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By P. M. Robinson, J. S. LI. Leach

The heats of solution oj' indiurrr, tin, lend, nrzd tellurium have been calculated from the measured heat effects when mechanical mixtres of indium and telLuium tin and tellurium, and lead and tellurium were added to liquid bismuth. The results are in good agreement xith publislzed values.s for the separate sollction of each eleltzent in bismuth. The heats oj solution of cadmium and tellurium calculated from the rneasuved heat effects on adding trechanical mixtures of these elements do not ugree zc,itl the published values jbv the separate solution of each element. It is shown that at 623°K Ile interaction between cadmium and tellurium dissolved in liquid bismuth is strong enough to led lo preciPitation of solid CdTc. The heats oj- jor-mation of CdTe at 273" nd 623°K (1)-c crilculated fi-or the measured heat ejlfecls. The calcnlaled az'erage deviation from the Kopp-l\'ez?,zunrz rule fov solid CdTe is less than 0.06 cat per g-atom- C over this lertzperalure range. Tlze importance 0.f these oDserl.ations to the determination of heals of formation hy metal solution calorimetry is considered. LIQUID metal solution calorimetry is a convenient method for determining the heats of formation of solid compounds. In this technique the heat of formation is the difference between the measured heat effects on dissolution of the compounds and of mechanical mixtures of the components in the liquid metal.' The heat of solution of the mechanical mixture may be calculated from the measured heat effect. At infinite dilution of the solutes, this heat of solution is equal to the sum of the heats of solution of the separate components. If the heat of solution of one of the components is known, the value for the other can be derived; if both are known, they may be used to check the accuracy of the calorimetric technique. The heats of formation of the tellurides of cadmium, indium, tin, and lead have recently been measured by metal solution alorimetr. The heats of solution of indium, tin, lead, and tellurium at infinite dilution in liquid bismuth at 623"K, calculated from the measured heat effects on solution of the mechanical mixtures, are in good agreement with the published values. The heats of solution of cadmium and of tellurium calculated from the measured heat effect on solution in bismuth at 623'K of mechanical mixtures of cadmium and tellurium, however, do not agree with values estimated from the literature. 1) EXPERIMENTAL PROCEDURE AND RESULTS The Heats of Solution of Indium, Tin, Lead, and Tellurium in Bismuth. The heat effects were measured when mechanical mixtures corresponding to the compounds In,Te, InTe, In2Te3, In2Te5, SnTe, and PbTe were dissolved in bismuth. The calorimetric procedure and the method of calculation have been described elsewhere.' The heats of solution of the mechanical mixtures were obtained by subtracting the change in heat content per gram-atom of the sample between the addition temperature (273°K) and the bath temperature (623"K), (H623°K - H273°K)S, from the measured heat effects. The calorimeter was calibrated with pure bismuth. The reported values of the measured heat effects are based on (HGoK - ^273oK)Bi = 4.96 kcal per g-atom.3 The measured heat effects are found to be linear functions of the solute concentrations of the bath in the dilute solution range. The values, extrapolated to infinite dilution, are listed in Table I, together with the heats of solution of the mechanical mixtures calculated using the published values of (H 623°K - H273°k)s for indium, tin, lead,3 and tellrium. All the error limits quoted in this work represent the spread of values obtained. The heats of solution in liquid bismuth at 623°K of mechanical mixtures of indium and tellurium in four different proportions were determined. Values of the heats of solution of the two components were then calculated from the resulting four simultaneous equations: The heats of solution at infinite dilution of tin and lead in liquid bismuth at 623°K were calculated from the heats of solution of the mechanical mixtures of tin and tellurium and of lead and tellurium using the heat of solution of tellurium calculated above. These values of the heats of solution are listed in Table I1 together with some published values for comparison.

Jan 1, 1967

By H. K. Birnbaum, H. B. Aaron

he authors suggest that a number of the types of yield phenomena which have been observed in high-purity fcc metals are due to dislocation interactions bccurring at the surface of the crystals rather than due to volume effects. Since rather different inter-pretationS2,7,12,14,15,21-23 of these effects have been suggested, it is of some importance to ascertain the role of the surface in these yield phenomena. It should be first noted that the high-purity fcc metals appear to exhibit several distinct types of yield phenomena. The "unloading yield point" which is observed on reloading the specimen after removing the applied load has been found to be independent of the time of holding in the unloaded condition. If however the specimen is aged while under load and re-tested without removing the load, a yield point is observed which does depend on the aging time and tem-perature. Feng and Kramer suggest that the removal of the unloading yield point on removing sufficient material from the surface of the specimen indicates that the effect is associated with dislocation interactions at the specimen surface. Their observations are counter to those of Haasen and Kelly5 and Birnbaum.12 Since the unloading yield points are extremely small (-2 pct of the flow stress) the results of the surface removal will depend on whether the material is removed uniformly over the gage length. The introduction of small etch pits or the removal of more material from one portion of the specimen than from another will result in preferential yielding and obliteration of the yield point. With the normal electropolishing techniques it would be difficult to avoid these effects. The data obtained by Aaron and Birnbaum, Fig. 10, on aluminum polycrystalline specimens indicate that, although the unloading yield point and the strain-aging yield point are not simply additive, a time- and temperature-dependent yield point is observed under conditions where no creep is observed. This does not agree with the results of Feng and Kramer but does agree with the results on copper15 and gold.7~23 The source of the discrepancy may be the procedure used by Feng and Kramer to correct their time-dependent yield points for the effect of creep. Since the strain-aging yield point is not independent of the pre-aging strain rate, Fig. 11, the effects of creep cannot

Jan 1, 1967

By David W. James

DURING a recent investigation of the transition from a planar to a nonplanar solid/liquid interface for the systems H20-NH4F and 0-AIR,' an apparatus was developed which enabled the morphology of the ice-water interface to be examined during the transition. The slightly curved interface was viewed at a glancing angle with a Bausch and Lomb X30 stereomicro-scope. The interface was obliquely illuminated by a polarized light source. It was thus possible to differentiate between small projections or depressions at the interface, both by a shadowing effect and by the way in which they distorted the colored interference fringes across a particular crystal surface. Many attempts were made to photograph the various stages of interface breakdown. Unfortunately, the limited depth of focus of the microscope rendered the system unsuitable for photographic recording. Visual examination, however, was facilitated by continuous adjustment of the microscope focus control. The following observations of the interface transition were recorded for dilute solutions of ammonium fluoride in water. They are compared with iller's postulated morphologies shown in Fig. 1. i) The initial departure from planarity was characterized by the appearance of a large number of small depressions or "pores" in the interface. ii) The pores were arranged in wavy rows all lying roughly in the same direction within a particular grain. iii) The pores did not appear to form near to grain boundaries. iv) The pores appeared in certain grains before others. v) The transition from the pore structure to the elongated cell structure, Fig. l(d), was difficult to follow. It occurred quite rapidly and no truly irregular cell structure, Fig. l(c), was noticed. vi) The elongated cells gradually became more uniform in size and shape, with straight cell boundaries. They remained elongated, however, and no regular hexagonal cells were observed, cf. Fig. l(e). Several conclusions may be drawn from these observations. Firstly, the appearance of a poxed or, more accurately, a pore structure can be used as a criterion for the onset of constitutional supercooling. Care should, of course, be taken to distinguish between the true pore structure and artifacts caused by splashed-back liquid, particles of oxide, or inefficient decantation of liquid retained between cell boundaries, as described by Spittle et al? Secondly, and contrary to the suggestions of Tiller el l., it seems that interfacial perturbations are characterized not by curved projections but by small depressions or pores. A recent independent investigation by Biloni, Bolling, and cole5 reported in this issue indicates that the depressions might be explained in terms of dislocations intersecting the solid/liquid interface. It is possible that the dislocation concentration is reduced in the vicinity of grain boundaries. This would then explain the grain boundary depleted areas noted in (iii) above. This work was partially supported by the Air Force Office of Scientific Research, Contract No. AF 49-(638)-1029.

Jan 1, 1967

By K. E. Manchester, C. B. Sibley

The feasibility of doping silicon to produce device structres by directly implanting impurity atoms has been demonstrated. Both phosphors and boron ions have been successfully implanted in silicon to produce electrical junctions. Junctions as deep as 1.2 p have been produced by phosphorus ions having energies the order of 80 kev. An electromagnetic separator has been used to controllably produce uniform, large-area implantations for evaluation experimentation. Correlations between junclion depths and ion energies huve been obtained. Orientation effects have been observed and it has been found that the (110) direction is the easy direction for implanting. Monitoring of thermal treatments oj implanted substrates by sheet-resistance measurement indicates a very mild thermal anneal removes most of the damage done during the implantation. These indications are further substantiated by reverse-current measurements of j,inctions Produced by implantation. Electrical characteristics of implanted junctions are compared with those of diffused junctions. We have been interi n the interaction of energetic ions in the III-V groups, in particular boron and phosphorus, with single-crystal silicon to produce type conversion for possible device use. A number of investigators, a few of whom are avies, Kornelson,3 and so forth, have reported on penetration of energetic ions into both amorphous and crystalline solids. While most work has been done with ions of the rare gas and alkali metal groups, some work has been reported by ing, erber,' and others6 in which ions of the 111-V groups have been implanted in single-crystal silicon. A large amount of this work has been done with ion energies in the 100-kev to 1.5-Mev range. An excellent review article has been written by caldin. We have concentrated on ion energies which are in the 10 to 80 kev range, with which over 1500 implanted junctions such as the one shown in Fig. 1 have been produced in silicon substrates with both phosphorus and boron ions. Fig. 1 is a 3-deg angle lap in which the n type area produced by 66 kev P is delineated and the junction is 9500A below the surface. EXPERIMENTAL Implantations reported in this paper were made with the ion source adjusted to produce ion currents in the range of 1 to 2 pa with accelerating voltages varied from 10 to 40 kv. When using doubly charged ions this produced 10 to 80 kev ions. This allowed substrate temperatures to remain below 100°C. Sam- ple movement resulted in beam impingement angle variation of 7 deg from the normal to the substrate surface. Substrate resistivities have been varied through the range of 0.001 to 500 ohm-cm and specimens oriented in three directions, (110), (Ill), and (loo), within 12 deg. RESULTS For the purpose of this paper, discussion of results will be limited to phosphorus implantations with mention of results for boron-implanted silicon. Similar results have been obtained for boron and will be reported at a later date. In Figs. 2, 3, and 4 depth penetration is shown

Jan 1, 1967

By Dan McLachlan

EXPERIMENTS on ionic solids,1 Cu-A1 alloys,2 and Fe-Si alloys3 have suggested that the ability of dislocations to cross-slip is one of the most important factors governing the nucleation and growth of fatigue cracks. These experiments necessarily had to be made on materials of different composition in order to vary the propensity for cross slip. However, re-

Jan 1, 1967

Jan 1, 1967

Jan 1, 1967

Jan 1, 1967

By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967

By R. Priestner, R. F. Krause

Solid, cylindrical crystals of a iron have been fractured at 10°K by the simultaneous application of tension and torsion stresses. Thus, a complex distribution of normal (sN) and shear (ss) stresses existed in a cleavage plane at fracture. In every crystal the clearage-plane normal was inclined to the specimen axis, so that a unique point, M*, in the operative cleavage plane was defined where the quantities sn and s2 N + s2 S) were maximized. It is shown that the maxirrzum resolved normal stress on the cleavage plane at fracture decreased as the resolved shear stress in the cleavage plane at M* increased. Thus, a normal stress la?*! for fracture was not satisfied. A fracture law which takes shear stress into account. and which predicts that (s2 N +s2S) should be constant, is to be preferred. However, the data is best represented by a linear dependence of sN on sS, sS which 110 physical significance can be attached. It is suggested that the fracture-nucleating -mechanism is a short-range one. A critical stress law has not yet been unequivocally established for the propagation of cracks in metals. Measurements of the tensile fracture stresses of variously oriented zinc single crystals1 failed to establish the normal stress law expressed by In Eq. [1], sN is the fracture stress, P, resolved normal to the fracture plane, and 0 is the angle between the fracture -plane normal and the stress axis. Similarly, a comprehensive investigation failed to verify the normal stress law for the tensile fracture of a-iron single crystals.' However, a subsequent investigation,3 using iron from the same ingot, presented fracture data which obeyed the normal stress law. It has been shown previously4,5 that the Griffith criterion for fracture6 does not predict such a normal stress law. This result is of particular significance in considering the fracture of metals, such as zinc and iron, which may fail by cleavage. In these metals fracture propagates in a well-defined "cleavage" plane, whether or not an applied stress is normal to it. When the cleavage-plane normal deviates from the direction of application of a uniaxial stress, for example, the crack propagates under the combined action of normal (sN) and shear (ss) stresses. When the presence of a resolved shear stress in the crack plane is taken into account, the Griffith criterion is expressed by4

Jan 1, 1967

Jan 1, 1967

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By E. Bicknese, R. Clark

The mechanism and rate of reduction of FeO at conditions similar to those in the stack of a blast furnace have been determined for temperatures from 980" to 1165°C. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal in a static system (no flow of reducing gas) have shown that the CO2-CO ratio of the product gas depends upon the relative reactivities of the Fe2O3 and charcoal. In a systern with a "hot blast" of CO and Nz (simitar to dry bosh gas), synthetic FeO, and actiuated coconut charcoal, the rate of reduction was not sensitive to the flow of reducing gas, and the rate-controlling step alas the chemical reaction at the metal-oxide interface. Wherz solid carbon was not present, a critical flow rate of reducing- gas had to be met in order to prevent a lowering of the reduction rate. The effect of a less-reactive carbon (blast-jurnace coke) and of a "natural" FeO on the mechanistn and rate, and the mininum amount of carbon necessary in the charge to tnaintain the reducing potential of the gas phase, have been determined. THE importance of iron oxide reduction processes has encouraged many studies of the process reaction kinetics. Despite this, the mechanism is not well-understood and three main theories have evolved, which can be stated as follows: A) the rate-controlling step is diffusion, either gaseous diffusion of the reductant or product gas through a porous solid,' or solid-state diffusion of iron and oxygen atoms through the so1id.2 B) The slow step is diffusion of reducing gas through a stagnant boundary layer. C) The reaction rate is controlled by the chemical reaction occurring at the metal-oxide interface and is proportional to the area of this interface.3 By increasing the velocity of the reducing gas to a flow rate beyond which no increase in the reduction rate is observed, critical flow rate, it may be possible to eliminate B as the slow step. However, as warnere points out, the establishment of a critical flow rate may only assure that the reaction is not limited by a reduction in the reducing potential of the gas and that B may still be the rate-determining step. Edstrom and Bitsianes and Seth and Ross8 show that A and C may both be correct for the reduction of the same oxide, depending upon the stage of the reduction, and that the relative importance of the two mechanisms varies with the porosity of the oxide. Themelis9 has derived expressions which express A, B, and C in terms of the fraction reduction, Rx, of a spherical particle. Thus, in the case of A a plot of In (1 - Rx) vs time must be linear and the time to reach a given reduction is proportional to the square of the particle diameter. For B a plot of (1 - Rx) vs must be linear and the time to reach a given reduction is proportional to the square of the diameter. For C a plot of 1 - (1 - RX)1/3 vs f must be linear and the time to reach a given degree of reduction should be proportional to the diameter. In the case of mixad controlled reactions, none of the plots are linear over their entire length. The results of previous studies, in which the rates of gaseous reduction of iron oxide were measured in the absence of carbon, may not correspond to blastfurnace practice because they ignore the effects of the Boudouard reaction. CO2 +C — 2CO The presence of carbon may alter the mechanism or the rate of iron oxide reduction through an enrichment of the gas phase by Eq. [1]. In this case, the presence of and reactivity of carbon become important. If the Boudouard reaction has no effect on the rate of reduction, the reducing gas could be supplied by some means other than the gasification of carbon at the tuyeres and carbon could, theoretically, be eliminated from the burden. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal were made to determine if the reactivity (surface area) of the Fe2O3 had any effect on the product gas composition. Two size fractions of Fe2O3 were reduced with charcoal in a static system (no flow of reducing gas). In each case the charcoal was -100 + 325 mesh and was 25 pct of the total charge. One fraction of the reagent-grade Fe2O3 was submicron in diameter. The other fraction was -100 + 200 mesh and was prepared from the former by compacting, sintering at 1300°C, crushing, and screening. In each experiment, the reaction vessel was filled with a mixture of CO and CO, which would be in equilibrium with FeO and iron at the reaction temperature. A furnace was heated to the desired temperature, the vessel was placed in the furnace, and the gaseous products of the reaction were collected and analyzed. The results of these experiments, Fig. 1, show that the gas phase associated with the submicron oxide is more oxidizing than that with the -100 + 200 mesh oxide. Therefore, in a static system, the relative rates of the reduction reaction and the gasification of carbon depend upon the reactivities of the Fe2O3 and charcoal. The reduction of FeO to iron is the most important reaction occurring in the blast furnace and is probably the slowest of the several reduction steps. The mechanism and rate of reduction of FeO in a system containing carbon and a flow of dry bosh gas have been studied. TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AlME

Jan 1, 1967

By W. L. Penberthy, H. J. Ramey

Experimental work on the combustion oil recovery process has consisted of both laboratory and field studies. Although field experiments are the ultimate test of any oil recovery process, they are costly, time consuming and difficult to analyze quantitatively. Laboratory combustion tube experiments can be opertzted far more rapidly and cheaply, but are subject to scaling and interpretation problems. This paper points out some important design problems, operational criteria and considerations in2portunt to interpretation of results. An analytical hcut model of movement of a burning front axiully along a cylinder with heat loss through an annular insulation was developed. The result was used to identify steady-state temperatrrre distributions both ahead of and behind the burning front, with and without heat loss. Results indicate potential operating limitations on the minimum burning front rielocity (or air flux) which may be used for any given combustion tube. Results also enable estimating the effective thermal diffusivity and over-all heat loss from experimental data and thickness of the brnning zone. Resu lts of operation of a combustion tube constructed recently verify this preliminary theory in the region immediately ahead of and behind the burning front surprisinRly well. INTRODUCTION Many field and laboratory studies of the forward combustion oil recovery process have been conducted since the early publications of Kuhn and Kochl and Grant and Szasz2 in 1953 and 1954. In view of the complex and costly nature of this type of investigation, it is not surprising that no complete theory of the nature of the forward combustion Drocess is yet available. However, gross effects are understood well enough that reasonable design procedures are available for planning field operations. Nelson and McNeil 3,4 have published two comprehensive papers concerning design procedures. One major consideration in planning field operations is the fuel concentration at the burning front. Fuel concentration controls air requirements — an important cost factor in forward combustion. Although fuel concentration can be estimated from field test results by various methods, results are subject to great uncertainty in view of natural limitations on experimental observations. Nelson and hlcNeil4 recommend that fuel concentration be determined from laboratory combustion tube studies. Fuel concentration is only one of many important factors which can be studied by combustion tube experimentation. An obvious goal of imporrance must be development of a comprehensive theory of the forward combustion process. If a theory of this process can be established which matches controlled laboratory experimentation, it should be possible to apply this theory to field operating conditions with some confidence. Laboratory combustion tube studies have already yielded important information concerning the combustion process. However, details concerning the design, construction and operation of combustion tubes are rare. Combustion tubes used by various investigators vary in size, length and mode of operation. Therefore, one purpose of this paper is to present considerations important to design, construction and operation of a combustion tube. In regard to previous combustion tube studies, attention is called to Refs. 1 through 9. These references describe a wide variety of equipment types and present a great deal of pertinent experimental data. In general, combustion tubes usually consist of thin-walled stainless steel tubes containing an oil sand pack mounted within a pressure jacket. Provisions have often been made to heat the tube ex tern a lly by separately controlled heaters to reduce heat losses. This step usually permits operation at low air fluxes (air rate per square foot burning front surface) similar to those encountered in field operations. Burning is usually conducted from the air inlet end of the tube to the outflow end. The tube orientation used has been vertical or horizontal. For vertical tubes, burning has been conducted vertically downwards. As a result of laboratory studies, many of the

Jan 1, 1967

By A. C. Losekamp, J. B. Conway

Thermal-expansion data for, tungsten, rhenium, tantalum, .molybdenum, niobium, W-25 pct Re, Ta-10 pct W, ant1 Mo-50 pct Re are presented covering the range from room tempature to 2500°C. In these measureMents, made in a resistively heated tungsten tube furnace operating in a helium atmosphere, data for rod and sheet specimens were found to be identical; in addition, arc-cast and sintered tungsten were found to yield essentially identical results. Optical rneasurenlents of thermal expansion .made in any atmosphere other- than vacuum are subject to a refraction error which can be quite substantial. Specimens tested in helium appear shorter than when tested in racuum and hence a special correction factor must be applied to the helium data in order to obtain accurate results. WHILE it is true that linear thermal-expansion data for many of the refractory metals have been measured to very high temperatures, it is also true that except in a few instances the data from various investigators are not in good agreement. This is particularly evident in the case of tantalum and niobium although some tungsten data have been reported which differ by as much as 40 pct from the data of other investigators. Due to the sensitivity of both tantalum and niobium with respect to impurity absorption during exposure to high temperatures, it is probable that this single factor accounts for the majority of the discrepancies in the thermal-expansion data for these metals. However, this same factor can probably not be employed to explain the existing differences in the tungsten data. In all probability, these are due to errors in the measurement technique, to material composition variations, or to changes which take place in the material during the heating process (e.g., additional densifica-tion resulting from heating a sintered specimen above the original sintering temperature). In view of the discrepancies which exist in the linear expansion data reported for many of the refractory metals, the current study was initiated in an attempt to resolve such differences. Also, no high-temperature linear thermal-expansion data were found to be available for several refractory metals. Providing such data was another objective of the current investigation. MATERIALS In this study test specimens were employed in either rod or sheet form and in several instances both arc-cast and sintered material were employed. Material compositions are presented in Table I. Helium gas was fed to the furnace at a rate of about 0.5 SCFH and no special purification procedures were employed. However, the helium contained less than 50

Jan 1, 1967

Jan 1, 1967

By K. E. Starling

Phase equilibria data were used to develop an equation-of-state correlation for complex hydrocarbon mixtures, thereby circumventing difficulties associated with use of pressure-volume-temperature data. Equilibrium phase data for two condensate reservoir fluids were used to determine equation-of-state parameters for hydrocarbons as heavy as C22H46 in a modified form of the Benedict-Webb-Rubin equation of state. Comparative tests of K-values from the resultant correlation were made with data for condensate reservoir, separator and gas plant absorber mixtures. Generally, for temperatures above OF and computed liquid densities below 0.55 Ib-mole/cu ft, the modified BIVR equation predicted K-values in close agreement with the experimental data. INTRODUCTION Accurate predictions of thermodynamic behavior for complex hydrocarbon mixtures are necessary for many calculations in the petroleum industry. Because of the relatively high cost of extensive experimental data, many correlations for prediction of phase behavior have been developed. Some of these, such as the correlation of K-values presented in the NGAA Equilibrium Ratio Data Book, are totally empirical.l Others, such as the Benedict-Webb-Rubin (BWR) equation-of-state method, are semitheoretical.2-4 Unfortunately, published correlation methods often do not accurately predict the phase behavior of complex hydrocarbon mixtures, principally because of inadequate representation of the effects of components heavier than decane. This paper presents a new approach to this problem in which basic equation-of-state relations including heavy hydrocarbon effects are applied. Equilibrium phase data for two condensate reservoir fluids containing hydrocarbons as heavy as C22H46 are used to correlate component K-values. The BWR equation was chosen as the prototype equation of state for this study because of its proven capability for accurately predicting phase behavior and thermodynamic properties of light - hydrocarbon mixtures? Research was directed toward development of BWR parameters for the heavy hydrocarbons and modifications of the mathematical form of the BWR equation for application to complex hydrocarbon mixtures. The new equation-of-state approach presented differs considerably from previous methods in that phase equilibria rather than PVT data are used for determination of equation-of-state parameters. It is an explicit approach since the parameters are determined directly from mixture data. As such, it does not encounter problems inherent in the implicit method used by Benedict, Webb and Rubin 2-4 and numerous other investigators—one in which mixture parameters were postulated to be functions of the pure component parameters. The pure component BWR parameters, in turn, were determined from experimental PVT data. This method has been limited to mixtures containing components lighter than decane because of lack of vapor phase PVT data. Studies have been reported in which BWR parameters have been determined explicitly from PVT data for binary mixtures.6-8 However, since small concentrations of heavier components have only a minor effect on PVT behavior, it is doubtful that these explicit methods would yield useful results for condensate systems. Ellington and Eakin9 have shown that the accuracy of K-values predicted by an equation of state developed from mixture PVT data probably would be more than an order of magnitude lower than the accuracy of the PVT data. On the other hand, an equation of state utilizing parameters developed from phase equilibria data should predict K-values with accuracy comparable to the accuracy of the experimental phase compositions. This work applies this explicit approach with the objective of improving hydrocarbon mixture phase behavior predictions. Results are evaluated by comparing predicted and experimental K-values at reservoir, separator and gas plant

Jan 1, 1967

By Mark J. Klein

The behavior of nitrogen in Cr-0.12 at. pct Y was studied in specimens of varying interstitial concentration and thermal history. It was found that soluble nitrogen can be introduced into this alloy by increasing the concentrations of either oxygen or nitrogen. For low nitrogen concentrations the nitrogen in solution is low relative to that in unalloyed chromium. However, the nitrogen in solution increases with increasing nitrogen concentration, approaching that in unalloyed chromium. When the alloy is supersaturated with nitrogen, the nitrogen precipitates readily from solution as a chromium nitride. The stress -induced relaxation of nitrogen is influenced by internal oxidation or internal nitrification of this alloy. THE addition of small concentrations of reactive elements such as yttrium have been found to enhance the low-temperature ductility of chromium.&apos; However, the mechanism by which the ductility is increased is not known. It has been suggested that this effect is caused by a drastic reduction in the concentration of nitrogen retained in solution and therefore a decrease in the number of dislocations locked by nitrogen, a factor that has been associated with an increase in ductility.1,2 However, a change in the type of interstitial precipitate induced by yttrium could also contribute to enhanced ductility of the alloy, since chromium nitride precipitates appear to be embrittling.&apos; In this regard, it has been shown that yttrium scavenges nitrogen in chromium to form YN,4 thus reducing the embrittling chromium nitride phase. However, the change in nitrogen solubility induced by yttrium and the partition of nitrogen between chromium and yttrium nitrides are not known. The object of this investigation is to study the effect of yttrium on the behavior of nitrogen in chromium to obtain information relevant to the mechanism by which scavengers enhance the ductility of chromium. EXPERIMENTAL PROCEDURES The experimental procedures used in this investigation have been described in detail elsewhere.5,6 Wires of Cr-0.12 at. pct Y, 15 cm in length and 1 mm in diam, were drawn from rods 0.6 cm in diam supplied by the General Electric Co. The grain size of the wires after recrystallization at 1150°C was somewhat nonuniform, varying from 0.006 to 0.06 mm in diam. The interstitial analysis for the wires in ppm by weight was about 160 0, 80 N, 12 C, and <2 H. Heat treatments were carried out after encapsulation of the specimens in quartz tubes containing argon. Changes in interstitial concentrations, or interstitial "loading" as it is termed in this study, were generally accomplished by annealing in oxygen, ammonia or methane at 1150°C. The internal friction was measured using a conventional torsional pendulum enclosed in an evacuated chamber. Electrical-resistivity measurements were made at liquid-nitrogen temperature.

Jan 1, 1967

By J. L. Huitt, D. K. Lowe

This laboratory flow study covers propping agent transporl in horizontal fractures as influenced by the characteristics of the propping particles, fluid and fracture. Correlations are presented for the transport of particles, deposition and fingering through dunes. For particles moving individually, the article velocity in some cases may be low compared to the hulk average fluid velocity; in other cases, the particle velocity may exceed the bulk average fluid velocity. At high propping agent concentration or low fluid velocity, the likelihood of particle deposition and dune formation increases. Fingering and channeling accompany dune formation. Dune formation can be limited to the outer region of tile fracture by adjustment of pump rate, fluid viscosity and particle concentration. A method is presented by which pump rate and fluid vircosity may he selected to control dune formation for given propping agent concentrations. INTRODUCTION The area and flow capacity of a fracture predominantly control the stimulation derived from hydraulic fracturing. Generation of fracture area exposes the rock matrix to a flow channel; the flow capacity of the fracture controls the flow through the channel to the wellbore under a given pressure gradient. This paper pertains to an important factor that affects the flow capacity of a fracture: the transport of the propping particles in the fracturing during the hydraulic fracturing treatment. With a better understanding of particle transport, fracturing treatments may be designed to obtain more effective distribution of the propping agent. RELATED STUDIES In recent years, the approach to obtaining high fracture flow capacity has been partial monolayer propping. Three papers1-3 have dealt with various facets of this concept. However, in some papers dealing specifically with particle transport, the results generally indicate that packing the propping particles within a fracture is inevitable. In early work&apos; with a sand slurry flowing in a pie-shaped flow cell, qualitative results showed that particle deposition in a fracture during transport should be expected. In other studies"" correlations based on slurry flow in vertical linear flow cells showed particle deposition was primarily a function of fluid velocity. In a recent paper the rate of sand advance (movement of dunes) in a horizontal linear flow cell was discussed. Subsequently, a method was given for designing fracturing treatments, based on the extent of sand advance during a treatment. In this work, particles whose diameter was small relative to the fracture width (i.e., dl W< 0.2) were primarily considered. The particle transport approaches that of sand transport in a stream bed. The industry trend, however, has been to use larger size propping agents. That is, particles with diameters approaching fracture widths predicted by Perkins and Kern.&apos;&apos; This trend has led to generally better fracturing treatments with particle relative sizes in the range 0.2 <d/W < 1.0. In all of the particle transport studies previously cited, the fluid characteristics were discussed. However, little or no attention was given to the parzicle characteristics. In this study the particles. as well as the fluid and fracture, are considered. VARIABLES AFFECTING PARTICLE TRANSPORT In the exploratory work to set LIP a program for this study, it was noted that particles within a batch moved at different velocities in a horizontal linear flow cell. In some cases the particles moved independently. In others there was particle interference. Also, particle deposition and fluid fingering occurred in some cases (Fig. 1). As a result of observing the easily distinguishab&apos;le types of particle movement, the particle variables as well as the fluid variables were included. In addition, the fracture width was included because the fluid velocity profile surely must affect the movement of the larger particles differently than that of smaller particles. Particle variables were density, diameter (based on a sphere of equal volumetric displacement), long and short dimensions, drag coefficient and velocity. Fluid variables were density, viscosity, yield shear strength and velocity. Fracture variables were the width and the angle between the plane of flow and a horizontal plane. Two factors which may prove to be important were omitted because of the complexity resulting from the parameters cited above. These are the fracture-surface roughness and gross irregularities that cause changes in the direction of flow. EXPERIMENTAL EQUIPMENT AND PROCEDURE A linear parallel-plate flow cell (Fig. 2) was used in the study. Lucite plates 1 in. thick formed the test section and permitted a viewing section 11 ft long and 10 in. wide. Spacing between the plates was adjusted with shims to give fracture widths 1/36 to 1/2 in. The model could be tilted to an angle of 45" with the horizonltal plane. Fluid flow was maintained with a Moyno positive displacement pump. Single particles were placed in the flow stream with a particle injector. A .4 - in. diameter plunger moving at a constant rate in a

Jan 1, 1967

By Richard I. Petritz

A brief review of today&apos;s processing of integvated circuits is given. The major trends in the development of advanced integvated electronics are identified as 1) the broadening of the integvated circuit concept to a large class of circuit function, 2) the processing of more complex circuits within relatively small chips of silicon, and 3) the processing of very large electronic functions on complete slices of silicon. This latter trend, called array technology, is then developed in detail. Emphasis is given to defining the key tech-nological problems. Current progress being made is illustrated. THIS paper will endeavor to identify the major trends in advanced integrated electronics technology. One of these, array technology, will be developed in some detail. The array technology discussion will identify the key problem areas. Since it is the scope of the entire meeting&apos; to present specific progress in the science and technology of integrated electronics, we shall indicate general directions being explored rather than discuss comprehensively solutions to the problems. In order to set the stage for the discussion of future trends in integrated-electronics technology, let us briefly compare the processes by which circuits are fabricated through discrete-device technology with that of integrated circuits technology. The reader is referred to the December 1964 issue of Proceedings of IEEE2 for a comprehensive review of integrated electronics. The article3 by Jay Lathrop is an excellent discussion of integrated-circuits technology. A discussion of the history of semiconductor technology is contained in Ref. 4. A) Current Status of Integrated Electronics. Fig. 1 (top) shows the process by which circuits are constructed from discrete devices. Key points are: 1) Slices containing large numbers of transistors or diodes are processed separately. 2) The slices are scribed into small chips (on the order of 15 mils on a side is about as small as can be conveniently handled) each chip containing one transistor. 3) Each device is specified separately—circuit -function specs are derived largely from device specs. 4) Circuits are formed by connecting together the discrete devices. 5) The number of circuit connections required is approximately equal to the number of devices. 6) There are potentially many more discrete devices per inch2 of semiconductor—only our lack of ability to handle them in discrete form prevents us from going to several orders of magnitude higher density iin Fig. 1, 400,000 transistors are discussed at 1.5 mils on a side). The bottom part of Fig. 1 illustrates the integrated circuit process. Key points are: 1) On the same slice of silicon, transistors, diodes, and resistors are processed grouped to do a complete circuit function. 2) While still in slice form, the components are interconnected into circuit functions by an evaporation process, eliminating the need for separate interconnection steps later. Dramatic improvements in cost and reliability are realized. With a simple flash of metalization thousands of interconnections are reliably made. 3) The slices are scribed into chips which contain complete circuit functions. 4) The circuit functions are specified-not each component in the circuit. This important point was missed by some of the early opponents to integrated circuitry. They argued that, with device yields at x pct, integrated circuit yields would be pct, where n is the required number of devices to make a circuit. This argument leads to extremely low yields for integrated circuits. The fallacy of the argument is that in integrated circuits each device is not specified separately. Furthermore, since a device is forever integrated into a specific circuit function, it need meet only the requirements for that particular function. Discrete devices, on the other hand, are tightly specified so that they can be applied to a variety of circuit functions. 5) Extremely high packing densities are achievable because one need only make the basic devices as large as the circuit demands. Their size is not dictated by handling requirements. A current example

Jan 1, 1967