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By K. C. Hong, R. B. Jensen

The problem of determining the optimum set of steam volumes and cycle lengths for a single well undergoing multicycle steam stimulation in order to maximize the cumulative discounted net income has been formulated mathematically and programmed for a digital computer. The mathematical fonnulation of the problem and the method for its solution are discussed in this paper. The oil production performance during each stimulation cycle was simulated by either a constant percentage or a harmonic decline. Using simple analytical expressions for production performance, the cumulative discounted net income and cumulative time of operation were related to the pertinent process and cost parameters and two principal process control variables (cycle length and steam injection volume). The discrete maximum principles was used to transform the equations for cumulative time of operation and cumulative discounted net income into a set of simultaneous equations. The simultaneous equations then were solved by trial and error on a digital computer to determine the set of cycle lengths and stem injection volumes that gives maximum cumulative discounted net income over the project life. INTRODUCTION Steam stimulation is a process for improving the oil recovery rate from wells producing high-viscosity crudes. The process is applied on an individual well basis and is executed in a series of cycles, each consisting of three phases: steam injection, soaking (steam condensation), and production. Significant increases in production rate following the stimulation operation result from heating the reservoir around the wellbore. As heat is removed with produced fluids and dissipated into nonproductive formations, the production rate declines, usually to near the prestimulation value. Typical production responses are given in case histories reported by Owens and Suter,l and are depicted in Fig. 1. Duration of the production phase is equal to the time for the oil production rate to decline to some specified value and is called the cycle length. (Cycle length is defined as the producing portion of the cycle and does not include the downtime required for steam injection and soaking operations.) Termination of the production phase coincides with the start of steaming for the next cycle. The process is continued, cycle by cycle, until it becomes unprofitable. Models 2-4 have been developed to simulate behavior of a single well during one cycle of steam stimulation and have been used to investigate the effects of system and operating conditions on the production responses. However, these investigations have not shown how the models can be used to determine a most profitable set of operating conditions for a multicycle stimulation project. Perhaps these models are too complicated mathematically to be adapted readily to an optimization study. This paper presents a method for optimizing a multicycle steam stimulation project based on simple production performance models. First, the performance of a steam-stimulated well during each cycle was simulated by either a constant percentage or a harmonic decline model. Using these simple analytical expressions for production performance, the cumulative discounted net income (before tax) and cumulative time of operation for each cycle were related to the pertinent process and cost parameters and two process control variables—the cycle length and the steam injection volume. Finally, the profit function to be maximized was formed. The analogy between the above problem and problems of optimizing multistage decision processes that have been reported extensively in the chemical engineering literatures5-10 in recent years has led this investigation to the use of the discrete maximum principle.5-7 This principle was used to transform the equations for cumulative discounted net income and cumulative time of operation into a set of simultaneous equations characterizing the optimum operating conditions in terms of the two control variables. These equations

Jan 1, 1970

By J. H. Schulman, M. H. Buckenham

Although much interest has been taken in the use of mixed collectors in flotation, this investigation is probably the first in which oppositely charged collectors have been considered. The results obtained and the techniques used could well be applied in the behavior of other mixe the behavior of other mixed collector systems and could possibly explain the effective flotation results which have been reported when various collector combinations have been used. Collectors conventionally employed in flotation systems are soluble in water, but many of their homologs of longer hydrocarbon chain length are insoluble. The properties and behavior of these insoluble compounds may be conveniently studied when they are spread as monolayers at the air/water interface on the Langmuir-Adam trough. Although some extrapolation is involved in applying effects observed at this interface to the solid/liquid interface where the action of collectors is most important in flotation, the technique nevertheless is most useful for the study and interpretation of flotation phenomena. Of particular interest in this field are investigations on the insoluble monolayers of the fatty acids, alkyl sulfates and alkyl amines; the penetration of these insoluble monolayers by soluble surface active components and their interaction with metal ions from the underlying solution.'-' Unfortunately, the insoluble xanthates and related compounds do not exhibit stable monolayer properties due to rapid oxidation at the air/water interface and, therefore, cannot be studied directly in this way. These approaches have enabled Leja and Schulman8 to suggest mechanisms explaining dynamic attachment of mineral particles to air bubbles involving collector-frother interaction and the adsorption of collectors onto mineral surfaces. In this and other papers 9-12 considerable evidence is presented to support the concept of collector-frother and metal ion-monolayer interaction and to emphasize the value of monolayer techniques in elucidating the flotation system. Molecular interactions resulting from monolayer penetration are determined by the nature of and the association between both the polar and nonpolar groups of the two molecules concerned. Stable complexes are formed on penetration when interaction takes place between both the polar and nonpolar groups, and although the resultant complexes are not necessarily true chemical compounds, the properties of the molecularly associated complexes are very different from those of the individual components. Shortening of, or changes from, a straight hydrocarbon chain in one of the reacting molecules reduces considerably the stability of the associated complex as do changes in temperature, pH and substrate composition. The effect of hydrocarbon chain length becomes most important when observed effects are to be applied in flotation studies where soluble homo-logs and, therefore, much shorter hydrocarbon chain lengths are used. The present investigation is based on Langmuir trough work carried out by Bowcott,l3 who studied the penetration of insoluble amine monolayers by potassium lauryl xanthate. Bowcott observed that cetyl amine monolayers were readily penetrated by xanthate, but found that with time the high film pressures resulting from penetration and association fell off, indicating decomposition and ejection of xanthate from the film. This decomposition was pH dependent. Of particular interest in this work were studies on an equimolecular mixed monolayer of the fully N-substituted ammonium compound, for example, cetyl trimethyl ammonium iodide (CTAI) and potassium cetyl xanthate. Despite the fact that the CTAI is water soluble and the xanthate on its own is incapable of forming a monolayer, the mixed film was stable up to a surface pressure of 67 dynes per cm. In this condensed state the xanthate was stabilized against atmospheric oxidation, although iodine injected beneath the film caused an immediate collapse. The stabilizing of xanthate against oxidation by association with an alkyl trimethyl ammonium bromide (TAB) could be important in flotation, and a study of the performance and behavior of mixed collectors therefore was undertaken. A modified Hallimond tube operated under controlled conditions was used to evaluate flotation. Surface tension measurements were made to investigate the properties of the soluble

Jan 1, 1963

By A. N. Crownover, H. T. Kennedy, E. P. Miesch, C. H. Bowman

The paper presents correlations of (l) molar volume of gaseous hydrocarbon mixtures with pressure, temperature, composition and properties of the C,-plus fraction; (2) shrinkage of oils during flash and differential liberation of gas, including the calculation of formation volume factor under various conditions; and (3) bubble-point pressure with temperature, composition and characteristics of C, plus. The data on which the correlations are based comprise 1,615 measurements on 900 hydrocarbon systems, including numerous systems containing nitrogen, hydrogen sul-fide and carbon dioxide. In each correlation, the number of data points covered and the accuracy is substantially greater than in previously available work. Thus, the equation yielding molar volumes of gases has an average deviation of 2.04 per cent, applied to mixtures having temperatures up to 313F and pressures up to 9,800 psis, compared to 2.37 per cent for the Benedict-Webb-Rubin equation applied to the same data, and 4.53 per cent for the method based on the law of corresponding states. he equations resented are all explicit in the dependent variable, and require no iteration on the digital cow puter. INTRODUCTION The ease and accuracy of determining the composition of hydrocarbon mixtures, compared to the difficulty of measuring their properties under reservoir conditions, makes it desirable to utilize composition as the key to physical behavior to the greatest possible extent. As a result, there are available correlations between composition, or easily measured characteristics dependent on composition, and practically every important engineering property of reservoir fluids. The task confronting us is one of finding more exact relationships between important variables rather than extending correlations to new properties. This paper describes new correlations of molar volumes of gases, formation volume factors, and bubble-point pressures with composition, temperature and where possible, pressure. Each correlation is obtained by employing a sufficiently large amount of data so the calculated properties are probably as least as accurate as the measurement on which they are based. MOLAR VOLUME OF GASES Although many equations of state have been proposed for pure gases, only a few methods are applicable to hydrocarbons at conditions comparable to those in petroleum reservoirs. Still fewer arc useful in describing the behavior of mixtures, with which the petroleum engineer is largely concerned. The correlation presented here involves procedures similar to those of Alani and Kennedy The van der Waals equation is modified to make a and b functions of temperature instead of being constants for each material.This is a cubic equation, which may have either one or three real roots. The lowest root corresponds to liquid volume, while the highest applies to gas. When the procedure was applied to 703 pressure-temperature points of 164 gases of known composition and volume, the average deviation was 12.08 per cent, and the standard deviation 8.15. The above calculations were made using the constants derived for liquids by Alani and Kennedy and the mixture equation developed by them. A closer approximation to measured molar volumes is obtained by employing different sets of constants for different areas on the pressure-temperature chart, and by changing the relationship between a,,, and b,,, for mixtures and the a, and b, for individual hydrocarbons. The various sets are shown in Table 1, and the areas for which they are recommended are plotted in Figs. 1 through 7. In these figures, the area designated by zero is in the critical region for pure materials, and the values obtained for them may be unreliable. For normal mixtures, however, the area may be added to any of the bounding areas without substantial error. The new relationships employed are

Jan 1, 1966

By R. J. Sherman, M. R. Achter

Creep rates have been measured for nickel at 1200°F in air and in vacuum, and related to the depth of surface cracks in the specimens tested in the two environments. The surface cracks were observed to grow faster in air than in vacuum in both short-time and long-time tests. Crack depths, however, could be correlated with creep rates only in the short-time tests. Although no cracks were observed in a relatively brittle Ni-Cr-A1 alloy creep tested at 1300°F, the appearance of alloy specimens fractured after interruption in creep indicated that there was a decrease of intergranular cohesion resulting from the diffusion of atmospheric gases into grain boundaries. PREVIOUS investigations1-3 have demonstrated that the effect of atmosphere on the high-temperature strength of nickel and nickel-base alloys may be reversed by changes in the stress or temperature of the test. At high stress and low temperature the creep-rupture life is longer in vacuum than in air, while at high temperature and low stress the relative strengths are reversed. A mechanism to explain this behavior was proposed based on two competing processes. Oxidation hardens and strengthens a metal, but adsorption of gas, by lowering surface energy, reduces the work required to propagate an intergranular crack. The controlling process is determined by temperature and stress. Basic to this mechanism is the concept that environment determines the ease of propagation of intergranular cracks and thus affects creep rate and rupture life. To explore the mechanism in greater detail, this investigation was undertaken to determine the effect of atmosphere on crack initiation and propagation rates in nickel1 and a relatively brittle Ni-Cr-A1 alloy.3 EXPERIMENTAL PROCEDURE The materials were the same as used previously. Nickel of 99.8 pct purity had the following impurity content: 0.02 pct Co, 0.03 pct Fe, 0.02 pct Mg, 0.03 pct Si, and 0.008 pct C. Rods were cold swaged from 1/2 in. to 3/8 in. in diam and machined into speci- mens with gage sections 1/4 in. in diam by 1-1/4 in. long. They were annealed in vacuum at 1600" F for 1 hr to achieve a grain size of 0.07 mm. The alloy was composed of 19.1 pct Cr, 3.6 pct Al, 1.7 pct Si, 0.57 pct Fe, 0.10 pct Mg, 0.027 pct C, 0.004 pct S, and the balance Ni. Sheet specimens of 0.500-in. width and 1.25-in. gage length were machined from 0.033-in.-thick strip and annealed in vacuum at 2000° F for 2 hr, resulting in a grain size of 0.036 mm. Large amounts of an intergranular phase were introduced as a result of the anneal. Creep tests on both materials, using equipment previously described by Shahinian; were conducted in air and in a vacuum of 1 x 10-5 mm Hg. They were continued to rupture and interrupted at various stages of the test. Although extensions were measured from dial gage readings of movement of the lever arm, it is considered that valid comparisons of creep rate may be made in this manner.l Two parameters were measured metallograph-ically* on longitudinal sections of nickel specimens interrupted during creep—the mean depth of surface cracks 2, and the density n as the number of cracks per unit length of surface. They were combined into one parameter by the relation p = n-d [1] As used here, p is equal to the total of crack depths per unit length of surface. RESULTS Nickel. It is well known that the incidence of intergranular cracking is increased with increasing rupture life. Indeed, it is evident in Tables I and I1

Jan 1, 1962

By P. K. Weimer

Coinpletely integrated thin-film circuits inco?,porating more than 1000 active and passive elements have been fabricated reproducibly in the laboratory by evaporation of- all components. A 180-stage modified shift register comprising 540 CdSe TFT's, 360 resistovs, and 180 capacitors was deposited upon a glass substrate during one pump-down of the vacuum systeitl. Experimental units have been operated for more than 5000 hr at temperatures uP to 85°C without failure of any slages. The present pupper reviews the charvactevistics of evaporated thin-film transistors (TFT's) and discusses their application to integrnted circuils. INTEGRATED circuits most widely used today are based upon silicon technology, with the circuits formed on the surface of a block of single-crystal silicon1 or on a block of sapphire 2,3 upon which a thin layer of silicon has been deposited. Transistor patterns and interconnections are defined by photographic procedures using photoresist masking. Large groups of transistors are produced in batches which undergo many processing steps, some of which are carried out at elevated temperatures. Passive elements are formed by treatment of the semiconductor surface or are deposited by evaporation alongside the active elements. The size and complexity of the circuits are limited by defects in the devices and by the size of the available single-crystal chips. Capacitative coupling to the semiconducting substrate may also limit useful size and frequency response of the circuits. An alternative approach to integrated circuits is based upon the deposition by evaporation of all circuit components upon a noncrystalline, insulating substrate such as glass.4 Thin-film field-effect transistors,1'6 known as TFT's, can be deposited in large arrays on glass or plastic substrates at the same time the associated passive elements are being deposited. Although still in the research stage the all-evaporated approach is expected to offer certain advantages for many applications. In particular, the use of thin films upon a noncrystalline substrate offers the prospect of producing complex, large-area circuits not now feasible with single-crystal silicon. Important applications of this type include memory arrays for computers and imaging devices for television. The ease with which the evaporated TFT's can be deposited may permit continuous, automated production methods not possible with high-temperature batch processing. Recent advances7'8 in the fabrication of thin-film transistors have led to greatly improved reproduci-bility and life of the TFT's. Experimental circuits having over 1000 active and passive elements deposited upon a common glass substrate are currently being produced in the laboratory. The present paper reviews recent progress in the development of the TFT and in its application to integrated circuits. I) DESCRIPTION OF THE THIN-FILM FIELD-EFFECT TRANSISTOR The TFT is a field-effect transistor of the type having the control gate separated from the semiconductor by a thin insulating spacer. Although its operation resembles that of the silicon MOS transistorg its construction is based entirely on thin-film techniques. Fig. 1 shows a cross-sectional view of an evaporated TFT deposited upon a glass substrate compared with a silicon MOS transistor deposited upon single-crystal sapphire.3 The semiconductor in the TFT is a poly crystal line layer, of a material which can be readily evaporated, such as cadmium sulfide, cadmium selenide,l0 or tellurium." Silicon monoxide layers have usually served as the gate insulator, but other oxides, sulfides, and fluorides may be used. Film thicknesses range from a few hundred to a few thousand angstroms. The source, drain, and gate electrodes in the TFT are of metal. Qpical source-drain gap dimensions are 0.0003 x 0.030 in., with a gate strip whose width slightly overlaps the source and drain. The source and drain electrodes should make low impedance contacts to the semiconductor. With cadmium sulfide films, gold is a satisfactory material for underlying electrodes, while aluminum is preferable for overlying electrodes.12 Considerable variation in design of the TFT is permissible, with the electrodes being

Jan 1, 1967

By C. Chu

A theoretical investigation has been made of the forward combustion process using a one-dimensional linear mathematical model, taking into consideration the effect of the vaporization-condensation which occurs on the leading edge of the heat wave. This work involves the solution of five coupled partial differential equations. Besides the vaporization-condensation phenomenon, these equations account for conduction, convection, combustion, heat loss, diffusion and bulk fluid flow. For the one-dimensional linear model studied, the vaporization-condensation phenomenon does not induce appreciable change in the temperature at the combustion front; and its primary effect is to create a steam plateau and to increase the length of the heated zone ahead of the combustion front. This effect becomes more pronounced at lower pressures, higher porosities or reduced gas saturations. The peak temperature and the temperature profile on the leading edge of the heat wave stabilize after a certain period. The length of the steam bank remains practically constant, although the length of the water bank increases as the heat wave advances. INTRODUCTION The existence of the vaporization-condensation phenomenon in the heat-wave process and the important role played by the phenomenon have been recognized by several investigators. Kuhn and Kochl stated that steam plateaus were frequently observed on the temperature records of their experiments. The steam plateaus were attributed primarily to the vaporization and subsequent condensation of the interstitial water existing in the oil sand. Szasz2 suggested that both lighter hydrocarbons and water are vaporized on the leading edge of the heat wave, carried forward in the gas stream, and then condensed to create banks of oil and water. Martin et al suggested that the vaporization-condensation phenomenon is one of the main mechanisms of the heat-wave process, along with thermal expansion and viscosity reduction. Wilson et al. reported the existence of a steam plateau several inches in length in their small-scale tube-run experiments. However, this important phenomenon has never been taken into consideration in the numerous theoretical analyses by various authors. 5 The purpose of this work was to study the thermal aspects of a linear heat wave, taking into consideration the vaporization-condensation on the leading edge of the wave, to determine the effect of this phenomenon on the temperature profile of the reservoir, and to investigate how this effect varies when other process variables are changed. THEORY We consider a reservoir of porous medium of cross-sectional area A, extending from x = 0 to x = L. This reservoir contains, aside from the solid matrix itself, a gas phase and a "combined liquid phase" which is a combination of two immiscible liquid phases — namely, an oil phase and a water phase. The oil present in the reservoir is assumed to consist of three fractions, a noncondensable gas, a nondistillable residuum, and a vaporizable oil fraction which may be present in both the gas phase and liquid phase. Before the heat-wave process begins, preheating has taken place and has imparted an initial temperature distribution T,(x) to the reservoir. At the start of the process, a stream of oxygen-bearing gas is introduced through the face at x = 0. This gas supports the combustion of the residual fuel and supplies the heat throughout the process. In order to develop a tractable system of equations, the model properties are postulated as follows: (1) the system is isotropic and homogeneous; (2) there is a uniform fuel content throughout the reservoir; (3) combustion takes place in a moving vertical planar region of infinitesimal thickness; (4) the temperatures of the fluids and the solid matrix are identical; (5) radiation is negligible; (6) the gas and liquid saturations are uniform throughout the reservoir and remain unchanged

Jan 1, 1965

By P. A. Beck, Hsun Hu

It has been known for many years that in cold drawn polycrystalline aluminum the recrystallization texture is practically identical with the deformation texture.l,2,3 V. Goeler and Sachs4 stated that in cold rolled polycrystalline aluminum, too, the deformation texture is retained upon recrystallization. This behavior was interpreted by Dehlinger9 as an indication that each recrystallized grain inherits the orientation of the matrix in which it grew. However, Burgers and Basart showed6 that in deformed aluminum single crystals the orientation of the recrystallized grains strongly deviates from that of the matrix. Barrett demonstrated8 that even in deformed polycrystalline aggregates the local orientation within each deformed grain changes on recrystallization. No explanation has as yet been offered of how the aggregate texture can be retained, while the local texture is everywhere changing. According to Burgers and Louwerse6 the orientation change on recrystallization in compressed and rolled aluminum single crystals corresponds to a rotation around [112] axes lying in the active slip planes and perpendicular to active slip directions. This orientation change was rationalized by them on the assumption that the orientation of the recrystallized grains is determined by the orientation of the available nuclei, and that these nuclei are small fragments of the deformed crystal, rotated in the deformation process. Barrett pointed out,? however, that these assumptions were by no means proven, and that the total volume of material necessary for the nuclei is so small, that it must be available in any orien- tation whatever. It is, therefore, unlikely that an "oriented nucleation" theory could satisfactorily explain the orientation changes in recrystallization of a deformed crystal. Furthermore, in contradiction to Burgers and LOU-werse's conclusions, Barrett's results for the orientation change could be best expressed in terms of rotations around. [Ill] axes. Thus agreement is lacking not only in the interpretations but apparently even in the experimental results contributed by the various investigators. The orientation relationships on coarsening* in a highly oriented polycrystalline matrix were first investigated by Burgers and Basart.5 They produced a fine grained highly oriented matrix by the recrystallization of a compressed or rolled single crystal of aluminum, and studied the orientation relationships in three successive generations of crystals: the "deformation texture" in the single crystal, the recrystallization texture, and the coarsening texture. Burgers24 showed that the preferred orientation of each successive generation was almost always widely different from that of the preceding one, but that the coarse grains often approximately reverted to the orientation of their grandparent, the deformed single crystal. This observation, and the idea that the orientation of the coarse grains is determined by that of the available "nuclei," led to the concept that the coarse grains are nucleated by the remnants of the deformation texture.12,15 On the other hand, Bowles and Boas16 found, in a carefully conducted experiment, that in recrystallized fine grained copper of cube texture coarse grains grow in orientations which can be derived from the orientation of the recrystallized matrix by rotation around a [lll].] direction: the coarsening texture here does not appear to be related in any simple manner to the original rolling texture from which the cube texture had been obtained by recrystallization. It may be assumed that in a recrystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as "nuclei" for the coarse grains, provided that the conditions are favorable for their growth. The existence of a coarsening texture may be considered as an indication that grains with certain relative orientations with respect to the preferred orientation of their neighbors can grow much faster than others. This "oriented growth" theory was briefly suggested by van Arkel, as early as 1936,13 and it was mentioned by Burgers." Recently, C. G. Dunn produced direct

Jan 1, 1950

By J. Fageant, W. C. Ellis

All major regions in a progressively solidified germanium ingot were related through successive orders of octahedral twinning. The occurrence of lineage structure and the generation and survival of orientations are discussed. WHEN metals solidify in a temperature gradient a preferred orientation, or casting texture, usually develops. For example, in face-centered and body-centered cubic metals, most of the solidifying crystals have a cube axis, <loo>, aligned approximately in the freezing direction.&apos; In the solidification of diamond cubic metals this is not the case, since there is a natural tendency to form twin orientations.&apos; . In this paper, twinning relationships in cast germanium are described; some conclusions with respect to nucleation and survival of new orientations are discussed. In the first experiment, an ingot of high purity germanium, % in. in diameter and 1 % in. in length, was formed by progressive solidification4 from the bottom. The ingot was cut into 21 slices, each circular and about 0.030 in. thick. The top surface of each slice was polished and etched to reveal the regions of different orientations. Orientations were determined by the Laue X-ray back-reflection method. The uncertainty in the determined orientation relationships was l" or 2" when separate slices and films were involved. Frequently, however, advantage was taken of illuminating across a boundary when the patterns of the two orientations were recorded on the same film. The uncertainty then was less than 1". Often the twin relation was evident from common zones or individual reflections. Twin relationships were recognized through comparison of the values of the nine angles between cube poles of the two orientations with those calculated for successive orders of octahedral twinning. The birth and survival of each region can be reconstructed by visual examination of the etched slices shown in Fig. 1. In slice 21, where solidification began, many regions are present; these regions were found to be twin-related. Solidification appears to have started from one nucleus formed probably at the wall of the crucible.* Subsequent ori- entations were developed by nucleation on existing solid surfaces, and only in the twin relationship. This is an example of a general process of nucleation on a surface of existing solid and may be descriptively termed oriented nuc1eation.t In germanium, and other diamond cubic substances, the orienting habit is that of twinning on an octahedral plane.&apos; " The prevalence of straight traces in the polished surfaces of succeeding slices (Fig. 1) suggests that the twinning observed in the first slice persisted throughout solidification. This was confirmed by X-ray determinations. The schematic diagram of Fig. 2 shows the twinning relationships of the major regions throughout the ingot. Since all observed relationships are describable as twinning, it is reasonable to conclude that no random nucleation occurred in the freezing of the ingot. An alternative possibility would be that nucleation of a random nature occurred, but only those nuclei in twin orientations survived in subsequent growth. This is unlikely for there would be as good a reason for the growth of randomly oriented nuclei as for the growth of the many different orientations present after several orders of twinning. The many twin components contain a wide distribution of orientations, and did grow. In fact, they are the only ones found in the solid. The conditions of solidification of this ingot were such as to discourage nucleation of crystals wholly in the liquid. The rate of solidification was 0.125 in. per min. This slow rate of heat removal afforded but small opportunity for supercooling within the liquid —a condition needed to provide enough decrease in free energy for such nucleation. When nucleation occurs on an existing solid surface, the interfacial energy between the existing and forming regions is important in determining the new stable orientation. The new orientation is expected to be one which minimizes this energy. In the diamond cubic structure, the interface for the

Jan 1, 1955

By E. L. Kamen, H. D. Kessler, M. Hansen, D. J. McPherson

The highly reactive Ti-Mo and Ti-Cb alloys were prepared and heat treated under protective conditions. Phase diagrams were established based on micrographic and X-ray diffraction analysis and detection of incipient melting. ß titanium forms a continuous series of solid solutions with both molybdenum and columbium, whereas these metals are only slightly soluble in the a titanium modification. PREVIOUS work on the Ti-Mo and Ti-Cb systems was very limited and is discussed in succeeding sections of this paper relating to the respective phase diagrams. The diagrams in the present work were determined principally by micrographic analysis, because other methods such as thermal analysis and dilatometry are not suitable, due to the low diffusion rates of these alloys in the transformation range. X-ray analysis was believed less useful than micrographic analysis because: 1—On quenching certain high titanium alloys from above their transformation range, the body-centered cubic ß phase decomposes into acicular a (hexagonal close-packed) which room temperature X-ray diffraction techniques cannot differentiate from isothermal a. 2— High temperature X-ray techniques might be used, but are difficult to apply and are subject to error because of the high reactivity of titanium with gases such as oxygen and nitrogen. Although metallo-graphic study was the basic method used, X-ray diffraction analysis was applied to a limited extent, to further substantiate the findings. The transformation ranges on the titanium side of the Ti-Cb and Ti-Mo systems were studied both with DuPont Process A (magnesium-reduced) titanium alloys and with iodide titanium alloys. The Process A metal was used chiefly to bracket the transformation range in order to reduce the number of alloys given a particular treatment for the more accurate final study with iodide titanium alloys. Experimental Procedure The analyses of the metals used in the preparation of alloys for this study are presented in Table I. Melting Practice: Early in the work, a consumable electrode, arc melting furnace was used in the preparation of the Process A Ti-base Mo and Cb alloys. This type of furnace has been described by other investigators.&apos;, &apos; One of the major difficulties of the consumable electrode melting process was the prep- aration of homogeneous electrodes (with the mixture of coarse titanium sponge and fine powder alloying addition) which would give homogeneous ingots. Composition gradients encountered may have been due to a tendency for powdered alloying metals to drop away from the electrode in handling. This difficulty in the preparation of homogeneous alloys was overcome by the use of a nonconsumable electrode furnace for later work. This furnace is similar to the one used by Mc-Pherson and Fontana a Ohio State University. A diagram of the nonconsumable electrode arc furnace is given elsewhere.&apos; The source of power was a 400 amp dc welding generator. Electrode tips of tungsten (% in. in diam) were used for all columbium melts and for a limited number of molybdenum melts. Molybdenum tips were used for the majority of molybdenum alloy melts. Columbium tipped electrodes were tried, but disintegrated rapidly at currents above 300 amp. In the Process A titanium melting practice the metals were charged into the water-cooled spun copper crucible in the following forms: l—titanium: sponge (—4 + 16 mesh); 2—molybdenum: sections of 0.003 in. sheet (approximately ½ in. sq); and 3— columbium: powder compacts (? in. lumps broken from large section). After alternately evacuating and purging the furnace several times with argon or helium, the arc was struck against the metal charge,

Jan 1, 1952

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors&apos; values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.&apos; From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,&apos; and Arkharov&apos; all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,&apos; have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.&apos; In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

By Hsun Hu

Direct observations were made on the recrystalli-zntion of a cold-rolled (110) [001] crystal of 3 pct Si-Fe by annealing thin sections of the specimen inside the electron microscope during examination. Subgrain formation, presumably by polygonization, occurs rapidly, followed by a slow increase in the subgrain size before recrystallization can be detected. No migration of the subgrain boundaries was observed, and the formation of recrystallization nuclei by coalescence of subgrains is suggested. Re-c~ystallization characteristics of various texture components were individually examined. AS reported in a previous paper: orientations of the various deformation texture components in a 70 pct cold-rolled (110) [0011 crystal of 3 pct Si-Fe were completely confirmed by transmission electron diffraction patterns taken at various areas of the specimen. These orientations can be summarized as follows: Over most areas of the deformed crystal (111) planes are parallel to the surface. These areas correspond to either $- the two main defor: mation textures, the (111) [112] or the (111) [112].2-5 Within a few areas, (100) planes parallel to the surface are frequently found. These areas represent the minor deformation texture component, the (100) [Oll] type, which is derived from rotated Neumann bands.2&apos;4&apos;5 Only in very rare instances are (110) planes found parallel to the surface. This orientation corresponds to the very weak texture component of the (110) [001] type. In a pole figure, this (110) [0011 orientation is located within the orientation spread between the two main (111) [1121 type textures. Usually the electron diffraction patterns taken at various areas of the specimen are very simple ones, i.e., for any one area the pattern consists only of sharply defined spots of a single orientation. In some areas, however, more or less continuous rings of weaker intensities are superimposed on a simple pattern, indicating the presence of a wide range of additional orientations. In order to understand in detail the recrystallization of this cold-worked crystal, the recrywtallization characteristics of each of the various deformation texture components must be examined. This can best be done by using a high-temperature stage and transmission electron microscopy techniques, whereby small areas corresponding to the various texture components can be selected individually for examination. The present paper presents results obtained by this method. MATERIAL AND METHOD Specimens were prepared from a previously studied1 single crystal of a commercial grade 3 pct Si-Fe alloy with an initial orientation (110) [00l], cold-rolled 70 pct from 0.014 in. to 0.004 in. in thickness. Thin foils were prepared by electrolytic polishing as described in the earlier paper.&apos; Specimens of this thin foil were then mounted in a high temperature stage similar to the one designed by Whelan.6 A direct current was used as the heating source. The temperature of the heating grid was calibrated by means of a Pt vs Pt-10 pct Rh thermocouple in a vacuum chamber (0.01 to 0.02µHg). Maximum variation within the temperature range of 250o to 000°C was about ± 25°C. After the desired areas were selected for examination, the specimen was heated to a low temperature for some time while the selected area was constantly watched. When no further change in structure and orientation could be observed, a higher temperature was applied. Photomicrographs and diffraction patterns were taken from time to time during examination, with the heater temporarily turned off* while the photographs were

Jan 1, 1962

By John H. Schemel

Large Zircaloy-2 hammer or press forged bars did not exhibit the uniform excellent corrosion resistance to steam normally expected of the alloy in wrought form. Weight gains of coupons cut from forged bars were 40 to 60 mg per sq dm compared to the 28 mg per sq dm obtained on hot rolled sheet and strip. The mechanism of this corrosion and its relation to microstructure is discussed. After these observations, a solution heat treatment followed by rapid cooling was tried on coupons from eight heats of forged bars. The basket-weave structure resulting from the quench did not show agglomeration of intermetallic compounds. These coupons showed uniformly good corrosion resistance with weight gains very close to the 28 mg per sq dm expected of Zircaloy-2 after the 14-day steam test. A large forging was solution heat-treated and tested for structure, mechanical properties, and corrosion resistance. Corrosion resistance was excellent and uniform throughout the section. The normally anisotropic mechanical properties were changed to completely iso-tropic. Strength levels were raised while there was a small loss in ductility at the service temperature. Tempering of the quenched structure below the ß transus did not improve the ductility at the test temperature of 600°F. ZIRCALOY-2 end caps for nuclear fuel elements Zircaloy-2 is an alloy of 1.5 pct Sn, 0.1 pct Fe, 0.1 pct Cr, and 0.05 pct Ni, balance hafnium-free zirconium patented by Westing-house Electric Co. used in pressurized water reactors are machined from large hammer-finished forged bars. The bars forged for this application range from 3 1/2 in. to 7 1/2 in. squares. One of the tests used to evaluate Zircaloy-2 for this service is a 14-day exposure to very high-purity steam at 75oF and 1500 psi pressure. Normally wrought products will exhibit a black lustrous film of zirconium oxide after the test and show a weight gain of approximately 28 mg per sq dm. Coupons representing the forged bars exhibited a wide variety of corrosion results ranging from acceptable black coupons to some covered with white crystals of zirconium oxide that had weight gains of nearly 100 mg per sq dm. One of the most common effects was a white corrosion product that looked like a stain to some observers and the outline of massive metal grains to others. Very careful specimen preparation prior to the corrosion test did not affect the result and metallographic examination did not reveal a structural feature of a size and shape that would correlate with the corrosion product. In addition to the relatively poor corrosion resistance, the forged product was not as ductile as desired. The problem of obtaining uniform and more acceptable properties in these heavy-forged sections seemed to be a function of the microstructure of the metal and, in particular, the distribution of the intermetallic compounds. None of the four alloying elements however are appreciably soluble in a zirconium and are present as compounds which usually appear scattered randomly throughout the structure. Moudryl showed that the distribution of these intermetallic compounds in Zircaloy could be related to a ostringero corrosion failure. Grozier et al. discussed another structural defect that causes a similar corrosion effect. In this case, an elongated gas-void was determined to be the cause. M. L. Picklesimer held in his discussion of the Grozier paper that at least a part of the observed =stringersn were caused by the distribution of the intermetallic compounds. He proposed a

Jan 1, 1962

By S. C. Schaeker, A. W. Schlechten, A. H. Larson

PARRAVANO and Malquori&apos; studied the equilibrium of H2S-Hz with molybdenum and its lowest sulfide which they believed to be MoS2. Mc Cabe&apos; has shown that its composition is actually Mo2S3 and determined its dissociation pressure by means of Knud-sen effusion measurements. Stubbles and Richard- son3 have recently studied the equilibrium of gas mixtures of H2S-HZ with the two-phase solid mixtures of Mo-MozS3 and Mo2S3-MoS2. The latter investigators found that M02s3 deviated slightly from the stoichiometric composition, but they did not determine the homogeneous region of the disulfide phase. Morimoto and Kullerud, studied the Mo-S system by quenching, microscope, and X-ray methods and concluded that the disulfide is stoichiometric. The present investigation was concerned with the measurement of the sulfur vapor pressure variation with composition at 1100°C in the homogeneous region of "MoS2". These measurements were made by reacting: 1) molybdenum powder (99.97 pct Moj with sulfur vapor, and 2) MoS1.g9 (formed by reaction of Mo + H2S) with sulfur vapor in a quartz capsule. Conditions were controlled to form an equilibrated phase within the homogeneous region of the disulfide. The quartz capsule was sealed off initially under a vacuum and the residual gases were gettered by titanium powder contained in one end of the capsule. A mixture of Mo + S or MOS,., + S was in the other end. The section containing the titanium powder was heated for 24 hr at 700°C and then removed by flame sealing. The end of the capsule containing the charge was then heated to 1100°C. The other end of the capsule was maintained at a temperature which would produce the desired sulfur pressure in the capsule (liquid sulfur distilled from the charge mixture was retained in this end). After equilibration, the capsule was removed from the heating assembly and rapidly air-cooled. It is assumed that equality existed between the total sulfur pressures (PT) in the two ends of the capsule and not between the partial pressures of the different molecular species (S, SZ, Three separately controlled heating elements were used to maintain the proper temperature gradient over the length (approximately 12 in.) of the capsule. A thermocouple-Wheelco "Capacitrol" system was used for temperature control of the two end heating elements within 2"C. The center heating element was controlled directly by a " Power -stat". Separate controlling and measuring thermocouples were used for both end heating elements. Pt-Pt(l0 pct Rh) thermocouples were used for 1100°C and Chromel-Alumel thermocouples were used for lower-temperature control and measurement of the assembly. Silver foil was wrapped around the end of the capsule containing the liquid sulfur to insure a constant temperature zone. The thermal gradient over the entire length of the capsule was measured to: 1) ascertain that the length of the constant temperature zone of the liquid-sulfur end and the sulfide end was sufficient, and 2) ascertain that the liquid-sulfur zone was the zone of lowest temperature. The data obtained in this investigation are shown in Fig. 1 and Table I. The total sulfur pressure (PT) and p(S2) were calculated from the data of Braune et UZ.~ The compositions of the equilibrated disul-

Jan 1, 1964

By S. S. Shen, M. J. Pool, P. J. Spencer, J. R. Guadagno

VERY few thermodynamic data are available for rare-earth alloys, partly because of the difficulties of obtaining the metals in sufficiently pure form and also because of their comparative scarcity up to the present time. The rare earths form a very interesting series in the periodic table in view of the progressive filling of their 4f subvalence electron shell and would be expected to provide useful information with regard to alloying characteristics of transition elements. It has been found in recent calorimetric investigations that the heats of solution of a number of the rare-earth metals in liquid tin are highly exothermic.1-4 Exceptionally strong bonding between rare-earth and tin atoms is clearly indicated in the liquid solutions. Continued thermodynamic studies of the behavior of rare earths in solution could thus contribute a great deal to present theoretical knowledge of alloying behavior and would yield an insight into bonding of a strength hitherto unencountered in liquid alloys. The determination of the heats of solution of the pure components in liquid tin is an essential preliminary to calorimetric work of this nature. Heats of solution of praseodymium, neodymium, and samarium in liquid tin at 750" &apos; and the heats of mixing of Pr-Nd solid solutions&apos; have already been determined in this laboratory. The present investigations with lanthanum continue the study of rare-earth elements. Details of the construction and operation of the liquid metal solution calorimeter used in this work have been published previously by Pool and Peluso and no further description will be given here. The lanthanum used in heat of solution determinations was supplied by Lunex who quoted the purity as 99.9 pct. Their detailed analysis of the material is given in Table I. Samples of 0.0003 to 0.0005 g-atom were used for each run and great care was taken to remove all surface oxide prior to weighing. The samples were stored at all other times in a beaker of oil to prevent their otherwise rapid oxidation. The compounds LaSn (Cudu, L1P type structure) and La&, (structure not classified) were prepared from the appropriate quantities of the two pure components by arc melting under a purified argon atmosphere and once again great precautions were taken to avoid any subsequent oxidation of the specimens. Although no structural examination of the compounds was made, the consistency of thermodynarnic measurements carried out on twenty or so individual samples of each indicates that the compounds were in fact homogeneous, single phase alloys. Samples of the compounds consisting of 0.0003 to 0.002 moles were used in the calorimetric measurements. A solvent bath consisting of approximately 80 g of 99.9 pct pure Sn was used for each series of runs and its heat capacity was determined at regular intervals throughout the experiments using pure tin or tungsten calibration samples. Measurements were made of the heat of solution of lanthanum in liquid tin at 725", 750C, and 775°K and at compositions up to 2.21, 4.76, and 5.25 at. pct La at the three temperatures respectively. In every case, the heat of solution of lanthanum remained constant at its limiting value, within experimental limits, up to the highest lanthanum concentration investigated. Since no change in was observed, it was concluded that the liquid/liquid + LaSn, phase boundary had not been

Jan 1, 1969

By S. Luszcz, R. W. Vook, Fred Witt

In situ X-ray investigations were made on polycrys-talline silver films deposited by vacuum evaporation on (111) CaF2 and (100) NaCl single-crystal substrates at 80°K. The films were evaporated and annealed in an X-ray diffractometer attachment having a residual gas pressure of 2 x lo-&apos; Torr. All measurements were made without exposing the films to the atmosphere. Measurements were made on the films in the as-deposited state and after various annealing treatments. The intrinsic stacking and twin fault densities, the magnitudes of the uniform and nonuniform strains, and the crystallite sizes were determined. In addition the textures in the films were measured qualitatively. The results obtained for the as-deposited films on single-crystal substrates are in substantial agreement with previously reported results for silver films deposited on glass. Intrinsic stacking and twin faults, as well as uniform and nonuniform strains, were present in these films. During the various annealing treatments (up to 350°C) the faults and nonuniform strains annealed out. Considerable grain growth and texture changes occurred also. The effects were much greater for the NaCl substrate than for the CaFz substrate. The relative magnitudes of the grain growth in the variously oriented grains could be explained qualitatively in terms of the thermal strains and strain energies introduced into the differently oriented grains during the initial, irreversible anneal. These strains were due to the different thermal expansion coefficients of the film and substrate. X-RAY diffraction measurements on evaporated films deposited on substrates at low temperature have the advantage that many of the imperfections introduced into the film during deposition are "frozen in". Thus, the influence of a very important experimental variable, substrate temperature, on the imperfection structure of evaporated metal films may be studied. Moreover, the effects of annealing such films makes possible the study of thermally activated recovery processes in these films. The present study was designed to determine the influence of single-crystal substrates on the resultant film structure relative to the previous results obtained using glass substrates.&apos; To this end great care was taken to keep the experimental variables the same in the two cases. Different experimental conditions would, of course, result in films having different physical properties. Again the initial substrate temperature was in the neighborhood of 80°K and the films were subsequently annealed to 350°C. The pure metal silver was chosen for evaporation, primarily because of its relatively low stacking fault energy and consequent high fault density in the as-deposited state. The silver films were formed by evaporation onto air-cleaved {ill} CaF, and (100) NaCl surfaces cooled to 80°K in an X-ray diffractometer attachment2 having a base residual gas pressure of 2 X l0-&apos; Torr. The films were not exposed to the atmosphere until all of the X-ray data had been recorded. In this way one of the most important experimental variables, environment, could be well-controlled and reproduced. X-ray measurements were made at the temperature of deposition and included determinations of the diffraction line peak positions, line shapes, and integrated intensities. The peak position measurements were used to determine the intrinsic stacking fault densities and the average uniform strain in the film. The shapes of the diffraction lines provided information on the twin fault density, true crystallite size, and average nonuniform strain. The preferred orientation in the film was determined qualitatively from the integrated intensities. I) EXPERIMENTAL PROCEDURE The evaporator attachmentZ was charged with 99.999 pct Ag pellets positioned in a tantalum filament which had been outgassed previously at l0-8 Torr. The CaFz and NaCl single crystals were cleaved in air and then placed in position in the chamber so that their cleavage surfaces were on the diffractometer axis. The chamber was prepumped using a sorption pump, sealed off, and then baked at 150°C for 24 hr. The ion pump operated during the bakeout cycle. The substrate was then heated to 500° C by means of an auxiliary heater and kept hot until the rest of the chamber was cooled slowly to room temperature. This bakeout procedure consistently resulted in an ultimate pressure in the low lo-&apos; Torr range. The substrate was then cooled down on 80°K. Its temperature was monitored by a thermocouple wedged into the rear of the copper substrate holder. The diffracted intensity and peak position of the 111, 222, and 333 CaF, lines were measured prior to evaporation. Nickel-filtered, pulse-height-discriminated copper radiation was used. Similar measurements were made for the 200 and 400 lines from NaC1. These measurements were used as a lattice parameter check and to determine the thickness of the evaporated silver films from the attenuation of the substrate lines. The evaporation rates were approximately 3A per sec for both films while the maximum pressures during evaporation were 3 x lo- &apos; and 7 x 10"8 Torr for the CaF, and NaCl cases, respectively. The film thickness was measured by the attenuation of the CaF, and NaCl substrate lines and by at optical interference method. Values of 1700 and 1500A, respectively, were obtained for the silver

Jan 1, 1969

By Pradeep K. Rohatgi, Clyde M. Adams

An analysis of heal conduction in the freezing of a solution has been performed. The case considered is the semi-infinite mass of solution, bounded by a con-stant-temperature plane with one-dimensional heat flow, Numerical cooling rate and freezing rate distributions hare been calcutated for the particular case of unidirectional freezing of aqueous solutions against. a cold copper chill. The solution at each level parallel to the chill surface is subjected to a spectra of frcezing rates; the freezing rate is inilially lour., passes through a maximum, and then decreases until solidification is camplete. Arange and maximum freeeing rates are inversely proportional to the square of distance from the chill surface. The temperature of the chill surface in contact with the solution remains constant during solidification. Experimentally, it is observed that deudrite sparing increases linearly with distance from the chill surface; in the light of heat -flow analysis this means that the dendrile spacing is imersely proportional to the square root of the maximum freezing rate. SOLIDIFICATION of liquids is accompanied by rejection of latent heat at the solid-liquid interface. The over-all rate of liquid to solid transformation is governed by the rate of heat extraction. Analysis of the heat transfer in the liquid during freezing is important since it determines the freezing rate and resulting structure. A considerable amount of work has been done on metallic systems since solidification is frequently a major step in processing metals. Unidirectional freezing from heat sinks has been treated by several investigators.1-4 Much of the work has been limited to the simpler case of substances such as pure metals which freeze isothermally at a unique transformation temperature. In this case the thickness of the solid zone y, next to a chill surface. is a parabolic function of the time. 8. where a and b are constants. Eq. |1| is a close approximation giving the progress of solidification for the case in which there is a small but finite thermal contact resistance at the interface between the freezing liquid and the chill.&apos; It has been used with some success in connection with large steel ingots4 when the therma1 contact resistance is negligibly small (as is the case when water is brought into contact with the metal chill). The constant, b. becomes zero and Eq. [l] is then exact. even when the thermal properties of the chill and the freezing liquid depend on temperature. Analysis of unidirectional solidification of solutions is more complicated since the latent heat is evolved over a range of temperatures. Next to the all-solid zone in contact with the chill surface there is a solid plus liquid zone in which solidification takes place. Although the equations presented are considered quite general the numerical and experimental results are for freezing of aqueous solutions from a copper chill. I) EXPERIMENTAL PROCEDURE Solutions of potassium chloride, sodium chloride. and lithium chloride have been used. These solutions form a eutectic: a typical phase diagram is shown in Fig. 1. A solution at its liquid us temperature is poured into a tygon tube mounted on a relatively large copper chill. The chill is immersed in a freezing mixture of dry ice and acetone at -70°C. A thermocouple connected to a high-speed recorder was mounted near the top of the chill to measure the fluctuation in the temperature of chill surface in contact with the solution. In this system the progress of solidification can be visually observed through the tygon tube. After the specimens freeze to a desired height they are removed from the copper chill and stripped from the tygon tube. Longitudinal and transverse sections are cut from the specimen for micrographic examination. Specimens in the form of a thin slice are mounted on a transparent glass slide by freezing small drops of water around the periphery. They are then polished on a series of emery papers; the final finishing is done on a soft tissue paper. A Leitz Biological microscope was used for structural observations; photography was

Jan 1, 1968

By R. F. Hehemann, R. H. Goodenow

Thermal arrest, hot-stage microscopy, and transtnission electron microscopy techniques have been employed to study the transformations in low-carbon iron and Fe-9 pct Ni alloys. In continuous cooling experiments, each alloy transforms at an essentially constant temperature for cooling rates below the critical rate required for martensite formation. However, high-tenzperature transformation in pure iron takes place by a different mechanism than that in the 9 pct Ni alloys. Pure iron exhibits an equi-a a structure with a low and random dislocation density while the 9 pct Ni alloy exhibits a cell or lathlike substructure analogous to that of low-carbon martensite. This same substructure characterizes upper bainite in higher-carbon inaterials. UNTIL relatively recently, diffusionless transformations have been considered to take place by the same mechanism and have been termed mar-tensitic transformations.l-3 The most characteristic feature2 of this mode of transformation is the shape change produced by a shear deformation and growth of the product phase frequently occurs at an extremely high velocity approaching that of an elastic wave.4&apos;5 A different mechanism of diffusionless transformation was recognized first in Cu-Ga and other copper-base alloys.6,7 From the absence of surface tilting in these alloys, it has been concluded that transformation is not accomplished by the cooperative shear displacements that occur in mar-tensitic reactions. Transformation presumably takes place by the rapid movement of an incoherent interface which is capable of propagating across parent grain boundaries. Although the transformation is diffusionless in the macroscopic sense, advancement of these interfaces is accomplished by an atom by atom rearrangement. Transformations of this type therefore require thermal activation and are generally operative only at high temperature. Although requiring short-range diffusion at the interface, propagation still occurs so rapidly that the reaction cannot be suppressed with normal cooling rates.7 The resulting microstructures exhibit large, irregular-shaped regions of the product phase, which are essentially free of crystallographic features. Consequently, these reactions have been termed massive transformations. Transformation by the massive mechanism has been reported to occur in ferrous systems involving pure iron and binary alloys of iron with nickel, chromium, and silicon by Gilbert and owen.&apos; The Fe-Ni system is of special interest in that the massive transformation was observed in alloys with less than 15 pct Ni while alloys having more than about 28 pct Ni transformed by the conventional mar-tensitic mechanism. By employing cooling rates substantially higher than those used by Gilbert and Owen, Swanson and Parr have been able to suppress the massive transformation in alloys with 0 to 10 pct Ni9 and produce martensite as revealed by surface relief. The massive transformation in the alloys having less than 15 pct Ni was identified by the lack of surface relief and an irregular rather than clearly acicular microstructure.&apos; Speich and Swann, using thin-foil electron microscopy, identified three distinctly different structures10 in quenched binary Fe-Ni alloys. From 0 to 4 pct Ni the structure consisted of blocky grains of a with a low and random dislocation density. Alloys with 4 to 25 pct Ni exhibited a cell structure with a high dislocation density; and at greater than 25 pct Ni the structure consisted of internally twinned plates. The structural change at approximately 4 pct Ni suggests that alloys with low nickel content transform by a different mechanism than those with intermediate nickel contents and the transition from the cellular to the internally twinned structures at approximately 25 pct Ni is analogous to the transition from needles to internally twinned plates that occurs over a narrow range of carbon contents in Fe-C martensites.11,12 Conventional bainitic and martensitic modes of austenite decomposition operate in ternary Fe-C-Ni alloys having less than 10 pct Ni. This investigation was conducted in order to explore the conditions under which the massive, bainitic, and martensitic transformations occur and the relationships between these modes of decomposition.

Jan 1, 1965

By L. A. Weitzenkamp, N. M. Bashara

A study of the electrical conductivity of gold films less than 200 in thickness indicates a negative temperature coefficient of resistance and a thermal actiuatlon energy of less than 0.25 ev. The films consist of discrete metal islands of linear dimensions from a few angstroms to 1000A. Films were able to withstand applied fields up to 60,000 v per cm before breakdown occurred. A model for the conduction mechanism is proposed which involtes a Potential barrier due to work junction, irriage forces , and an electrostatic potential arising from separating an electron from a neutral island leaving behind a positively charged metal island. Activation energies of less than 0.25 ev ave consistent with this model, which includes a tunneling andor Thermal mechanism for conduction between the separate metal islands. An apparent satuvation effect in conductivity at high fields is observed experimentally. The saturation effect may be explained by the influence of the electrostatic contribution to the potential barriers for the transition through several islands adjacent to the original island which was activated to give up an electron. The proposed model gives Poor quantitative agyeement for the intermal electrical field between islands. ThIS paper will relate the structure of discontinuous metal films to the electrical properties and will emphasize the following topics: 1) the relation of the conduction mechanism to particle size and a comparison of particle size from electrical measurements with electron-microscope studies; 2) the saturation of the conductivity at high electric fields; and finally, 3) a comparison between the external field applied and the apparent field between particles. che- latter comparison points to a need for a modification in the model for the conduction mechanism first proposed by orter&apos; and expanded by Neugebauer and webb2 which will be dealt with in the discussion. The paper is based on results on gold films on glass microscope slides. The clms were vacuum-evaporated and were about lOOA thick, thickness being measured by interferometry. It has been observed that metal films of this thickness do not exhibit bulk metallic conduction. Films thinner than some critical thiclmess, depending upon substrate temperature and other factors, have conductivities which increase with increasing temperature with thermal activation energies of less than 0.25 ev. Electron-microscope studies3 have shown that these films consist of discrete metal islands having linear dimnsions from a few angstroms to approximately 1000A. When the metal is being vacuum-deposited on the substrate, islands on the order of a few angstroms appear first. As the deposition continues the islands may tend to agglomerate into larger particles and may eventually grow together into a continuous film,3&apos;&apos;&apos; In our tests the conductivity of the gold films was found to be about ten orders of magnitude less than the bulk conductivity of gold. When oxygen was introduced into the test chamber the conductivity decreased by a factor of about one-third. This can be related to an increase in work function for gold caused by adsorption of oxygen, as reported by Oullet and Rideal.s Exposure to an atmosphere of water vapor caused an increase in conductivity by a factor of 2 or 3 when a low field was applied. When the films were exposed to water vapor under a high field the conductivity increased by as much as two orders of magnitude. The activation energies measured were much less than the work function for gold, 0.25 ev or less, with the smaller activation energies observed for thicker films. It will be shown that the activation energy is a function of particle size and spacing. In general the model for the potential between metal islands would include the effective work function, the image force, the applied field, and an electrostatic term. The electrostatic contribution arises from the potential required to separate an electron from a conducting sphere. According to Neugebauer and webb2 the maximum potential due to the field and the electrostatic term only is

Jan 1, 1967

By W. L. Phillips

Single crystals of aluminum, brass, and copper oriented for (100) and (110) slip were extended at 25°, 400°, and 600°C in simple shear. Aluminum specimens oriented for nonoctahedral slip began to shear at a higher critical resolved shear stress than specimens oriented for octahedral slip. Parabolic stress-strain curves were obtained from zero strain. The initial rate of parabolic hardening was lower for specimens sheared on the (100) plane in a close-packed direction <110>, than for specimens sheared in a nonclose-packed direction <100>. metallographic evidence, however, showed that all slip traces could be explained in terms of (111) <100> slip. All attempts to cause nonoctahedral slip in copper and 70-30 a-brass single crystals were unsuccessful. Instead of shearing, the crystals bent, allowing {111} type planes to come into action. NONOCTAHEDRAL slip in aluminum has been reported under three different conditions: first, as the main mode of slip in tension experiments at elevated temperatures;&apos;-&apos; second, as the main mode of slip in direct shear experiments at room temperat~re; and third, as a minor mode of deformation, i.e., as cross-slip, in tension, shear, and bicrystal experiments at room and elevated temperatures."-l2 However, as far as the author knows, nonoctahedral slip has not been reported in either copper or 70-30 a-brass. The present study was undertaken to determine whether nonoctahedral slip could be obtained in aluminum, brass, or copper at room or elevated temperatures when the shear stress was approximately constant over the cross-section, a maximum at the center, or a maximum at the surface. EXPERIMENTAL PROCEDURE A detailed description of the crystal preparation and shearing apparatus has been given previo~sly. Cylindrical crystals 1/2 in. in diam and 8 in. long were grown from the melt in a temperature-gradient furnace. The aluminum contained 0.001 pct Zn, 0.001 pct S, and 0.001 pct Fe; the 70-30 brass contained 0.015 pct Pb, 0.001 pct Fe, 0.01 pct Ni, 0.02 pct Sn, and 0.005 pct Se; the copper was certified OFHC of 99.98 pct purity. All samples were electropolished prior to testing. The shear apparatus was a modified Bausch type. The strain sensitivity was 4 x lob4 Load was applied by clamping the rods attached to the shear plates in an Instron tensile machine. The rate of loading was 0.02 in. per min. In all cases a 1/8-in. gage length was used. For the tests performed at 400° and 600°C the shear plates, collars, and rods were made of stainless steel. These elevated-temperature tests were performed in an argon atmosphere. A) Aluminum at Room Temperature. Values of a and ß for the various slip planes and slip directions investigated are shown in Table I where a is the complement of the angle between the specimen axis and the slip direction, and ß is the angle between the specimen axis and the normal to the shear plane. The shear stress is a function of a (assuming ß - 0);10 when a is less than 27 deg, the shear stress on the slip plane for which the specimen is oriented has a maximum at the center of the crystal; at a = 27 deg the shear stress is constant across the slip plane; for a greater than 27 deg the shear stress is a minimum at the center. Fig. 1 shows the stress-strain curves for specimens cut from crystals 1, 2, and 5, which were sheared on the (010) plane in the [loll direction at room temperature. These three crystals have shear-stress distributions corresponding to the three dif-

Jan 1, 1962

By Jerome F. Kuzmick

Many investigations have been made on the effect of the variables of pressure, sintering temperature and sintering time on the physical and microstructural charactcristics of metal-powder compacts. Severa1 such investigations have indicatcd that pressure is the least important of these three factors in an attempt to secure a dense. strong compact by a simple coltl-pressing and sintering procedure. However, it was felt that a further study of the effect of pressure on pressed and sintered metal powder compacts might prove interesting, for the following reasons: In work done in the past on the effect of pressure, temperature. arid time, the, metal-powder compacts were subjected to long sintering periods, and temperatures right up to the melting point of the metal were applied. It was thought that pressure might exert a more profound effect under short-time simtering and within narrower ranges of temperature. such as normally would be applied in large-scale production of metal-powder parts. 2. It was hoped that something further might be learned of the nature of the bond in pressed and sintered metal-powder compacts. 3. It was thought that interesting infor mation concerning the work-hardening effect of pressure on the crystal structure. of sintered metal-powder compacts would be obtained. Procedure Rectangular bars, 2 by 1/2 by 1/4 in. were molded from the following metal powders: Atomizcd till powder, 325-mesh Atomized aluminum powder, 325-mesh Reduced copper powder, 100-mesh Electrolytic iron powder, 100-mesh Atomized 70-30 brass powder, l00-mesh The, till powder was molded at various pressures up to 40 tolls per sq. in. This was the maximum, because at higher molding pressures there was considerable extrusion of tin into the die wall, jamming the die plungers. The tin specimens were not -in tered, as this phase of the work was- done merely to see how much a very sold metal could be compressed. The aluminum powder was compressed at various pressures up to 50 lons per sq in. Higher pressures could not be used because of extrusion into the die wall The compacts were sintered one hour at 000 in pure dry hydrogen. The copper powder was molded at vari-ous pressures up to 96 tons per sq. in. One set was sintered at 750°C., another at 050 C. for one hour in pure dry hydrogen. The electrolytic iron powder was molded at various pressures up to 00 tons per sq. in. and sintered, one set at Soo°C and one set at 1300°C for one hour in pure dry hydrogen. Extra 325-mesh specimens were also prepared to study the effect of reduced particle size on grain structure. The brass powder was molded at various pressures up to 96 tolls per sq. in. and silltered for one hour. one set at 65o°C. and one set at 800°C, in pure dry hydrogeu.

Jan 1, 1945