Search Documents

By A. F. Bertuzzi, M. R. Tek, F. H. Poettmann

A method is presented for predicting pressure drop for two-phase fluid flow in horizontal pipes. A set of 267 experimental measurements randomly sampled from approximately 1,000 measurements from various literature sources was used. Pressure gradients calculated by the procedure developed and compared with the experimental values showed a bias of +0.82 per cent and a standard deviation of 20.8 per cent. The advantatges of this method over other available methods of predicting two-phase flow pressure drop are (a) its comparative simplicity of application, (b) its relative independence of flow patterns, (c) its accuracy, which on the basis of a statistical evaluation predicts pressure drop closer than other available methods, and, (d) its ability to satisfactorily correlate laboratory data from various sources while the correlations from these sources do not appear to agree with one another. The method has been reduced to a simplified graphical procedure, suitable for field use. A two-phase f factor is defined and correlated with parameters involving the flowing gas-liquid mass ratio, a Reynolds number for the gas phase, and a Reynolds number for the liquid phase. The choice of parameters allows the correlation to reduce to the usual f factor plot for the limiting conditions of (111 gas or all liquid. INTRODUCTION The mechanics and characteristics of two-phase flow systems have been of interest throughout the industry for some time. In numerous engineering installations such as pipe lines, chemical reactors, and heat exchangers, two-phase flow conditions are of every day occurrence. In oil production operations it has been desirable, in some cases, to consider transporting gas and oil together in a common pipe from oil field to process plant. The trend toward centrally located stock tank batteries in oil fields has resulted in longer gathering pipelines in which more than one fluid phase is flowing. The increase in the producing capacity of oil wells due to new production tech- niques has created the need for review and re-design of many surface gathering lines for properly handling the increased production. Optimum pipe size for the situations described above has become an important factor. The problem which is of interest here involves the ability to predict the relationship between pressure drop, fluid properties, fluid rates, pipe diameter, and pipe length. Although the literature1,5,10,13,18,19 contains various articles dealing with specific cases of the problem, Lock-hart and Martinelli17 proposed the most general solution. Their method has been later modified by Baker:1 Alves2 demonstrated that different flow patterns are possible for a flow mechanism defined by Martinelli such as gas turbulent, liquid turbulent. Baker explained deviations experienced with Martinelli's correlations on the basis that different flow patterns could exist for the same flow mechanism. Using Martinelli's method of correlatioil, Baker correlated data for each flow pattern for the turbulent-turbulent flow mechanism. Bergelin and Gazley6,7 presented a correlation for predicting gas phase

Jan 1, 1957

R. Culver, Colorado School of Mines I appreciated Professor Starfield's presentation, because his approach to blasting research reflects my feelings that a lot of practical work can be done toward making short-term advances that can be used by the blasting industry. We should not forget this in our attempt to obtain solutions to such idealized problems as a mathematical theory of cratering. The blasting industry would like very much to have the efficiency of the basic blasting processes improved from the range of 20 percent up into the range of 50 percent. And many of these problems should be approached and attacked in the laboratories. Blasting research at the Colorado School of Mines for the past two or three years has been aimed at improving the pre-splitting process, because we feel it will become increasingly important to the construction industry. We have attempted to develop a unified theory of how pre-splitting works; and the more we investigate, the more variables we find. We may never obtain an entirely satisfactory theory of pre-splitting, but we have developed a tentative explanation. One of our first conclusions was that we are making very poor use of the explosive in current pre-splitting practice. But to appreciate this we must first consider how pre-splitting works. A series of parallel boreholes are loaded with low density charges which are detonated simultaneously. (Delayed detonation has been tried, but most people agree that simultaneous detonation is best, and this is what we found.) Stress waves traveling out from each borehole interact with the stress waves from the two adjacent boreholes influencing the direction of the fractures that occur and propagate from each borehole. It has been suggested in private communication with Mr. Wilbur Duvall of the U. S. Bureau of Mines, that the fracture between the adjacent boreholes is a result of the net particle velocities above and below the pre-split plane which tend to set up a net tension along the pre-split plane. Regardless of what the exact mechanism is that causes the fracture to propagate from one borehole to the next, we know that it, in general, relies upon an interaction of the stress waves. However, if there is a large compressive stress normal to the pre-split place, it can practically eliminate any possibility of obtaining the desired pre-split by preventing the desired fractures from getting started. Aside from obtaining a fracture along the pre-split plane, the other major aim of pre-splitting is to minimize the fracturing that occurs around the borehole. We do this by drilling a large hole and putting a small charge in the middle of it. This results in a badly decoupled charge which is very inefficient; most of the energy is used in compressing the air in the borehole. Out of discussions about how pre-splitting works, we decided that perhaps there was some other explosive geometry which would make more efficient use of the explosive, and result in optimizing the pre-splitting process. Starting in the laboratory with small plexiglas blocks, we found that a fully-coupled explosive charge of 5 grains/in. of PETN gave random fractures extending about I in. from the borehole. A 1/4 in. plexiglas plug fit into a 1/4 in. hole in a similar block with the same fully coupled charge gave random fractures extending out only about 1/2 in. due to the energy absorbed in fracturing the plug. If the plug was split longitudinally but otherwise using the same geometry, it was possible to drive a fracture about 2 in. in either direction from the borehole, with an even smaller amount of fracturing around the borehole.

Jan 1, 1967

By Max W. Ball

An intelligent discussion of the oil situation and its needs, whether from the standpoint of the prospector, the operator, the engineer, or the public administrative officer, must be founded upon a knowledge of the law under which oil lands are obtained. A consideration of new legislation must be prefaced by an understanding of the present law and its results. This paper undertakes to present no new remedy for the ills of the present situation, no new solution of the problems the oil business is facing. It attempts merely to summarize the present law, its provisions, its origin, its development, and its effects. The discussion does not pretend to be exhaustive from a legal standpoint. It aims to avoid legal intricacies which tend to. confuse rather than clarify. It seeks but to present the essentials of the existing situation. The title to government lands known to contain valuable deposits of petroleum may be acquired only under the terms of the placer law as embodied in Section 2329 et seq. of the Revised Statutes. As a preliminary to considering the desirability of this situation it is profitable to examine into its origin. Origin of the Law Congress has left no room for doubt as to the legal applicability of the placer law to oil lands. The Act of Feb.11, 1897(29 Stat., 526), provides: "that any person authorized to enter lands under the mining laws of the United States may enter and obtain patent to land containing petroleum or other mineral oils, and chiefly valuable therefor, under the provisions of the laws relating to placer mineral claims.' . The immediate cause for the passage of this Act was stated in a brief report in the, House of Representatives (there was no debate in the Senate) to be a decision of the Department rendered Aug. 27, 1896 (Union Oil Co., 23 L. D., 223), directing the cancellation of an oil placer entry on the ground that land containing petroleum cannot be located and entered as a placer mine. The report of the Public Lands Committee of the House contains the following interesting statements Congressional Record, vol. xxix, p. 1409):

Jan 1, 1915

By A. U. Seybolt, J. L. Walter

The effects of the addition of 0.5 pct ThO2 (by volume) on the grain structure and texture of heavily rolled tungsten sheet were studied. Powder metallurgy ingots were rolled to sheet, 0.001 in. thick, and samples were annealed at temperatures from 1200" to 2500°C. The heating rate to the anneal temperature was varied from 3°C per min to 6500°C per min. The orientations of the largest grains were determined by X-ray diffraction. The disposition and loss of the ThO2 particles were determined by electron transmission microscopy and the activation energy for remozlal of the thorium was measured by mass spec-troscopy. Heating rates below about 800 C per min produced large, highly elongated grains. Higher heating rates produced much smaller, less elongated grains. The grain structure and texture of the slowly heated samples were identical to the structures and textures of heavily rolled tungsten foil conventionally doped with aluminum, silicon, and potassium but the recrystallization temperature was about 200°C lower. There was stringer-like dispersion of larger ThO2, particles superimposed on a uniform dispersion of fine particles. The particles increased in size and decreased in number with time at temperature. The loss of particles was accompanied by formation of grain boundary voids and surface pits. The activation energy for removal of the ThO2 was about 40 kcal per mole. THE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of heavily rolled sheet1 or drawn wire."4 Thus, "doped" tungsten sheet, rolled to 0.001 in. and recrystallized, develops a structure consisting of large, highly elongated grains of a specific preferred orientation.' It has been shown that the elongated grain structure was caused by a dispersion of particles, identified as mullite (Al6si2O13),1,4 in strings parallel to the rolling direction in sheet or to the wire axis. Identical results were obtained for iron which was doped with glass and rolled to 99 pct reduction of thickness and recrystallized.5 Again, the glass particles were disposed in strings parallel to the rolling direction. The strings retarded boundary migration in the lateral direction but grain growth was able to proceed relatively unhindered along the direction parallel to the strings.1,5 In both the doped tungsten and the glass-doped iron, the particles were highly plastic during the high-temperature deformation. Since mullite melts at about 1800°C and the glass employed melts at about 810ºC, the particles were probably molten during the recrystallization anneals (above 1800°C for the doped tungsten and 850°C for the glass-doped iron). There are indications in the literature that particles not plastic at hot-working temperatures (up to about 1550°C for tungsten) may also impart elongated grain structures by primary recrystallization of worked alloys. Examples are dispersions of tantalum carbide in chromium,6 and ThO2 in nickel where elongation ratios of recrystallization grains of up to 20:l were obtained.7 Strings of ThO2 particles in W-ThO2 wire have been seen by Rieck.8 In view of the available evidence, it was of interest to extend the previous studies of doped tungsten and glass-doped iron to include W-ThO2 sheet materials. Of specific interest was the grain structure, preferred orientation, recrystallization temperature, and disposition of the thoria particles. EXPERIMENTAL PROCEDURE A) Material Preparation. About 380 g of blue tungsten oxide (approximate composition WO3) was wet with a sufficient amount of aqueous solution of Th(N03)4 to provide 0.5 vol pct ThO2. The wet mixture was stirred to distribute the doping material uniformly throughout the powder. Stirring was continued while the mixture was heated until it was completely dry. The dried, doped mixture was then reduced to tungsten powder by heating at 850°C for 2 hr in a stream of dry hydrogen. The doped tungsten powder was hydropressed in a rubber sack at pressures of 50,000 psi to produce an ingot approximately 2 cm diam by about 5 cm long. Next, the pressed cylinder was heated in hydrogen for 2 hr at 1350°C to render it strong enough for machining. The cylinder was machined to a square cross section of 1.6 by 1.6 cm with rounded corners. Finally, the bar was heated for 2 hr at 2150°C in hydrogen to provide a sufficiently dense mate rial to withstand the hot-rolling operation. Prior to rolling, the ingot was reduced in thickness by about 20 pct by forging at 1550°C. This served to increase the density of the material and to widen it slightly for better rolling characteristics. The forged ingot was then rolled at 1550°C to a reduction of 45 pct of thickness, following which the rolling temperature was reduced to 1300°C and the slab rolled, with several reheats, to 0.050 in. Further reduction was accomplished at 800°C in tungsten sheet packs to a total reduction of about 99.85 pct. B) Annealing Treatment and Observation of Structure. Small samples of the rolled foil were annealed in one of two ways. Some of the samples were suspended in a covered tungsten can and annealed at temperatures from 1200" to 2200°C for various times in vacuum of l0-7 to 10-6 mm Hg. The can was heated by induction and temperatures were determined by optical pyrometry

Jan 1, 1970

By Ralph V. Higgins

This paper concerns the magnitude of the amount of supersaturation that occurs in an underground reservoir during the flow of oil and gas to wells and to the amount of undersaturation that occurs during repres-suring of an oil reservoir where some effective permeability to gas exists. The study is based on earlier laboratory findings of other investigators on the rate of diffusion of gas in oil as a function of the depth of oil. Utilizing these relationships and the principles of reservoir mechanics, a quantitative estimate of undersaturation and super-saturation was calculated. The results showed that the diffusion of the gas is rapid enough that for all practical purposes no supersaturation exists during the flow of oil to wells or undersaturation during repressuring in reservoir sands having some effective permeability to gas. The reason diffusion of the gas virtually keeps the oil saturated is the long time required in radial flow for oil to reach the well and the slow rate at which pressure in reservoirs is increased during repressuring. INTRODUCTION Knowledge of the phase relationships during flow of gas and oil in an underground reservoir is essential to operating the reservoir in the most efficient manner. In material-balance calculations and in fluid-flow studies, the oil is assumed to contain all the gas that it will dissolve at given temperature and pressure. Pressure-volume-temperature relationships are normally obtained in the laboratory using "bottom-hole" or combined samples of the reservoir fluids. In such laboratory determinations equilibrium is obtained between the oil and gas in the pressure cells by mechanical agitation. During the flow of oil and gas in reservoirs, however, no comparable agitation occurs to mix thoroughly these fluids to aid in effecting equilibrium between the two phases. During repressuring of a partly depleted underground reservoir, the gas is usually injected into the reservoir faster than the oil can absorb it; consequently, the oil is undersaturated. On the other hand, as the oil flows through the reservoir to the wells during producing operations the pressure decreases faster than the gas in solution can diffuse through the oil to the gas phase. The oil therefore is supersaturated with gas. Where the oil is undersaturated, gas diffuses away from the gas-oil interface, and where it is supersaturated the gas diffuses toward the interface. In either case the gas moves from a higher to a lower saturation. This report contains the results of a study of the factors influencing the degree of nonequilibrium of the phase relations of oil and gas in porous mediums during the flow of oil through reservoirs to wells and also during the injection of gas into partially depleted sands. Data from an underground reservoir are presented and the degree of supersaturation during the flow of the oil through the reservoir to the well is approximated. Also data from another reservoir are used and the degree of undersaturation during the repressuring operation is calculated. In addition, the flow rates of oil in laboratory experiments and in underground reservoirs are compared, as data from the laboratory are often used to interpret events in the reservoir, and the rates of flow influence appreciably the degree of nonequilibrium. Much of the contents of this report was prepared in 1943; but, because of other activities during and since the war, the manuscript was left untouched until 1952, when it was decided to include an estimate of the amount of undersaturation during repressuring as well as supersaturation during flow.

Jan 1, 1955

By Harlowe Hardinge

The sound made by ball, pebble and rod mills has long been used by the operator as the "telltale" of their operation. The nature of this sound depends upon local conditions and the type of mill used. By experience an operator can tell whether the mill is running properly or not. Some operators are able to detect the difference in sound much better than others and get better results running the same mill under the same conditions. The automatic operation of a mill using sound as the fundamental means for maintaining control presents many problems. The satisfactory solution of these problems requires, for given operating conditions, a greater average output, with improved product for subsequent processing, than can be obtained by manual control. Relation of Sound to Useful Grinding Energy Experience has taught us that there is a difference in character as well as in intensity of sound between a mill grinding wet and one grinding dry, in open or closed circuit, to obtain a coarse or fine product, on the same material, to say nothing of the effect with a variety of different materials. Broadly speaking, a wet-grinding mill operates best at a lower sound level than the same mill grinding dry, with other conditions the same. Several reasons for this variation in sound intensity under these conditions can be advanced, but the important point is that there is a difference, based upon practical results. Since these reasons may be more or less involved, and may be subject, to much discussion, only one will be considered here. It is apparent that two balls hitting together or a ball striking the lining, if there is no intervening material, will produce the maximum sound. If a complete cushion of material is placed between the balls or ball and liner, so that the energy is dissipated without doing useful work, the balls will be unable to create enough pressure or force to fracture the particles, and the sound will be at a minimum. At some point in between—that is, where there is sufficient material between the balls or ball and liner so that the ball will fracture the particles without mashing them unduly—the sound

Jan 1, 1939

By Harlowe Hardinge

The sound made by ball, pebble and rod mills has long been used by the operator as the "telltale" of their operation. The nature of this sound depends upon local conditions and the type of mill used. By experience an operator can tell whether the mill is running properly or not. Some operators are able to detect the difference in sound much better than others and get better results running the same mill under the same conditions. The automatic operation of a mill using sound as the fundamental means for maintaining control presents many problems. The satisfactory solution of these problems requires, for given operating conditions, a greater average output, with improved product for subsequent processing, than can be obtained by manual control. Relation of Sound to Useful Grinding Energy Experience has taught us that there is a difference in character as well as in intensity of sound between a mill grinding wet and one grinding dry, in open or closed circuit, to obtain a coarse or fine product, on the same material, to say nothing of the effect with a variety of different materials. Broadly speaking, a wet-grinding mill operates best at a lower sound level than the same mill grinding dry, with other conditions the same. Several reasons for this variation in sound intensity under these conditions can be advanced, but the important point is that there is a difference, based upon practical results. Since these reasons may be more or less involved, and may be subject, to much discussion, only one will be considered here. It is apparent that two balls hitting together or a ball striking the lining, if there is no intervening material, will produce the maximum sound. If a complete cushion of material is placed between the balls or ball and liner, so that the energy is dissipated without doing useful work, the balls will be unable to create enough pressure or force to fracture the particles, and the sound will be at a minimum. At some point in between—that is, where there is sufficient material between the balls or ball and liner so that the ball will fracture the particles without mashing them unduly—the sound

Jan 1, 1939

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts' law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By Richard Franchot

DISCUSSION of a paper is sometimes more in-teresting in what has not been said than in what is said. In the present case the paper is mainly directed to certain thermo-dynamic relation-ships in the blast furnace. Careful reading of the dis-cussion fails to show a single use of the term, heat unit, or its equivalent. If we wish to know very-much about the furnace action it is necessary to count calories or B.t.u. Nothing much is. said about the availability of heat at high temperatures, although it will be generally admitted that in seeking underlying limiting factors in the furnace economy the hearth heat relations offer-the most promising clues. Those discussing the paper, with exceptions of course, apparently have failed to recognize an outstand-ing fact. It is a fact that the heat actually generated by the air oxygen in CO formation (including the blast heat) is in excess, after charging off radiation, etc., by from 70 to .90 per cent over the heat absorbed in melting the iron and slag and calcining the stone reduction by CO absorbing no heat. The fact stands out as plainly as does the fact that the furnace functions largely as a gas producer. The surplus heat is there. It is in the picture. Why not take a look at it, face the fact? That the surplus heat is necessitated by the hearth conditions admits of very little if any doubt. The furnace is really two separate pieces of apparatus: the hearth, doing certain work, and the superimposed shaft, doing certain other work. The combustion of fuel in the hearth, primarily serving the hearth pur-poses, generates much more heat and gas than the shaft requires, or can use, in smelting work. The result is surplus heat makes still more gas in the heat-absorbing reaction between CO, and coke; what is left of the surplus going to top heat. Here we have a simple yet adequate sketch of the furnace action. Having obtained a fairly comprehensive view of the existing heat relations of both hearth and shaft, the way to improvement seems quite plain. Either do more of the work above the hearth or put more heat into the hearth. Since there is already a great surplus of heat above the hearth, probably little needs to be done by way of increasing the proportion of the work done in the shaft. The shaft can, however, probably do much more work than it is now doing provided that a way, can be found to get more work, done in the hearth. The hearth heat is nicely balanced. Losses by radiation and water cooling and other losses are already taken care of. Any increase of hearth heat development could be utilized in taking care of increased smelting work. Aside from the possibility of increased blast heat, there is one sure way of putting more heat into the hearth, and this is to blow more air. And since the shaft already has more gas than it needs, the increased gas resulting from the greater blast volume can be withdrawn from the bosh after it has done its work in the hearth. Now an increase of burden will cool the shaft, cut down solution loss and thereby supply addi-tional coke in the hearth to burn with the additional air blown. The hearth heat per pound of coke charged will be proportionately increased. The balance between hearth and shaft will be better. Gruener's ideal will be more nearly attained, if not exceeded. Most inter-esting of all perhaps, the more the burden is increased, the more coke will reach the hearth and the more burden can be added. The effect is to be cumulative.

Jan 3, 1927

By J. C. Williams, M. J. Blackburn

Several of the decomposition processes that can occur in supersaturated phases in a Ti:11.6 wt pct Mo and a Ti:20 wt pct V alloy have been studied by transmission electron microscopy. The deformation induced "marternsitic phase" in the Ti:Mo alloy has been found to have a bcc or bct structure rather than the previously reported hexagonal structure. The morphology of&apos; the transformed region is a rather complex asserrlblage of twins, twinning occurring in one or more systems; this internal twinning has been found to occur on (112). The w phase is formed in both alloys on aging and is present in the Ti:Mo alloy after quenching. The structure of this phase has been confirmed as hexagonal in both systems, however, differences in morphology and stability are found between the two alloys. Thus in the Ti-Mo alloy the w phase has an ellipsoidal morphology with the major axis lying parallel to <111>ß or [0001]w while in the Ti-V alloy the phase forms as cubes, the cube faces lying parallel to {100}ß or {2021}w Some observations on the particle sizes, volume fraction, and composition of the w phase in the Ti-Mo alloy are listed. The mode of formation of The a phase from the (ß + w) structures is also different in the two alloys. In the Ti-Mo alloy the a phase is formed by either a cellular reaction or by the growth of isolated needles, whereas in the Ti-V alloy the a phase is nucleated at an w:ß interface and grow to consume the w phase. Some of the difjerences in behavior of the w phase are attributed to the mismatch between it and the solute enriched ß matrix in which it forms. MaNY transition elements tend to stabilize the bcc or ß-phase when added to titanium. In general two types of phase diagrams are produced, either a ß-stabilized (ß-isomorphous) system, e.g., Ti:Mo, -Ti:V, Ti:Nb, or a ß-eutectoid system, e.g., Ti:Cr, Ti:Fe, Ti:Mn. In previous papers&apos;-4 the phase transformations in the a-phase and (a + ß)-phase alloys have been described and this work has been extended to ß-stabilized systems. Specifically, transformations in the alloys Ti:20 wt pct V and Ti:11.6 wt pct Mo have been studied; in both of these alloys the ß phase is retained at room temperature when quenched from the ß-phase field. A number of phase transformations can occur in such metastable ß phases and the two alloys were chosen to include most of the transformations reported for ß-stabilized systems. We list these possible phase transformations below. Ti:11.6 Mo quenched from >780°C to retain the ß phase: a) The w phase can form on quenching.5 b) Martensite can be produced by subzero cooling or deformation. Two martensite habit planes have been reported in Ti:Mo alloys; (334)ß and (344)ß=6 c) On aging at temperatures <-550° C the w phase is formed before the a-phase.5,7 d) On aging at temperatures >550°C the a phase is formed.7 e) The martensite can be tempered. It has been reported that the a phase rather than the ß phase is precipitated during tempering.&apos; Ti:20V quenched from >660°C to retain the ß phase:9 a) At aging temperatures <260°C separation into two bcc phases occurs. b) The w-phase is produced prior to the a phase on aging at temperatures <-400°C. c) At temperatures 2400°C the a phase is formed directly. T-T-T diagrams describing the temperature and time regimes for the formation of these phases have been published7,9 for a Ti:12 pct Mo and a Ti:20 pct V alloy. We have attempted to investigate these transformations using transmission electron microscopy, however thin foils undergo a spontaneous transformation in all conditions except the equilibrium (a + ß) structure. This transformation has been reported previ0usly10,11 and we will comment on its morphology and nature in the various sections of experimental results. EXPERIMENTAL The compositions in wt pct of the two alloys investigated were: Ti:11.6 Mo, 0.100 02, 0.006 N2, 0.0015 H2 Ti:20V, 0.0574 O2, 0.0111 N2, 0.005 H2 These alloys were cold-rolled to 0.020 in. thick sheet. Specimens were heat treated in vacuum or in inert gas at temperatures >500°C and in a circulating air furnace at temperatures <500°C. Thin foils were prepared using standard techniques, described in detail previously." Dark field micrographs were obtained using high resolution technique. RESULTS Martensitic Transformation in Ti:11.6 pct Mo. Detailed study of the deformation induced martensite is not possible due to a spontaneous transformation which occurs near the edge of thin foils as shown in Fig. 1. Similar transformations have been observed in iron-" and copper-base13 alloys as well as other titanium alloys, but some observations specific to the Ti:1l.6 Mo alloy are listed below. a) The boundaries of these transformed regions are glissile and move under the influence of the electron beam during examination. b) Selected area diffraction indicates the transformed regions have the same structure as the matrix, being separated by tilt boundaries. The misori-

Jan 1, 1969

By C. E. Lesher

THE Disco* process for the production of low temperature coke and its immediate predecessor, the Wisner or Carbocite process have been described in the voluminous literature of low temperature carbonization.1 This paper will describe the development of the process from the first attempt at commercial operation by the American Gas and Electric Co. at Philo, Ohio, Yn the 1920&apos;s to the successful operation in 1949 by the Disco Co., a division of the Pittsburgh Consolidation Coal Co., of the 1000-ton per day Disco plant near Pittsburgh, see Figs. 1-2. In the 1924 coal industry depression following the hectic post World War I expansion, the northern Appalachian, unionized bituminous coal fields were affected first and foremost, and Western Pennsylvania as hard as any. Competitive market pressure was heaviest on the lower grades of steam coals, notably the from the Panhandle district where ash and sulphur are inherently higher than in the same Pittsburgh coal bed to the east along the rivers. The firm structure of Panhandle coal while favoring the prepared sizes, depressed the usefulness and value of the finer sizes. Panhandle slack and nut slack were marketed with difficulty at consistent, and at times considerable, loss. Many solutions were suggested, and the Pittsburgh Coal Co. investigated all. Lower delivered prices through lower mine costs and more advantageous freight rates were obvious goals, but equally obvious were the difficulties of self attainment of either in any substantial measure. Selling Btu&apos;s in pipes was abandoned as an idea after a thorough study of the economics of distribution of what was then, and is even now, the only developed continuous process of complete gasification of bituminous coal-producer gas. Although the coal company purchased huge blocks of electric power, it sold not a car of coal to the central power stations. Public utilities controlled the markets for electric current, and it was found that no matter at how low a cost current might be put on the bus bars by the coal company, distribution to its widely scattered coal mines made such an enterprise practically impossible. Consolidation of underground operations and a huge modernization program of mining operations in the 1920&apos;s were but preparation for the introduction of mechanical cleaning of the coal for market, particularly the smaller sizes of steam, gas, and by-

Jan 1, 1953

By C. E. Lesher

THE Disco* process for the production of low temperature coke and its immediate predecessor, the Wisner or Carbocite process have been described in the voluminous literature of low temperature carbonization.1 This paper will describe the development of the process from the first attempt at commercial operation by the American Gas and Electric Co. at Philo, Ohio, Yn the 1920&apos;s to the successful operation in 1949 by the Disco Co., a division of the Pittsburgh Consolidation Coal Co., of the 1000-ton per day Disco plant near Pittsburgh, see Figs. 1-2. In the 1924 coal industry depression following the hectic post World War I expansion, the northern Appalachian, unionized bituminous coal fields were affected first and foremost, and Western Pennsylvania as hard as any. Competitive market pressure was heaviest on the lower grades of steam coals, notably the from the Panhandle district where ash and sulphur are inherently higher than in the same Pittsburgh coal bed to the east along the rivers. The firm structure of Panhandle coal while favoring the prepared sizes, depressed the usefulness and value of the finer sizes. Panhandle slack and nut slack were marketed with difficulty at consistent, and at times considerable, loss. Many solutions were suggested, and the Pittsburgh Coal Co. investigated all. Lower delivered prices through lower mine costs and more advantageous freight rates were obvious goals, but equally obvious were the difficulties of self attainment of either in any substantial measure. Selling Btu&apos;s in pipes was abandoned as an idea after a thorough study of the economics of distribution of what was then, and is even now, the only developed continuous process of complete gasification of bituminous coal-producer gas. Although the coal company purchased huge blocks of electric power, it sold not a car of coal to the central power stations. Public utilities controlled the markets for electric current, and it was found that no matter at how low a cost current might be put on the bus bars by the coal company, distribution to its widely scattered coal mines made such an enterprise practically impossible. Consolidation of underground operations and a huge modernization program of mining operations in the 1920&apos;s were but preparation for the introduction of mechanical cleaning of the coal for market, particularly the smaller sizes of steam, gas, and by-

Jan 1, 1953

By J. Rogers. K. L. Sutherland, E. E. Wark, I. W. Wark

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts &apos;he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

By E. E. Wark, I. W. Wark, J. Rogers. K. L. Sutherland

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts &apos;he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

By L. D. Wooddy, W D. Moore

Water drives may be natural or artificial. For the case of a natural water-drive reservoir, the volume of water influx corresponding to reservoir pressuve-production history may be calculated by means of the material bal-ance-unsteady state equation. For the artificial water drive or pattern injection water flood, the material balance equation is sufficient to determine the reservoir pressure-production, injection history. However, for both cases to reliably predict reservoir performance, it is necessary to calculate the saturation distribution of the reservoir fluids at different stages of depletion. This paper consolidates the various equations used to determine the performance of water-drive reservoirs into one approach that is applicable to any reservoir that has a natural water drive or is to be produced by water injection. The numerical procedure has been simplified considerably, and the solution is adaptable to either hand calculations or digital computer operation. INTRODUCTION A water-drive reservoir is one in which the predominant source of energy for production of oil results from the encroachment of water into the oil zone. The water drive may be either natural or artificial. Water invasion takes place by expansion of water in the aquifer as a result of the pressure decline transmitted from the oil reservoir. Because water is practically incompressible, a natural water drive requires an extensive aquifer containing a volume of water many times the volume of oil in the reservoir. Provided the permeability of the formation is reasonably high, a moderate decline of reservoir pressure usually causes adequate water influx. If the reservoir pressure decline becomes excessive because of low permeability or a high rate of production, part of the oil production may result from the liberation of dissolved gas which may cause excessive quantities of free gas to be produced along with the oil. In extreme cases, reservoir pressure may decline so rapidly as to cause the oil to be produced predominantly by dissolved gas drive, leading to abandonment of the reservoir before the advancing water has had a chance to flush the entire reservoir. In reservoirs that are not connected to extensive aquifers, an artificial water drive may be created by injecting water into or around the lower edges of a reservoir. Sometimes water is injected within the reservoir through wells interspersed among the producing wells. When injection is carried out in such fashion, the reservoir is in effect subdivided into a number of separate producing segments, in each of which the displacement of oil is simultaneously taking place, and the shapes of which are fixed by the well patterns employed. Because of the natural tendency of oil and water to segregate according to their relative densities, water will tend to migrate downdip regardless of where injected. Accordingly, the injected fluids can be retained within the intended reservoir segments only when conditions are unfavorable to their migration under the force of gravity. Pattern injections are usually confined, therefore, to reservoirs having low structural relief, or low permeability, or when production and injection rates are such that fluid movements in the reservoir are dominated by the pressure gradients rather than by the force of gravity. In the case of natural water-drive reservoirs and artificial water-drive reservoirs in which the water is in-

Jan 1, 1958

By M. Hansen, C. C. Wang

THE 6 phase of the Cu-Sn system (Cu,Sn, = 32.53 pct Sn) was considered to be stable down to room temperature until Owen and Iball showed by X-ray analysis that it undergoes a eutectoid decomposition into the a and e phases at a temperature near 300°C. Their findings have been confirmed by other investigators,2-5 a11 of whom used X-ray diffraction studies of powdered specimens. The transformation temperature has been reported by various authors as lying between 300" and 380°C. To our knowledge, no microscopic evidence of the eutectoid reaction has been published, as yet. It was in connection with other work that longtime annealings at 300°C were conducted with alloys containing 22, 32.6, and 35 pct Sn (nominal compositions) prepared from electrolytic copper and electrolytic tin and cast in a small iron mold. The specimens were first annealed at 700°C for 5½ hr and quenched from 400 °C after cooling to, and annealing at, that temperature for 9½ hr. After this treatment the sample with 22 pct Sn was cold worked for 15 pct reduction in thickness; the 32.6 and 35 pct alloys were too brittle to be cold worked. The final anneal at 300°C was done in a sealed pyrex glass bulb for 63 days. Fig. 1 represents the microstructure of the annealed alloy with 22 pct Sn. It shows primary a solid-solution crystals in a matrix of the (a + 8)-eutectoid formed at 520 °C. The a crystals contain 8 inclusions which precipitated from a due to the decrease in the solubility of tin in copper with fall in temperature. The decomposition of the 8 phase into a (light) and E (dark) can clearly be seen in some areas of the (a + 8)-eutectoid matrix. However, the decomposition is far from being completed, even after the long-time anneal used. Figs. 2 and 3 depict the microstructures of the annealed 32.6 pct alloy, which was intended to consist entirely of 6 phase. Due to some loss in copper on melting, the composition is slightly higher in tin. Accordingly, the sample after quenching from 400 "C consisted of grains of the 8 phase with the e phase arranged along the grain boundaries and as a Wid-manstatten precipitate within the 6 grains. After an annealing time of 63 days, the eutectoid decomposition, 6 + a + e, is still in its early, initial state. The pearlitic type of eutectoid is nucleated at the c crystals, preferably those surrounding the grain boundaries of the 8 phase. The appearance of the (a + €)-eutectoid in the 35 pct Sn alloy was very similar to that shown in Figs. 2 and 3. Again, the eutectoid decomposition nucleated at the 6 phase and proceeded from there into the 8 areas. As is evident from Fig. 2, the rate of decomposition of the 6 phase at 300°C is extremely sluggish: In the representative area shown only about 5 pct of the 8 phase has undergone the eutectoid trans- formation after annealing for 63 days. On the other hand, Owen and Williams2 have reported that X-ray photographs of powdered samples with between 17.5 and 34 pct Sn did not show 8 lines after annealing for only five to seven days at 300°C. This is in accordance with the fact that the rate of reaction in powdered samples is higher than in massive specimens, as a result of the excess free energy of the powder (due to its greater surface area). The authors wish to express their thanks to C. A. Johnson for preparation of the micrographs.

Jan 1, 1952

By W. M. Reilly, Martin E. True, O&apos

A technique, equipment, and a compound have been developed and field tested for sealing tubing joint thread leaks without removing the tubing from the well. This eliminates the necessity of killing the well with possible damage to the producing formation, which could result if it were exposed to drilling mud. A thread sealing compound, developed and tested in the laboratory, is introduced into the tubing and squeezed into the joint to eliminate the leak. A high percentage of successful field applications have eflected an appreciable cost reduction in repairing leaking tubing strings in East Texas and in the Louisiana Gulf Coast area. INTRODUCTION In producing oil and gas wells the industry has been plagued with a never ending problem of tubing connection leakage. This situation is becoming increasingly more significant as more gas wells are placed on production and as higher pressures are encountered at greater depths of current drilling. Substantial progress has been made in minimizing thread leaks by careful handling and cleaning of joints and by the use of improved sealing compounds in combination with controlled makeup. But even with the use of the best known methods and sealing materials during initial makeup, occasional leaks through tubing joint threads appear inevitable. In some instances, tubing joints in high-pressure gas wells have been found to leak gas at relatively less pressure than that at which the tubing had been tested satisfactorily using liquid. Many expedients have been employed to prevent the physical replacement of tubing when leaks have developed. Perhaps the most commonly used is the sodium silicate treatment in which the solution is lubricated into the tubing to form a crystalline plug in the leak. Generally, any benefit realized is of a temporary nature. In addition to field studies on handling and makeup of tubing, extensive laboratory work has been undertaken on the development and testing of thread dopes.&apos; Also, substantial effort has been devoted to testing tubing joints using high-pressure gas as a pressure medium.&apos; The results of this work have emphasized that tubing joints are susceptible to occasional leaks, especially when subjected to relatively high differential pressures. To cope with the problem of leaking connections, an extensive investigation was undertaken to devise means of sealing leaks without removing the tubing from the well and without reducing the inside diameter of the tubing. The purpose of this paper is to present a technique, together with the associated equipment and compound, which have been developed for effecting a seal of leaking tubing in place. DISCUSSION Work was initiated simultaneously on two ventures: (1) to develop a satisfactory leak sealing compound and (2) to develop tools necessary to find the leak and place the compound. Leak Sealing Compound In the development of a sealing compound, tests were conducted on those compounds commercially available which include: (1) conventional thread lubricants, (2) thermo-setting resins and (3) other materials which held promise of effecting a seal. Although none proved completely satisfactory in their available form, two commercial compounds proved nearly equally effective in sealing leaks during laboratory tests after proportioned quantities of graded silica had been added. Field usage has indicated that the preferred compound is one prepared of an aluminum-stearate base thinned to the proper constituency and carrying a mixture of fine mesh graphite and graded silica. The compound developed by Humble Oil & Refining Co. is designated as Tubing Thread Leak Sealant 800. Placement Tools and Technique In developing tools to detect joint leaks and to place the sealing compound, work was done initially on wireline equipment. Preliminary designs were completed of a tool somewhat on the order of a pressure bomb to test individual joints with gas at high pressure to determine if the joint was leaking. An entirely different tool equipped with opposed packers was intended for placement of the sealing compound at high pressures in each leaking joint. The application of these tools

Jan 1, 1958

J. B. Cohen (AVCO Mfg. Co.)-The model presented by the authors is only one of several possible mechanisms for low-temperature aging. It is true that the motion of dislocations to the copper atoms, followed by diffusion along the dislocation lines, is one such mechanism. However, the details of such a process which would :result in copper-rich platelets on (100) planes in the f.c.c. matrix are not clear. Furthermore, there is at least one other mechanism that may be used to e.xplain the authors&apos; results, so that the data do not clearly favor the Turnbull model. The zones may form by "normal" diffusion. The diffusion constants would be higher at room temperature than extrapolated data would suggest due to vacancies trapped in the specimens in the quench. The diffusivity would then be multiplied by the ratio of the number of vacancies present at the solution temperature to that present at room temperature. These vacancies could remain in the alloy specimen for long times at room temerature, due to interaction with the copper atoms. &apos; The activation energy for diffusion is smaller than that for bulk diffusion at elevated temperatures for it is only that for the motion of vacancies existing after the quench; after these are used up, the aging process effectively ceases. It is somewhat questionable if the laws governing transformation kinetics can be directly applied to changes in elastic moduli, especially in the case of aging where the structure and the composition of the zones may be changing during aging, If such laws are assumed, it is possible to explain the exponential factor of % with this vacancy model. It is probable that the structure of the zones and the matrix match only on (100) planes. Certainly the precipitates that form in this system after various aging treatments show orientation relationships similar to those of the zones. Strains on the edges of the zone may set up fields which do not allow the zone to grow in an edgewise manner. The exponent in the growth of a thin plate in a direction perpendicular to its face would be %. It may also be that copper atoms are attracted to dislocations. If this is the rate-controllin factor in the growth process Ifthisthen an exponent of % or % may arise. The writer would like to know if the authors have tried plotting l/a; proportional to as might be expected for "dislocation drainage." R. H. Doremus (General Electric Research Laboratory)—An important new method for following the growth of Guinier-Preston zones is presented in this paper, and I wish to congratulate the authors on their experiments. Their interpretation of the results, however, is doubtful in certain respects. To determine the exponent m in Eq. [4] the authors plotted -log at against t to various powers (their Fig. 6). The initial value of frequency used for these plots was found by extrapolating the data to zero time. In Fig. A the data from their Fig. 2 are plotted against a linear, rather than logarithmic, time scale. To obtain graphs similar to their Fig. 6 for these data one must use an initial frequency of about 52720; such a plot for m = % is shown in Fig. B. The straight line in Fig. B fits the data in an intermediate range only. The curve drawn in Fig. A was mapped from this line; comparison of

Jan 1, 1960

By D. Turnbull, J. H. Hollomon

IN the most general sense, solidification refers to the formation of crystalline material from either a gas or a liquid. However, in this symposium, only the formation of crystals from liquids will be considered. Thus, in our present study the problem of solidification becomes that of determining the mechanism of the transition from a liquid to a crystalline solid, and our particular interest is in the transformation of metals from the liquid to the crystalline state. Metal liquids are seldom composed of only one kind of atom. Often solute atoms are added intentionally to make an alloy, or they may be present accidently because of incomplete purification. Furthermore, there may be small solid particles of various other crystals present in the liquid. Such small crystals may persist if their melting points are higher than any temperature to which the liquid is heated. Prior to solidification, the liquid metal usually is poured from one container to another. The second container, called the mold, usually is at a lower temperature than the container, or the crucible, in which the metal is liquified. The first solid that forms upon contact with the mold generally is of a different composition than the liquid, usually containing fewer foreign atoms or dissolved impurities. Heat is evolved upon solidification and is dissipated through the surroundings. Tree-like crystals, or dendrites, grow from the container walls and branch into the melt, enriching the remaining liquid in impurity atoms. In some alloys the remaining, relatively impure liquid continues to solidify until no liquid remains and the branches of the original crystal are cemented together. In other alloys, particles with a second type of crystal structure appear before solidification is complete. First the nature of the liquid and the solid states will be considered and then the mechanism of the initial formation of crystals from pure and alloy liquids. Later the problem of the growth of these crystals and the complexities of solidification in a mold, where the temperatures are not uniform and the composition of the melt changes continuously, will be discussed. LIQUID AND CRYSTALLINE STATES A liquid is an aggregate of atoms arranged with no apparent regularity (over distances of more than a few atom diameters). Nevertheless, any given atom generally has a definite number of nearest neighbors at definite distances, and thus order may be said to exist over a short range. In a crystal, on the other hand, a regular array of atoms continues for many hundreds or thousands of atom diameters, and a long-range order is apparent. Thus, a crystal having long-range order can be reproduced by linear translations for 10-5 cm or more of some fundamental unit possessing short-range order. A crude illustration of the difference between liquid and crystalline structures can be obtained by comparing the possible arrangements of oranges in a crate. If the oranges are simply dumped into the crate haphazardly until it is filled, the oranges will represent a static model of a liquid.

Jan 1, 1951

By P. Hudock

Thin films of PbS and CdS have been deposited on insulutiug- sapphire substrates by euzploying a subliwzation technique rising near-equilibriurum conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have mobilities approachitzg values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. By performing the depositiotz of a compound within a small chamber heated to a UNiform temperature within a Vacuum systerrz, it is possible to approach equiilibrium cod-tions r.~litl~irs the chamber. In this way; the sublimation and condensation proceed under near equilibrium co?zditions, and it was found that the properties of dePosited corrzpounds were similar to those of the source material. Oriented PbS films on sapphire have a roor?l- temperature unobility of 700 sq cm per v sec and a T-5/2 temperature dependence characteristic of bulk crrystnls. CdS layers on sapphive Izazse a resistivity ~uhich is corrlpamble to the resistivity of the souvce crystals over a range of four ordem of rrlagnitude. Irz contrast, Ihe resistivity of CdS films prepared by conventional evaporation depends largely upon the substrate terrzperat~ire and postheating treatrrletlt, vather than upon the properties of&apos; the solirce rrraterial. In the case oj the CdS films the achievment of high carrier mobility required the cargful exclusion of cont~~~~ii~unts from the films. The steps taken to accomplish this included presublimation of the source material, performance of the deposition at a backg-m~ozd pressure less than 10-8 Torr, and a solvent extraction with liquid cadminum, similar to that described by Aven and woodbury. The deposition of ,films under near-equilibrium conditions is being op-plied to other classes oj COmpounds. II should he of 1:allce ,tor llle deposition of nny matevial that decomposes in the vapor state. THIN films of PbS and CdS have been deposited on insulating sapphire substrates by employing a sublimation technique using near-equilibrium conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have Hall mobilities approaching values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. Depositions were performed in a small quartz sublimation cell shown in Fig. 1 that contained the compound and the single-crystal sapphire substrate. The substrates were etched in tapered solutions of hot phosphoric acid, rinsed in deionized water, dried, and transferred to the cell under dry nitrogen. Graphite crucibles and substrates were used in experiments where it was necessary to provide an inert test vehicle for the analytical determination of impurities in the source crystals and deposited films. The crucibles and substrates were machined out of spectrographic-grade graphite having less than 1 ppm of impurities. A quartz mask was sometimes used to define a pattern which could be used for Hall and resistivity measurements. Close spacing between the compound and substrate was maintained to insure better transport of each component from the source material.

Jan 1, 1968