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By Roger A. Gregg, Barry J. Piearcey

MANY of the nickel-base superalloys developed recently for use in the as-cast condition exhibit a massive "white-etching" constituent1 in the inter-dendritic regions. Commercial alloys in this category are SM 200,* IN 100, INCO 713, and Nicrotung. The appearance of a similar microconstituent in nickel-rich Ni-A1-B alloys has been reported by Schijbel and Stadelmaier. Their investigation revealed that this constituent was the binary eutectic of the terminal nickel-base solid solution and the inter metallic based on Ni3A1. This binary eutectic is degenerate and NhA1 is the major phase. At lower temperatures the eutectic composition lies within the NkA1 phase field and under equilibrium conditions is single-phase NisAl. Taylor and F&apos;loyd3 have shown that in Ni-Al-Cr alloys containing at least 8 at. pct Cr, liquid compositions which solidify by the eutectic reaction in the nickel-rich portion, precipitate nickel-base solid solution and NiAl rather than nickel-base solid solution and NkA1 in the binary Ni-A1 system. Since the nickel-base alloys contain chromium in excess of 8 at. pct and are further alloyed with one or more of the elements titanium, cobalt, molybdenum, or tungsten, it is possible that the eutectic could contain NiAl rather than NisAl. In addition, Benson4 has reported that in low-nickel austenitic high-temperature alloys, which possess Ni/(Al + Ti) atomic-weight ratios <18.0, the Ni (Al, Ti) phase may precipitate from the melt during solidification. Since SM 200 and similar high-temperature materials were developed from alloys which were designed for solution treatment, the appearance of a eutectic would indicate that the limit of solid solubility has been exceeded. The purpose of this note is to confirm that the massive white constituent in the complex nickel-base alloys investigated is based on the binary eutectic Ni + NbAl and that the limit of solid solubility need not be exceeded to produce it, in common with other observations of cast alloys. Successive polishing of a sample of SM 200 showed that, in agreement with Schobel and Stadelmaier, particles of the constituent were spherulitic and in particular were a) situated between cored dendrite arms, Fig. 1, and b) nucleated at the surface of dendrites, Fig. 2. The Ni/(Al + Ti) atomic-weight ratios for the nickel-base alloys which were observed to contain the massive eutectic constituent in the interdendritic regions are 12.1 (Nicrotung), 9.2 (IN loo), 19.5 (INCO 713), and 14.5 (SM 200). However, the results of X-ray analysis of these alloys in the as-cast condition failed to reveal the presence of the Ni (Al, Ti) phase. An electron microanalyzer was therefore employed to analyze the composition of this constituent in SM 200. The results of analyses of representative particles are as follows5: 8.4 at. pct Ti, 8.8 at. pct Co, 5.5 at. pct Cr, 0.9 at. pct W, 12.8 at. pct Al, and 63.6 at. pct Ni. Assuming that

Jan 1, 1964

By L. F. Mondolfo, W. T. Collins

A study of the relationship between undercooling for nucleation and structure in Sn-Cu alloys with 0.1 to 5 pct Cu has shown that in hypereutectic allojls the halo of tin that surrounds the primary crystals of Cu3Sn5 is larger, the larger the undercooling for nucleation o,f the tin. This increase of halo size results in a decrease of coupled eutectic, and, in alloys far from the eulectic composition, may produce its complete disappeavance, with the formation of a divorced eutectic structure. This was confirnred by the excrrnination of other alloys in which divorced eutectic slructuves are formed, and leads to the conclusion that they ave only an extrenle case of halo forrtzalion , which results when the two phases freeze one at a time and solidification of the first is completed Defove the second starts. It was also found that under proper conditions of nucleation all types of eutectic structures can be formed in the sartte system , and therefore divorced eutectics, like normal and anomalous, are not characteristic of the syslett~, but are mainly controlled by nucleatiorz. Dizlovced eutectics are formed when the phase that tutcleates the eulectic vequires a large undevcooling for ils nucleation and when the cotnpositiorz of the alloy is far from the eutectic., on the side of the primary phase that does not nucleate the other phase. It is recommended that the tevm "divorced" be used in preference to degenerate because it is more desct-iptice of the morphology and mode of forinalion of the structures. ThE variety of structures found in eutectic alloys has been extensively investigated and classified. The most accepted classification is the one by ~cheil,&apos; in which three different types of eutectic were distinguished: 1) normal, 2) anomalous, 3) degenerate (divorced). ATornlal eutectics are typified by the simultaneous growth of the two phases ("coupling") by which the two phases appear as interpenetrating crystals. The presence of a crystallization front, in which the two phases grow side by side, creates the eutectic grains, with the boundaries where the fronts meet. The presence of eutectic grains is the .distinguishing feature of a normal eutectic, according to Scheil. Straumanis and Brakss2 examined the Cd-Zn system and showed that there was a crystallographic relationship between the phases. Later, others4 also investigated additional systems and found definite crystallographic relationships in the coupled eutectics. The anornalous eutectic shows much less coupling than the normal; the two phases are intimately mixed but &apos;grow without a uniform crystallization front—a consistent crystallographic relationship— and the eutectic grain is conspicuously absent. As in the normal eutectics faster rates of growth result in a finer structure, but there is not the typical uniform spacing of normal eutectics. The degenerate eutectic shows no coupling; in fact the two phases attempt to minimize their area of contact and to form separate crystals. It has been suggested5" that slow cooling may favor this type of structure. Scheil believes that normal eutectics are formed when the two solid phases are present in more or less equal proportions, whereas both anomalous and degenerate eutectics form when one of the phases is present only in small amounts. spengler7 extended much farther this qualitative relationship between the eutectic type and the ratio of the two phases, and added a relationship to the melting point of the constituents. On this basis he proposed two equations for determining into which of Scheil&apos;s classifications an alloy belongs. The first equation is: where TI is the melting temperature of the lower-melting component, Tp of the higher-melting component, and Te the eutectic temperature. The second equations is: where is the volume percent of the lower-melting phase and $2 of the higher-melting phase at the eutectic composition. If 0 and/or 4 are in the range 0.1 to 1, a normal eutectic is formed; if in the range 0.01 to 0.1, anomalous; if less than 0.01, degenerate. Although the examples given by Spengler show a good agreement with the formulas, chadwick found that the Zn-Sn eutectic is normal to all growth rates, even though the volume ratio is 12/1, and Davies9 reports that the A1-AlgCo2 eutectic is normal, with a volume ratio of more than 30/1. Many more discrepancies of this type can also be found. Neither Scheil nor most of the other investigators have considered nucleation as a factor in the formation of divorced eutectics. Daviesg states that divorced eutectics form when neither phase acts as

Jan 1, 1965

By Alfonso Rizo-Patrón, A.M. Gaudin

Previous studies of activation in flotation have directed attention to the action of the activator on the mineral to be floated rather than to the relationship of the activator to the collector. The latter phase of the problem, however, seems to have definite scientific, if not also practical, interest. In the investigation reported in this paper, experiments were carried out, largely with quartz as subject, barium as activator, and oleate as collector. The results obtained indicate that a I: I ratio of collector ion to activator ion gives optimum results, and that a 2:1 ratio almost fails to achieve activation and flotation. Yet, a 2:I ratio would have been expected on stoichiometric grounds, had the coating been a normal salt of the activator ion with the collector ion, since barium is a divalent cation and oleate a monovalent anion. To interpret and rationalize the observations, considerations of the crystal chemistry of quartz are helpful. The point of view to which these considerations lead may be of general applicability to systems involving suspensions of solids in liquids; they confirm that an adsorbed coating is inescapable. Apparatus and Supplies The experimental work consisted in barium-ion abstraction tests, hydrogen-ion and hydroxyl-ion abstraction tests, flotation tests, and determinations of the surface of the crushed quartz. The flotation machine was built according to the design of D. W. McGlashan.* It consists of a drill press in which the bit has been replaced by a stainless-steel impellor surrounding a stainless-steel sta-tor, as in the Fagergren laboratory machine. The air intake is controlled by a valve, and the cell consists of a beaker. The quartz was obtained from vein quartz stored in large chunks. It was first crushed to 20 mesh, then sized on a 28-mesh screen. The 20 to 28-mesh size alone was retained for use. This size was freed of coarse iron by passage through a Ball-Norton magnetic separator, bleached with boiling hydrochloric acid to remove residual abraded iron, washed with distilled water until the washings were thoroughly free of ferrous, ferric, and excess hydrogen ion, and stored in covered Pyrex beakers under water until used. The barium was used as barium chloride, Baker&apos;s analyzed C. P. The oleate was used as sodium oleate. It was prepared from sodium hydroxide, Baker&apos;s analyzed C. P., and oleic acid purified by R. R. de Arellano3 in the laboratories at the Massachusetts Institute of Technology. The purification procedure was elaborated from the recent $researches of Brown and Shinowara.2 It consisted in: (I) saponification of olive oil with potassium

Jan 1, 1943

By Alfonso Rizo-Patrón, A. M. Gaudin

Previous studies of activation in flotation have directed attention to the action of the activator on the mineral to be floated rather than to the relationship of the activator to the collector. The latter phase of the problem, however, seems to have definite scientific, if not also practical, interest. In the investigation reported in this paper, experiments were carried out, largely with quartz as subject, barium as activator, and oleate as collector. The results obtained indicate that a I: I ratio of collector ion to activator ion gives optimum results, and that a 2:1 ratio almost fails to achieve activation and flotation. Yet, a 2:I ratio would have been expected on stoichiometric grounds, had the coating been a normal salt of the activator ion with the collector ion, since barium is a divalent cation and oleate a monovalent anion. To interpret and rationalize the observations, considerations of the crystal chemistry of quartz are helpful. The point of view to which these considerations lead may be of general applicability to systems involving suspensions of solids in liquids; they confirm that an adsorbed coating is inescapable. Apparatus and Supplies The experimental work consisted in barium-ion abstraction tests, hydrogen-ion and hydroxyl-ion abstraction tests, flotation tests, and determinations of the surface of the crushed quartz. The flotation machine was built according to the design of D. W. McGlashan.* It consists of a drill press in which the bit has been replaced by a stainless-steel impellor surrounding a stainless-steel sta-tor, as in the Fagergren laboratory machine. The air intake is controlled by a valve, and the cell consists of a beaker. The quartz was obtained from vein quartz stored in large chunks. It was first crushed to 20 mesh, then sized on a 28-mesh screen. The 20 to 28-mesh size alone was retained for use. This size was freed of coarse iron by passage through a Ball-Norton magnetic separator, bleached with boiling hydrochloric acid to remove residual abraded iron, washed with distilled water until the washings were thoroughly free of ferrous, ferric, and excess hydrogen ion, and stored in covered Pyrex beakers under water until used. The barium was used as barium chloride, Baker&apos;s analyzed C. P. The oleate was used as sodium oleate. It was prepared from sodium hydroxide, Baker&apos;s analyzed C. P., and oleic acid purified by R. R. de Arellano3 in the laboratories at the Massachusetts Institute of Technology. The purification procedure was elaborated from the recent $researches of Brown and Shinowara.2 It consisted in: (I) saponification of olive oil with potassium

Jan 1, 1943

News has just been received that Flight Commander William T. Hall, a Junior Member of-the Institute, was killed in action on Saturday, May 19, 1917. According to the&apos; Toronto Star, Commander Hall was 24 years of age, a native of Toronto, and a grandson of the late William Kersteman. During the four years of his course in mining at the School of Practical Science, Toronto University, he passed every examination with honors. When war was first declared Commander Hall endeavored to join the artillery as an officer, and for that purpose secured a provisional lieu- tenancy with a Hamilton battery, but he did not receive an overseas appointment, and on being graduated as a mining engineer in 1915, he was offered a position in Chile, which he accepted. He left Toronto on May 27, 1915, and was engaged in Chile as a mining engineer for nearly a year. In the latter part of April, 1916, he decided to offer himself again for service at the front. He crossed the Andes and sailed for Liverpool, where he landed on May 13, 1916. On May 27, 1916, Capt. Hall was given a commission as lieutenant in the Royal Flying Corps. He went to the front on Sept. 1, 1916, and remained there continuously. On April 4, 1917, he was promoted from lieutenant to the rank of flight commander. No details of how Commander Hall came by his death have as yet been received.

Jan 1, 1918

By Allan E. Martin, Harold M. Feder, Irving Johnson

The cadmium-uranium system was studied by thermal, metallographic, X-7-ay and sampling techniques; special emphasis was placed on the establishment of the liquidus lines, The single inter metallic phase, identified as the compound UCd11 melts peritectically at 473°C to form a-umnium and melt containing 2.5 wt pct uranium. The cadmium-rich eutectic (0.07 wt pct uranium) freezes at 320.6°C. Solid solubilities in uraizium and cadmium appear to be negligible. Between 473°C and 600°C the liquidus line is retograde. NO publication relating to the cadmium-uranium phase diagram was found in the literature. The establishment of this diagram was of considerable interest to us because of a possible application of the system to the pyrometallurgical reprocessing of nuclear fuels. Analysis of liquid samples, metallographic examination, thermal analysis, and X-ray diffraction analysis were used to establish the phase diagram from about 300° to 670°C. Particular emphasis was placed on the establishment of the liquidus lines. The same system was concurrently studied in this laboratory by the galvanic cell method.&apos; Both studies benefited from a continual interchange of information. MATERIALS AND EXPERIMENTAL PROCEDURES Stick cadmium (99.95 pct Cd, American Smelting and Refining Co.) contained 140 ppm lead as the major impurity. Reactor grade uranium (99.9 pct U, National Lead Co.) was most often used in the form of 20-meshspheres. This form was particularly suitable because it does not oxidize as readily as finer powder. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The liquid sampling technique is described elsewhere2 alumina crucibles (Morganite Triangle RR), tantalum stirring rods, tantalum thermocouple protecthecadmiumtion tubes, Vycor or Pyrex sampling tubes, and grades 60 or 80 porous graphite filters were used. Uranium dissolves in liquid cadmium rather slowly. In order to achieve saturation of the melts it was necessary to modify the procedure of Ref. 2 by the use of more vigorous stirring and longer holding periods (at least 3 hr) at each sampling temperature. The samples were analyzed for uranium by spectro-photometry (dibenzoyl methane method) or by polar- ography. The analyses are estimated to be accurate to 2 pct. Thermal analysis was performed on alloys contained in Morganite alumina crucibles in helium atmospheres. Standard techniques were employed; heating and cooling rates were about 1°C per min. For the determination of the peritectic temperature, Cd-10 pct U charges were first held for at least 50 hr at temperatures in the range 435° to 460°C to form substantial amounts of the intermediate phase. For the determination of the effect of cadmium on the a-p transformation temperature of uranium, charges of Cd-25 pct U (-140+100 mesh uranium spheres) were first held near the transformation temperature, with stirring, to promote solution of cadmium in the solid uranium. The holding times and temperatures for these treatments were 18 hr at 680°C for the cooling run and 28 hr at 630°C for the heating run. Alloy specimens for X-ray diffraction and metallographic examination of the intermediate phase were prepared in sealed, helium-filled Vycor or Pyrex tubes. Ingots from solubility runs and thermal analysis experiments also were examined metallographically. Crystals of the intermediate phase were recovered from certain cadmium-rich alloys by selective dissolution of the matrix in 20 pct ammonium nitrate solution at room temperature. Temperatures were measured with calibrated Pt/Pt-10 pct Rh thermocouples to an estimated accuracy of 0.3°C. However, the depression of the freezing point of cadmium at the eutectic is estimated to be accurate to 0.05°C because a special calibration of the thermocouple was made in place in the equipment with pure cadmium just prior to the measurement. EXPERIMENTAL RESULTS The results of this study were used to construct the cadmium-uranium phase diagram shown in Fig. 1. This diagram is relatively simple; it is characterized by a single intermediate phase, 6 (UCd11), which decomposes peritectically, and which forms a eutectic system with cadmium. The solid solubilities in the terminal phases appear to be negligible. An unusual feature of the diagram is the retrograde slope of the liquidus line above the peritectic temperature. The Liquidus Lines. The liquidus lines above and below the peritectic temperature are based on three separate solubility experiments. The data are shown in Fig. 1 and are given in Table I. It is apparent from the figure that the solubility data obtained by the approach to saturation from higher temperatures fall on substantially the same lines as those obtained

Jan 1, 1962

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram&apos; shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By Henry Schaefer

Solution by electric analogy of performance problems of reservoirs containing oil and gas has heretofore depended upon a process of successive approximations based on material-balance calculations, because of variation in fluid compressibility. By the addition or subtraction of electric condenser capacity, the analogy network can be adjusted automatically for changing compressibility due to evolution of gas in the reservoir. The addition of a condenser is accomplished by an electronic circuit, which is described; subtracting a condenser is done by merely opening the electrical circuit by means of a relay. Introduction V. Paschkis and H. D. Baker1 first developed in this country a method of applying the analogy of flow of electric current in noninductive circuits to solution of heat-flow problems and suggested its application for certain other problems, such as flow of fluids or mass transfer and chemical diffusion. Necessary details for applying the analogy to flow of fluids in porous media were developed by IV. A. Bruce;= he classified3 the types of analysis and predictions that can be made by the analogy in class I, when the reservoir contains oil but no gas for the period under consideration; in Class 2, when both oil and gas exist in the free state in the reservoir sometime during the period under consideration. Duplication of bottom-hole pressure history and predictions for class I reservoirs can be obtained directly by electric analogy. Until now, the solution of problems pertaining to reservoirs in class 2 was obtained by successive approximations along with material-balance calculations. The object of this paper is to present a method for simplifying the application of electric analogy to class 2 reservoirs, resulting in a solution of these problems as direct as is possible for class I reservoirs. This is accomplished by an electronic control circuit, which adjusts the analogy network for changing compressibilities of fluids contained in the reservoirs. Analogy Network In electrical phenomena the analogy to two-dimensional fluid flow in a porous media is that of current flow through an ideal conducting sheet. This sheet, perfectly insulated on both sides, has resistance and capacitance uniformly distributed throughout its area but is of negligible inductance. The need for having the surface boundaries perfectly insulated is that good correspondence may be had with a permeable fluid-conducting stratum bounded above and below by impermeable media. 111 actual application the ideal conducting sheet, which has distributed parameters, is replaced by a network having lumped values of resistance and capacitance—the resistances are series elements and the capacitances are shunt elements. The larger the number of lumped

Jan 1, 1947

By Henry Schaefer

Solution by electric analogy of performance problems of reservoirs containing oil and gas has heretofore depended upon a process of successive approximations based on material-balance calculations, because of variation in fluid compressibility. By the addition or subtraction of electric condenser capacity, the analogy network can be adjusted automatically for changing compressibility due to evolution of gas in the reservoir. The addition of a condenser is accomplished by an electronic circuit, which is described; subtracting a condenser is done by merely opening the electrical circuit by means of a relay. Introduction V. Paschkis and H. D. Baker1 first developed in this country a method of applying the analogy of flow of electric current in noninductive circuits to solution of heat-flow problems and suggested its application for certain other problems, such as flow of fluids or mass transfer and chemical diffusion. Necessary details for applying the analogy to flow of fluids in porous media were developed by IV. A. Bruce;= he classified3 the types of analysis and predictions that can be made by the analogy in class I, when the reservoir contains oil but no gas for the period under consideration; in Class 2, when both oil and gas exist in the free state in the reservoir sometime during the period under consideration. Duplication of bottom-hole pressure history and predictions for class I reservoirs can be obtained directly by electric analogy. Until now, the solution of problems pertaining to reservoirs in class 2 was obtained by successive approximations along with material-balance calculations. The object of this paper is to present a method for simplifying the application of electric analogy to class 2 reservoirs, resulting in a solution of these problems as direct as is possible for class I reservoirs. This is accomplished by an electronic control circuit, which adjusts the analogy network for changing compressibilities of fluids contained in the reservoirs. Analogy Network In electrical phenomena the analogy to two-dimensional fluid flow in a porous media is that of current flow through an ideal conducting sheet. This sheet, perfectly insulated on both sides, has resistance and capacitance uniformly distributed throughout its area but is of negligible inductance. The need for having the surface boundaries perfectly insulated is that good correspondence may be had with a permeable fluid-conducting stratum bounded above and below by impermeable media. 111 actual application the ideal conducting sheet, which has distributed parameters, is replaced by a network having lumped values of resistance and capacitance—the resistances are series elements and the capacitances are shunt elements. The larger the number of lumped

Jan 1, 1947

By A. E. Blakeslee

Morphological and electrical properties of GaAs epitaxial layers are influenced not only by changes in the nominal substrate orientation but also by small amounts of misorientation from the exact crystal planes. Deviations up to 5 deg from {11IA}, {11IB}, and (100) planes were investigated. Growth rates increase progressively with angle, approximately I u per hr per deg. Size and density of growth pyramids fall off with increasing angle, but other effects that are deleterious to the surface may occur which are heightened by increased misorientation. Carrier concentration decreases and electron mobility consequently increases as the angular offset increases, except in the case of strong compensation, where the mobility trend is reversed. It has long been known that changes in the crystallo-graphic orientation of the substrate may cause pronounced effects on the morphological properties of vapor grown semiconductor films. Reports of orienta-tion-dependent growth rates and surface characteristics are as old as the literature on epitaxy itself. shawl has recently published a comprehensive study of the dependence of growth rate on substrate temperature and orientation in epitaxial GaAs. It is also well-known that misorienting the substrate surface a few degrees away from the nominal low-index crystal-lographic plane often produces a much smoother epitaxial surface. This was reported by Tung2 for silicon, Reisman and Berkenblit3 for germanium, and by Kontrimas and Blakeslee4 for GaAs, and use is commonly made of this fact in the semiconductor industry to help guarantee smooth vapor deposits. The effects of substrate orientation on the carrier concentration and mobility of vapor grown GaAs were first documented by williams5 in 1964 and have been observed by several other authors since then,6,7 but no one has yet reported a careful study of how small changes influence these properties. We have made such a study and have found that sizable differences in growth rate, morphology, carrier concentration, and mobility can indeed be observed for epitaxial films grown on substrates that are oriented by progressive small increments away from the exact crystal plane. EXPERIMENTAL Early in the investigation an arsine synthesis system of conventional design8 was employed to produce growths on {111A}-oriented GaAs substrate crystals. In that early work, pronounced effects on carrier concentration and electron mobility were observed as a function of slight misorientation from this low index plane. That observation led to the more careful study that is reported here. An AsC13 system, differing in major aspect from those commonly in use today9 only in that the reactor is vertical rather than horizontal, was used for the detailed study. The gallium source was at 900°C and the substrates were at 750°C. The flow rate of pal-ladium-diffused H2 through the AsCl3 bubbler was 200 cu cm per min, and the flow rate of bypass H2 was also 200 cu cm per min. The substrates consisted of chro-mium-doped semiinsulating GaAs to facilitate elec-trical evaluation of the overgrowth by means of Hall and conductivity measurements on conventional eight-legged Hall bridges. They were misoriented by 0 to 5 deg from the {111A}, {111B}, and (100) planes, toward the (100) from the {111A} and {111B} and randomly toward the <111A> or <111B> from the {loo). The crystals were oriented for sawing by the Laue back-re-flection technique, which is good only to about ±1/2 deg; but after polishing or sometimes after epitaxial growth the wafers were checked by a diffractometer technique which is accurate to about * 0.1 deg. After lapping, the wafers were polished with NaOCl after the technique of Reisman and Rohr,10 and just before use they were cleaned in NaOC1, thoroughly rinsed with de-ionized water, and blown dry with nitrogen. Each run employed four wafers, each misoriented by differing amounts from one of the three major faces, and at least two runs were made for each orientation. The runs were continued long enough to provide at least a 15-µ or thicker layer. SURFACE MORPHOLOGY The appearance of all the films that were grown in a given run always changed from wafer to wafer as a function of increasing misorientation, but not always in the same regular fashion. At least three different trends were observed. These are more easily seen than described, and reference to the series of photo-

Jan 1, 1970

By Frank C. Greene

The year 1941 was uneventful in oil and gas development in Missouri. No new pools were opened and several areas with promising structures, in the northwestern part of the state, were disappointing when drilled. In looking for an explanation of these failures, it is suggested that it will be necessary to find areas in which the lower beds of the Mississippian are upfolded, in order to obtain production in northwestern Missouri. To do this, geophysical exploration or test drilling far enough into the Mississippian beds to get cores or cuttings of definitely established age appear to be the best methods. Although not leading to new production, drilling in Missouri established two new state records, one for depth and another for the amount of rotary drilling. An important well† in sec. 24, T. 19 N., R. 11 E., Pemiscot County, in the southeastern corner of the state, was drilled with a rotary to 4740 ft., several hundred feet deeper than any previous hole. The total footage drilled by rotary rigs of various types was 31,135 ft. and that by cable tools, 29,166 feet. The total number of completions was 85, of which 18 were gas wells with an initial open-flow capacity of 12,528,000 cu. ft., and 67 were dry holes. Of the latter, 19 were drilled into Mississippian or older formations. Table I gives a summary of activities by counties.

Jan 1, 1942

By Frank C. Greene

The year 1941 was uneventful in oil and gas development in Missouri. No new pools were opened and several areas with promising structures, in the northwestern part of the state, were disappointing when drilled. In looking for an explanation of these failures, it is suggested that it will be necessary to find areas in which the lower beds of the Mississippian are upfolded, in order to obtain production in northwestern Missouri. To do this, geophysical exploration or test drilling far enough into the Mississippian beds to get cores or cuttings of definitely established age appear to be the best methods. Although not leading to new production, drilling in Missouri established two new state records, one for depth and another for the amount of rotary drilling. An important well† in sec. 24, T. 19 N., R. 11 E., Pemiscot County, in the southeastern corner of the state, was drilled with a rotary to 4740 ft., several hundred feet deeper than any previous hole. The total footage drilled by rotary rigs of various types was 31,135 ft. and that by cable tools, 29,166 feet. The total number of completions was 85, of which 18 were gas wells with an initial open-flow capacity of 12,528,000 cu. ft., and 67 were dry holes. Of the latter, 19 were drilled into Mississippian or older formations. Table I gives a summary of activities by counties.

Jan 1, 1942

By John C. Sawyer

The mechanism of catastrophic oxidation of chromium and 446 stainless steel is examined. Data are presented to show that accelerated oxidation of these two materials, as caused by lead oxide, can occur in the absence of a liquid layer contrary to presently accepted theory. An alternate theory is proposed in which the rate of accelerated oxidation is a function of the rate at which lead oxide destroys the protective oxide formed on the base metal. An example of the application of the theory is given for the catastrophic oxidation of chromium in the presence of lead oxide. WHEN stainless iron-, nickel-, or cobalt-base alloys are heated in air to moderate temperatures in the presence of certain metallic oxides, oxidation will proceed at an accelerated rate. This phenomenon, often called "catastrophic oxidation", is most pronounced for the stainless steels. With these alloys the condition is so severe that large masses of oxide will form on the surface of the alloy in 1 hr or less at temperatures of 1200o to 1700oF. While a number of oxides are known to cause this effect, PbO, V2O5, and Moo3 are the most familiar, having been the subject of one or more investigations which have appeared in the literature.1-7 In presenting the results of these investigations, many of the authors have offered possible explanations to account for the more rapid rate of oxidation observed; however, the liquid layer theory as proposed by Rathenau and Meijering 2 has been the most commonly accepted mechanism. The liquid layer theory proposes that a low-melting oxide layer is formed on the surface of the alloy as the result of the interaction of the alloy oxide and the contaminating oxide. When the temperature of oxidation is above the melting point of the oxide on the surface, a liquid layer will form and oxidation will proceed at an accelerated rate. At temperatures below the melting point of the surface oxide, oxidation will proceed more slowly in the normal manner. It is argued that the rates of diffusion of oxygen and metal ions through the liquid layer are extremely rapid thereby accounting for the high rate of oxidation. Various experimental data have been presented to show that the temperature at which accelerated oxidation first becomes apparent coincides with the melting point of the eutectic oxide which would be present on the surface. Some exceptions have been observed, e.g., silver will oxidize in the presence of Moo3 at temperatures below the lowest melting eutectic; on the other hand, stainless steel will not be catastrophically oxidized at 1500oF in a molten bath of PbO and SiO2. In reviewing the various theories which have been used to explain catastrophic oxidation, Kubaschewski and Hopkins 8 favor the liquid layer theory, but note that, ".. .as experimental observations are not altogether in agreement with this theory (liquid layer theory), one should consider it a necessary but not a sufficient condition." In contemplating the liquid layer theory, it appears that sufficient evidence has not been presented to establish the theory beyond question. As a means of further clarification, a program of research was undertaken to determine in greater detail the mechanism of accelerated oxidation as caused by lead oxide. The first part of the program deals with a comparison of the oxidation of both AISI 446 stainless steel and chromium metal in the presence of lead oxide, vs the oxidation of these two materials in air alone. These comparisons are made at a number of different temperatures, most of which are below the melting point of the surface oxides. The second part of the program is concerned with a presentation of an alternate theory of accelerated oxidation exemplified by the system Cr-PbO-Air. PROCEDURE AND RESULTS Several experimental methods are commonly used to follow the progress of oxidation. One of these, the weight-gain method, was chosen for this work. This procedure requires that a specimen of the alloy be weighed, oxidized for a given period of time at an elevated temperature, and reweighed—the difference between the two weights being noted. The weight gain of the specimen represents the amount of oxygen acquired from the atmosphere to transform a portion of the specimen to oxide. In those cases where there is a tendency for the specimen or oxide to volatilize at the testing temperature, additional data must be collected so that a correction factor can be determined. This factor must be applied to the weight change in order to ascertain the actual amount of oxidation which has taken place. The specimens used for this work were 1 1/2 in.

Jan 1, 1963

By Philip R. Strand, O. F. Stewart

Vermiculite is the name generally applied to the group of hydrated ferromagnesian aluminum silicates that are characterized by the ability to expand when heated. This process, called exfoliation, results in a lightweight product of commercial value. Most uses of vermiculite are for the expanded material. The chief markets are in construction, agriculture, and horticulture, with lesser uses in general industry. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit, a perfect basal cleavage which causes splitting into thin laminae that are soft, pliable, and inelastic. The structure of vermiculite is basically that of a talc. The prominent monoclinic crystal faces are often marked by lines at 60° and 120°. Hardness varies from 1.5 to 2 or more; specific gravities are between 2.1 and 2.8; color varies from almost clear to amber, bronze, brown, green, or black. Vermiculite feels like talc, especially when wet. Although much research has been performed on the chemical and structural composition, there is not yet complete agreement on the exact formula. This is to be expected when different workers have examined the many different varieties. Vermiculite is not considered to be a single mineral species but a family of related minerals. The structural formula for a trioctahedral vermiculite may be written: (H20)-(Mg,Ca,K)-(A12,Fe,Mg)-(Si,A1,Fe)4O10 (OH) 2 Hydrobiotite also occurs with vermiculite and is usually considered a vermiculite for commercial uses. When heated quickly to elevated temperatures, vermiculite expands by exfoliating at right angles to the cleavage into wormlike particles. The name vermiculite is derived from the Latin vermiculare, to breed worms. This characteristic of expansion is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The decrease in bulk density of commercial grades is usually approximately 10 times, from 50 to 5 lb/ft3, but varies depending on the quality, size, and furnace efficiency. Individual flakes may expand up to 30 times. Vermiculite may also be expanded by soaking in chemicals such as hydrogen peroxide, weak acids, and other electrolytes. Color change during expansion is dependent upon the type of vermiculite and furnace conditions. Heating in an oxidizing atmosphere produces a dull gray or tan color, whereas a reducing atmosphere can produce a bronze or gold color. The expansion of the vermiculite crystal results in large pores being formed between the platelets. Thus, exfoliation makes available a large increase in void volume which is important in the application of vermiculite as a chemical carrier. Mathieson and Walker (1954) state vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation exchange capacity, organic complexing ability, and variable interlamellar distance are very similar to those of montmorillonite. The cation exchange capacity of vermiculite is one of the highest of all the clay minerals. The interplatelet space is accessible to penetration by some electrostatically neutral molecules. Water and glycerine are two common substances whose molecules may be so imbibed. In the natural state and under normal atmospheric conditions, water occupies the spaces between the silicate layers. The crystal d-spacing is near 14.2A. By differential thermal analysis, it has been determined that the water

Jan 1, 1983

By W. G. Pfann

In zone-melting, a small molten zone or zones traverse a long charge of alloy or impure metal. Consequences of this manner of freezing are examined with impurerespect to solute distribution in the ingot, with particular reference to purification and to prevention of segregation. Results are expressed in terms of the number, size, and direction of travel of the zones, the initial intermsofsolute distribution, and the distribution coefficient. IF a charge of binary solid-solution alloy is melted and then frozen slowly from one end, as for example in the Bridgman method of making single crystals,&apos; coring usually occurs, with a resulting end-to-end variation in concentration. Such coring, or normal segregation, is undesirable where uniformity is an object. On the other hand, for certain systems, it can be utilized to refine a material by concentrating impurities at one end of the ingot.&apos;. &apos; In the present paper a different manner of freezing will be examined with respect to the distribution of solute in the ingot. A number of procedures will be indicated which have in common the traversal of a relatively long charge of solid alloy by a small molten zone. Such methods will be denoted by the general term zone-,melting, while the process described in the preceding paragraph will be called normal freezing. It will be shown that, in contrast to normal freezing, zone-melting affords wide latitude in possible distributions of solute. Segregation can either be almost entirely eliminated or it can be enhanced so as to provide a high degree of sttparation of solute and solvent. A number of simplifying assumptions will be invoked which, while not entirely realizable in practice, nevertheless provide a suitable point of departure for more refined treatments. Moreover, our own experience with zone-melting has shown that, for certain systems at least, the analysis holds quite well. The present paper will be confined to a discussion of principles and a general description of procedures. Comparison with experiment is planned for later publication. Normal Freezing Before considering zone-melting, segregation during normal freezing will be reviewed briefly. If a cylinder of molten binary alloy is made to freeze from one end as in Fig. 1, there usually will be a segregating action which will concentrate the solute in one or the other end of the ingot. If the constitutional diagram for the system is like that of Fig. 2, then the distribution coefficient k, defined as the ratio of the concentration in the solid to that in the liquid at equilibrium, will be less than one and the solute will be concentrated in the last regions to freeze. If the solute raises the freezing point, then k will be greater than one and the solute will be concentrated in the first regions to freeze. The concentration in the solid as a function of g, the fraction which has solidified, can be expressed by the relation: C = kC0 (1-g)k-1 [I] where C, is the initial solute concentration in the melt. Eq 1 is based on the following assumptions: 1—Diffusion in the solid is negligible. 2—Diffusion in the liquid is complete (i.e., concentration in the liquid is uniform). 3—k is constant. Concentration curves representing eq 1 for k&apos;s from 0.01 to 5.0 are plotted in Fig. 3. This equation, in one form or another, has been treated by Gulliver,³ Scheuer,4 Hayes and Chipman5 for alloys and by McFee2 for NaCl crystals. It is derived in Appendix I. It should be pointed out that the k which is calculated from the phase diagram will be valid only in the ideal case for which the stated assumptions are correct. In all actual cases, the effective k will be larger than this value for solutes which lower the melting point, smaller for solutes which raise the melting point, and will probably vary during the beginning of the freezing process. For simplification it will be assumed that the ideal k is valid. Zone-Leveling Processes The processes of this part are designed to produce a uniform, or level, distribution of solute in the ingot. Single Pass: Consider a rod or charge of alloy whose cross-section is constant and whose composition, C2, is constant, although permissibly varying on a microscopic scale." Such a charge might be a rapidly frozen casting or a mixture of crushed or powdered constituents. Cause a molten zone of

Jan 1, 1953

By Ralph Hultgren, Bernard York, David W. Mitchell

It is a well-known fact that magnesium-alloy castings are apt to be coarse grained if the melt is not superheated several hundred degrees above the melting point before casting. (The casting temperature varies according to the shape of the mold. A typical casting temperature is perhaps 1400°F.) British practice is to heat to 900°C. (1650°F.) for 15 min., cool rapidly to casting temperature, and cast.&apos; In Germany superheating is carried out at 850&apos; to 900°C. (1560° to I650°F.) depending on the amount of scrap used. It is stated that further refinement will be obtained by prolonging the period of superheating or by increasing the superheat temperature to 950°C. (I740°F.).2 In the United States superheating is carried out at 1600&apos; to 1700°F. (871&apos; to 927°C.), perhaps even higher in some places. It is stated that superheating effects are found as low as 1500°F. (816°C.), but several hours are required.3 These commercial treatments lead to grain sizes in sand castings that may vary from 4 to 8 grains per sq. mm.! in heavy sections and from 60 to IOO in 1/2-in. sections to perhaps 380 in thin sections. It is also generally known that the refining effect of superheating is lost if the melt is held for some time at lower temperatures before casting. Aside from these very qualitative statements, there is little to be found in the literature as to the effect of temperature and time of superheat on the final grain size. Because of the uncertainty of these factors, the Office of Production Research and Development of the War Production Board placed a research contract with the University of California, supervised by the War Metallurgy Committee. This research, which was done under the "Restricted" Project NRC-550, is the basis of this paper, which has been released for publication by the O.P.R.D. The material studied was an alloy prepared from carbothermic magnesium. The temperatures required for grain refinement proved to be widely different from those used in practice, as described in the statements in the first paragraph. This difference is attributed to the fact that the magnesium in the specimens was of carbothermic origin instead of the electrolytic magnesium in common use. Materials and Methods The magnesium alloy studied was one of the most popular sand-casting alloys, with a nominal composition of 9 Per cent aluminum, 2 per cent zinc, and 0.1 per cent (minimum) manganese and the balance magnesium. This is designated

Jan 1, 1945

By William J. McCaughey, Richard L. Barrett

For sixty years—in fact, ever since the inception of the basic steelmaking process —basic slags have been the subject of study by chemists, metallurgists and petrog-raphers! with the purpose of providing a better understanding of the reactions between the slag and the metal during the refining process. The result of this work and of the researches of mineralogists and physical chemists into the chemistry of oxide systems is a considerable body of literature dealing not only with slags themselves but with equilibrium relationships in systems synthesized from pure components. Since any actual slag is a multicom-ponent system more complex than any yet worked out in the laboratory, a complete solution to the problem is still far away. The writers have recently published a paper1 which they believe sheds light on the role of the slag in the elimination of phosphorus and it is the purpose of the present paper to discuss the metallurgical applications of that work. Since the pioneer investigations on the constitution of basic slags carried on by Stead and Risdale, Carnot and Richards, Hilgenstock and others in the I88o&apos;s, a considerable body of literature on this subject has appeared. Many of the more important of these papers were summarized in the previous paper,l therefore they will not be reviewed here. PetRographic Study The present writers have had occasion, over a period of years, to examine petro-graphically a great number of basic steel-making slags having a very wide range of chemical compositions and made under various conditions of operating practice. Although certain of these slags exhibit some unusual features, it is a remarkable fact that the great majority of mature slags show certain typical characteristics, which persist throughout the wide range of chemical compositions. The typical mature slag usually appears under the microscope to consist of two phases. The phase of primary crystallization is light colored and doubly refracting. If separated mechanically and subjected to chemical analysis, it is found to consist essentially of SiO2, CaO, and P2O6. Sometimes, although not usually, two such silicate-phosphate phases are found. The other conspicuous phase is dark in color and optically isotropic, and occurs as the interstitial material between the grains of the light colored phase. This dark colored interstitial phase when analyzed is found to consist essentially of FeO, Fe2O3, MnO, and MgO. In some &apos;lags high in iron oxide, particularly those from low-carbon heats, dicalcium ferrite is found. This phase is dark reddish brown in color and anisotropic.

Jan 1, 1944

By William J. McCaughey, Richard L. Barrett

For sixty years—in fact, ever since the inception of the basic steelmaking process —basic slags have been the subject of study by chemists, metallurgists and petrog-raphers! with the purpose of providing a better understanding of the reactions between the slag and the metal during the refining process. The result of this work and of the researches of mineralogists and physical chemists into the chemistry of oxide systems is a considerable body of literature dealing not only with slags themselves but with equilibrium relationships in systems synthesized from pure components. Since any actual slag is a multicom-ponent system more complex than any yet worked out in the laboratory, a complete solution to the problem is still far away. The writers have recently published a paper1 which they believe sheds light on the role of the slag in the elimination of phosphorus and it is the purpose of the present paper to discuss the metallurgical applications of that work. Since the pioneer investigations on the constitution of basic slags carried on by Stead and Risdale, Carnot and Richards, Hilgenstock and others in the I88o&apos;s, a considerable body of literature on this subject has appeared. Many of the more important of these papers were summarized in the previous paper,l therefore they will not be reviewed here. PetRographic Study The present writers have had occasion, over a period of years, to examine petro-graphically a great number of basic steel-making slags having a very wide range of chemical compositions and made under various conditions of operating practice. Although certain of these slags exhibit some unusual features, it is a remarkable fact that the great majority of mature slags show certain typical characteristics, which persist throughout the wide range of chemical compositions. The typical mature slag usually appears under the microscope to consist of two phases. The phase of primary crystallization is light colored and doubly refracting. If separated mechanically and subjected to chemical analysis, it is found to consist essentially of SiO2, CaO, and P2O6. Sometimes, although not usually, two such silicate-phosphate phases are found. The other conspicuous phase is dark in color and optically isotropic, and occurs as the interstitial material between the grains of the light colored phase. This dark colored interstitial phase when analyzed is found to consist essentially of FeO, Fe2O3, MnO, and MgO. In some &apos;lags high in iron oxide, particularly those from low-carbon heats, dicalcium ferrite is found. This phase is dark reddish brown in color and anisotropic.

Jan 1, 1944

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1941 are available at Institute headquarters, unless otherwise noted They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS TECHNICAL PUBLICATIONS in Classes A-Metal Mining, 13-Milling and Concentration, H-Industrial Minerals, and I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every other month Technical Publications in Classes C-Iron and Steel Division, D-Nonferrous Metallurgy and E-Institute of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly TECHNICAL PUBLICATIONS in Class G-Petroleum Division are distributed in PETROLEUM TECHNOLOGY, which is issued every other month TECHNICAL PUBLICATIONS in Classes F-Coal Division, J-Mineral Industry Education Division, K-Mining Administration, and L-Geophysics, are issued as separate pamphlets An Institute member is entitled to one copy of any printed TECHNICAL PUBLICATION or CONTRIBUTION Copies of TECHNICAL PUBLICATIONS listed have been mailed to members of the Institute according to their registration by classes CONTRIBUTIONS and other TECHNICAL PUBLICATIONS will be sent upon request A member may purchase an additional copy of a TECHNICAL PUBLICATION or a CONTRIBUTION at one cent a page, minimum charge, 25¢ Nonmembers may purchase any CONTRIBUTION or a TECHNICAL PUBLICATION of the F, J, K, or L classes at the same rate, but the nonmember price per copy for METALS TECHNOLOGY, MINING TECHNOLOGY or PETROLEUM TECHNOLOGY is $1 25 domestic, $1 35 foreign countries. TECHNICAL PUBLICATIONS (separate pamphlet form), $2 per annum domestic, $2 50 foreign. METALS TECHNOLOGY, $7 per annum domestic, $7 80 foreign (Iron and Steel Division and Institute of Metals Division ferrous and nonferrous papers) MINING TECHNOLOGY, $6 per annum domestic, $6 60 foreign (metal mining, milling and concentration, Industrial Minerals Division, and mining geology papers) PETROLEUM TECHNOLOGY, $6 per annum domestic, $6 60 foreign Bound volumes have been mailed to members that have requested them, and MINING and METALLURGY Is mailed each month A member is entitled to one volume a year on his membership and he may purchase for $2 50 one copy of a volume not already received, additional copies of the same volume, $5 Nonmembers in the United States may purchase the volumes listed at $5 each, outside of the United States and its possessions, $5 6o Extra single copies of MINING AND METALLURGY, 25¢ current issue, back numbers 500 each to members, to nonmembers 50¢ current issue and $1 each, back issues Subscription price to nonmembers and to members for extra copies, $3 per annum domestic, $4 00 foreign.

Jan 1, 1941

By H. O. McLeod, J. M. Campbell

This paper presents the results of the data obtained in the first stage of a long-range study at high pressures of the system, vapor-hydrate-water rich liquid-hydrocarbon rich liquid. The data presented are for the three-phase systems in which no hydrocarbon liquid exists. Tests were performed on 10 gases at pressures from 1,000 to 10,000 psia. One of these was substantially pure methane, and the remainder were binary mixtures of methane with ethane, propane, iso-butane and normal butane. Several conclusions may be drawn from the data. 1. Contrary to previous extrapolations, the hydrocarbon mixtures tested form straight lines in the range of 6,000 to 10,000 psia which are parallel to the curves for pure methane, when the log of pressure is plotted vs hydrate formation temperature. 2. The hydrate formation temperature may be predicted accurately at pressures from 6,000 to 10,000 psia by using a modified form of the Clapeyron equation. The total hydrate curve may be predicted by using the vapor-solid equilibrium constants of Carson and Katz&apos; to 4,000 psia and joining the two segments with a smooth continuous curve between 4,000 and 6,000 psia. 3. The use of gas specific gravity as a parameter in hydrate correlations is unsatisfactory at elevated pressures. 4. The hydrate crystal lattice is pressure sensitive at elevated pressures. INTRODUCTION Prior to 1950 many studies had been made of the hydrate forming conditions for typical natural gases to pressures of 4,000 psia.""&apos;"&apos;"" Most of these attempted to correlate the log of system pressure vs hydrate formation temperature, with gas specific gravity as a parameter. One of the more promising correlations was made by Katz, et al, which utilized vapor-solid equilibrium constants. The only published data above 4,000 psia are those of Kobayashi and Katz7 for pure methane to a pressure of 11,240 psia. In the intervening years, most published charts for the high-pressure range have represented nothing more than extrapolations of the low-pressure data, with the methane line serving as a general guide. The reliability of these charts has become increasingly doubtful (and critical) in our present technology as we handle more high-pressure systems. The portion of our high-pressure hydrate research program reported here was designed to: (1) investigate the reliability of existing charts; (2) obtain actual data on gas mixtures to 10,000 psia; and (3.) develop a simple hydrate correlation that was more reliable than those which simply used specific gravity as a parameter. Binary mixtures of methane and ethane, propane normal butane, or iso-butane were injected into a high-pressure visual cell containing an excess of distilled water. Hydrates were formed and then melted to observe the decomposition temperature of the hydrates at pressures from 1,000 to 10,000 psia. EQUIPMENT The equipment consisted of a Jerguson 10,000-lb high-pressure visual cell, a 10,000-1b high-pressure blind cell and a Ruska 25,000-1b pressure mercury pump. The visual cell was placed in a constant-temperature water bath controlled by a refrigeration unit and an electric filament heater. A Beckman GC-2 gas chromatograph was used in analyzing the gas mixtures after each run was completed. EXPERIMENTAL PROCEDURE After evacuating the gas system, the heavier hydrocarbon was injected into the high-pressure mixing cell to that pressure necessary to give the desired composition. This cell then was pressured to 1,100 to 1,200 psia by methane from a high-pressure cylinder. The mixing cell holding the gas contained a steel flapper plate and was shaken intermittently over a period of 15 minutes. After mixing, the valve to the high-pressure visual cell containing excess distilled water was opened, and the gas mixture was allowed to flow into the cell. The temperature in the water bath was lowered 10" to 15&apos;F below the estimated hydrate decomposition point. As a first check, the temperature was increased at a rate of 1°F every six minutes to find the approximate point of decomposition. It was again lowered 1.5° to 5°F to form hydrates. The temperature was raised to within l° of the estimated decomposition point and then increased 0.2F every 10 to 15 minutes until the hydrates decomposed. This procedure was repeated at various pressures to obtain 7 to 13 points for each mixture between 1,000 and 10,000 psia. After completion of the hydrate decomposition tests, the gas mixture composition was analyzed with a calibrated gas chromatograph. These gas analyses have an estimated error of ± .1 per cent.