and structure of the inclusions were expained an the basis of known equilibrium phase diagrams for the appropriate systems. Additional work is needed to explain some of the observations of this paper. HENRY Marion Howe&apos;s contributions to the metallurgical profession include his many writings, the wisdom that he imparted to his students, and the inspiration that he gave to the many scholars, teachers, and industrialists who knew him personally. It was Professor Howe&apos;s intimate colleague, Albert Sauveur,1 who, in the first Howe Memorial Lecture, could have been speaking for the metallurgist of our generation as well as his own when he wrote, "...how many of us on the point of going astray were called back to the right path by Howe&apos;s guiding torch?" More than a quarter of a century later, Francis Foley,2 one of the last in the Howe Lecture series who worked directly with the great man, delivered the ultimate tribute, "...truth, in its time is so hard to identify." While Professor Howe strove to be right, "he was content if he provoked the reader to take the next step along the path to greater knowledge." Like so many of my predecessors, I sought guidance for this lecture by referring to Professor Howe&apos;s two classic texts, Metallurgy of steel,3 and Metallography of Steel and Cast Iron: the former book interpreting the facts as he saw them near the start of his career, and the latter—published 26 years later—pointing to many fertile fields for metallurgical investigation. Those of us who harvest the fruits of Henry Marion Howe&apos;s contributions to the metallurgical profession now look with wonder at the tremendous legacy he has provided. It is rewarding to study his writings and to recognize the anticipation of such aspects of modern ferrous metallurgy as: 1) Direct reduction 2) Steelmaking reactions 3) The approaches and benefits of degassing 4) Solidification mechanisms 5) Habits and behavior of nonmetallic inclusions 6) Recrystallization phenomena 7) Slip and slip propagation 8) Dislocations 9) Discontinuous deformation 10) Microscopic and macroscopic segregation

Jan 1, 1970

By C. W. Volek, G. Mandl

Steam-injection tests in the field have shoum that heat transport into the oil/water region, ahead of the steam zone, may have a significant effect on the production process. Earlier theoretical work on reservoir heating by hot-fluid injection can be used to describe the growth of the steam zone, but only if heat transport from steam zone into oil/water region is neglected. It therefore became necessary to re-examine and extend the earlier theory. It was found that this theory ceases to be consistent with the physical model of the process at a certain critical time, tc, which depends on reservoir thickness, temperature, and quality of the steam. The critical time marks an important change in the heat flow across the condensation frovt: the heat flow, which is purely conductive during 0 < t < tc&apos; becomes predominantly convective at t = tc. Accordingly, at t = tc, the equation which governs expansion of the steam zone changes. On the basis of the new equation, an approximate description for the steam-zone growth during t > tc is developed by making use of upper and lower bounds for the exact solution of the problem. The boundary conditions for heat and mass flow inside the oil/water region are established, and a simple method of detennining the saturation at the downstream side of the condensation front is presented. Experimental results show that the theory gives an accurate description of steam-zone expansion before the critical time. At times near critical time, and also after critical time, experimental data show theoretical steam-zone volumes to be high. Even so, the accuracy of the calculated steam-zone volumes is sufficient for practical purposes. THEORY OF STEAM-ZONE GROWTH INTRODUCTION The engineering evaluation of steam-drive processes is based mainly on a mathematical description of reservoir heating by hot fluid injection presented several years ago by Marx and Langenheim.l This theory can be used to determine the growth of the steam zone,2 provided the flow of heat from the steam zone into the liquid zone ahead of the condensation front (Fig. 1) is neglected. Since we must expect, however, that heat transport into and inside the liquid region (the region between condensation front and production wells) will affect both the water/oil flow and the growth of the steam zone, it is necessary to re-examine and to generalize the Marx and Langenheim theory as applied to steam drive, which will hereafter be termed the "old" theory. Observations made in several field tests emphasize the need to study the heat flow across the condensation front (CF). On several occasions it was discovered that heat was transported in the liquid zone far ahead of the advancing CF, resulting in an early breakthrough of warm water. This seems to occur most often when high injection pressures are applied, when "wet" kONINKLIJKE/SHELL EXPLORATIE EN PRODUKTIE LABORATORIUM RIJSWIJK, THE NETHERLANDS SHELL DEVELOPMENT CO. HOUSTON, TEX.

Jan 1, 1970

By C. R. Barrett, N. N. Singh Deo

The high-temperature steady-state creep behavior of a series of dilute copper-silicon alloys was studied to determine the effect of stacking fault energy on the creep-rate. The steady-state creep rate is, when taken at equivalent diffusivities decreases with decreasing stacking fault energy. The stress and temperature dependencies of is suggest that creep is a difusion controlled dislocation climb process. Electron microscopy studies of the creep substructure revealed: 1) the subgrain size is not a function of the stacking fault energy in these alloys, 2) the dislocation density not attributed to the subgrain walls seems to be higher during primary creep and decreases to a lower steady value during steady-state creep, and 3) the dislocation density during steady-state creep decreases with decreasing stacking fault energy. In the past few years numerous investigators have studied the influence of stacking fault energy on high-temperature creep strength. Most of these investigators have confined their attentions to studying the relationship between steady-state creep rate, is, and stacking fault energy, ?, when samples are tested under conditions of comparable stress and temperature. For the case of fcc metals, it was initially shown by Barrett and Sherbyl and since confirmed by many others2"4 that is decreases with decreasing ?, often following an empirical relation of the form i ?m where m is a constant about equal to 3. The application of theory to explain this observation has not been entirely successful. One of the main difficulties has been the almost complete lack of structural information (dislocation density, subgrain size, and so forth) for samples with different stacking fault energies, tested under high-temperature creep conditions. weertman5 has attempted to explain the stacking fault energy dependence of is on the basis of a dislocation climb mechanism. Assuming that both the rate of dislocation core diffusion and the ease of athermal jog formation decreases as ? decreases Weertman has argued that the rate of dislocation climb and hence the creep rate should also decrease as ? decreases. One questionable aspect of Weertman&apos;s analysis is the assumption that core diffusion down extended dislocations is slower than core diffusion down unextended dislocations. The only experimental work done in this area, by Birnbaum et al.6 on nickel and Ni-60 Co, has shown the core diffusivity to increase with decreasing ?. Theories of steady-state creep based on the diffusive motion of jogged screw dislocations often seem unable to predict even the qualitative nature of the es- relationship. Assuming that Weertman is correct in his assumption that the dislocation jog density decreases with decreasing ? then the jogged screw theories predict an increasing dislocation velocity with lower ?. It is usually assumed that the increase in dislocation velocity implies a corresponding increase in creep rate. However, two other factors must be considered before such a statement can be made. That is, we must know how both the mobile dislocation density and the effective stress (the difference between applied stress and internal stress) vary with ?. Significant changes in either one of these factors could outweigh any change in dislocation velocity accompanying a change in ?. And with the slower rates of recovery expected in low stacking fault energy materials it seems likely to expect both mobile dislocation density and effective stress to be dependent on ?. Sherby and Burke7 have suggested that stacking fault energy influences the creep rate in an indirect way. These authors cite evidence that the steady-state subgrain size generated during high-temperature creep is a function of ? decreasing with decreasing ?. Assuming the creep rate to be proportional to the area swept out by each expanding dislocation loop and that subgrain boundaries are good barriers to dislocations, then the creep rate should be proportional to subgrain area, hence increasing as ? increases. A critical evaluation of any of the above theories requires more quantitative information concerning the dislocation substructure generated during high-temperature creep. Accordingly this investigation was undertaken with an aim of studying the influence of stacking fault energy on tbe steady-state creep characteristics of a series of dilute copper-silicon alloys. Special emphasis was placed on studying the strain dependence of both the dislocation configuration and density. MATERIALS AND PROCEDURE Dilute copper-silicon alloys of the compositions shown in Table I were tested in tension at constant stress. The relative stacking fault energy of these alloys has been determined and is shown in Table 11. An Andrade-Chalmers lever arm was used to maintain constant stress and testing was carried out in a water

Jan 1, 1970

By Y. Oka, H. Majima

When a rock particle is subjected to an external force, internal stresses and deformations are experienced by the particle. Assuming that the breakage of a rock is mainly due to tensile stresses generated by the action of a pair of concentrated loads, F, directed in compression towards the loading points at the shortest distance, as illustrated in Fig. 1, the stress and deformation experienced by a particle of irregular shape can be determined with the aid of the theory of elasticity. According to the photoelastic experiments made by one of the present authors,&apos; the stress states in a rock particle of irregular shape are quite similar to that of an inscribed sphere of diameter x, as indicated in Fig. 1, but accompanied by the faint stresses, in the vicinity of the particle outside of the inscribed sphere. Therefore, the stress components in an irregularly shaped particle can be estimated by referring to stress components in a sphere. Applying polar spherical coordinates to an elastic spherical body, as shown in Fig. 1, the stress components are all expressed as multiples of F /x2 and more or less influenced by the loading angle and Poisson&apos;s number m. In general, the energy w, acting on a rock particle is defined as the product of loading compression F

Jan 1, 1970