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By R. L. Schmidt, J. D. Verhoeven

The diffusion coefficients and electrotralzsport mobilities of aluminum, gallium, and arsenic have been determined in molten germanium with the capillary reservoir technique. The diffusion coefficients are slightly higher than those determined by the solidification technique of Brirton et a1.1 It was found that aluminium and gallium migrate to the cathode in molten germanium) whereas arsenic migrates to the anode under an electric field. A possible technique for producing p-n junctions by means of electric field freezing is discussed in view of the experimental data. In the past decade or so the literature has abounded with articles concerning the solid-state properties of the semiconducting elements germanium and silicon. It is surprising by comparison how little has been published concerning the liquid-state properties of these materials. In the production of doped germanium or silicon the diffusion coefficient of the dopant in liquid germanium or silicon is an important quantity. Yet, to the best of our knowledge, no one has ever made a direct measurement of the diffusion coefficient of solutes in either molten germanium or silicon. A number of authors'-4 have determined some diffusion coefficients by the indirect technique developed by Burton et al.1 This technique appears to give numbers of the correct order of magnitude but it does depend upon a number of assumptions in the analysis and also requires prior knowledge of the viscosity of the melt. In the present work a more direct measure of the diffusion coefficients of arsenic, gallium: and aluminum in molten germanium has been made. It has been shown independently by two groups of authors5, 6 that, when an electric current is passed through the interface of a solidifying metal containing an impurity, the resulting electrotransport in the liquid boundary layer at the interface offers a mechanism for control over the redistribution of the impurity accompanying the solidification. These authors show that the degree of control is proportional to the mobility, U of the impurity atoms in the liquid boundary layer, where the mobility is defined as the drift velocity relative to the solvent per unit electric field. In principle the results apply to the solidification of a doped semiconductor and offer an interesting technique for control of the doping of a semiconductor. In the present work the mobilities of aluminum, gallium, and arsenic were determined in molten germanium in order to evaluate the potential usefulness of electro-transport as a technique for solute control when applied to the solidification of doped germanium. EXPERIMENTAL PROCEDURE Both the diffusion coefficients and the mobilities were measured using high-purity alumina capillaries and a resistivity technique for analysis. A schematic diagram of the electrotransport apparatus is shown in Fig. 1 and the details of the cell design are shown in Fig. 2. For the mobility experiments electrical contact with the bottom of the capillary was made with graphite, as shown in Fig. 2. In order to prevent electrical contact with the melt the graphite was coated with a thin layer of alumina using a plasma spray torch. The cell assembly, a graphite electrode, and another assembly containing two blank capillaries were fastened to the lavite disk shown in Fig. 1. To make a run the system was evacuated and the doped germanium was outgassed at the operating temperature of 1030°C. The cell and blank capillaries were then submerged beneath the melt and a slightly positive pressure of helium was introduced to fill them. After passing current through the cell for a given time the cell and blank capillaries were raised from the melt and the furnace was shut off. The temperature of the cells dropped below the freezing point of germanium within 1 to 2 min after the furnace was shut off.

Jan 1, 1968

By D. Havlena, A. S. Odeh

The material balance equation used by reservoir engineers is arranged algebraically, resulting in an equation of a straight line. The straight line method of analysis imposes an additional necessary condition that a successful solution of the material balance equatiott should meet. In addition, this algebraic arrangement attaches a dynamic ineuning to the otherwise static material balance equation. The straight line method requires the plotting of one variable group vs mother variable group. The sequence of the plotted points as well as the general shape of the resulting plot is of utmost importance. Therefore, one cannot progrm the method entirely on a digital computer ar is usually done in the routine solution of the material balance equation. If this method is applied, then plotting and anaIysis are asential. Only the appropriate equations and the method of analysis and interpremtion with comments and discussion are presented in this paper. Illustrative field examples for the various cases treated are deferred to a subsequent writing. INTRODUCTION One of the fundamental principles utilized in engineering work is the law of conservation of matter. The application of this principle to hydrocarbon reservoirs for the purpose of quantitative deductions and prediction is termed "the material balance method of reservoir analysis". While the construction of the material balance equation (MBE) and the computations that go with its application are not difficult tasks, the criteria that a successful solution of the MBE should fulfill have always been a problem facing the reservoir engineer. True and complete criteria should embody necessary and dcient conditions. The criteria which the reservoir engineer uses possess a few necessary but no sufficient conditions. Because of this, the answers obtained from the MBB are always open to question. However, the degree of their acceptability should increase with the increase in the number of the necessary conditions that they should satisfy. Generally, the necessary conditions commonly used are (1) an unspecified consistency of the results and (2) the agreement between the MBE results and those determined volumetrically. This second criterion is usually overemphasized. Actually, the volumetrically determined results are based on geological and petrophysical data of unknown accuracy. In addition, the oil-in-place obtained by the MBE is that oil which contributes to the pressure-production history,' while the volumetrically calculated oil-in-place refers to the total oil, part of which may not contribute to said history. Because of this difference, the disagreement between the two answers might be of paramount importance, and the concordance between them should not be overemphasized as the measure of correctness of either one. In this paper, a third necessary condition of mathematical as well as physical significance is discussed. It is not subject to any geological or petrophysical interpretation, and as such, it is probably the most important necessary condition. It consists essentially of rearranging the MBE to result in an equation of a straight line. This straight line method of the MBE solution has invalidated a few long time accepted concepts. For instance, it has always been advocated that if a water drive exists, but one neglects to take it into account in the MBE, the calculated oil-in-place should increase with time. The straight line method shows that in some cases, depending on the size of the neglected aquifer, the calculated oil-in-place might decrease with time. The straight line method requires the plotting of a variable group vs another variable group, with the variable group selection depending on the mechanism of production under which the reservoir is producing. The most important aspect of this method of solution is that it attaches a significance to the sequence of the plotted points, the direction in which they plot, and to the shape of the resulting plot. Thus, a dynamic meaning has been introduced into the picture in arriving at the final answer. Since the emphasis of this method is placed on the interpretation of the sequence of the points and the shape of the plot, one cannot completely automate the whole sequence to obtain "the best value" as normally done in the routine application of the MBE. If one uses the straight line method, then plotting and analysis are musts. The straight line method was first recognized by van Everdingen, et al,2 but for some reason it was never fully exploited. The advantages and the elegance of this method can be more appreciated after a few cases are carefully treated and worked out by it. SOLUTION OF THE MATERIAL BALANCE EQUATION SATURATED RESERVOIRS The MBE for saturated reservoirs written in AIME symbols is

By Basil B. Zavoico

ALTHOUGH the American petroleum industry was affected by the Second World War from its early beginning it was not until Dec. 7, 1941- that the industry was placed on full war footing. Even throughout most of 1942 the American overseas operations were limited and not until late in the year did expansion of military activities, more particularly the offensive in North Africa, affect the domestic supplies to such an extent that critical deficiencies developed locally in this country, particularly along the East Coast. The definite outlook for greatly expanded offensive operations by the United States on both Atlantic and Pacific fronts makes certain that during 1943 the domestic situation will. not be alleviated; rather it may become even more critical even though additional transportation facilities, now being built and planned. will be completed from the southwestern producing states to the East Coast.

Jan 1, 1943

By Foster Fraas

That variations in the humidity of the air and in the moisture content of a mixture of broken solids being separated electrostatically cause trouble is not new.' Much of the reputation for unreliability commonly ascribed to the electrostatic separation processes is probably due to this one factor alone. Some operators dry thoroughly before separating; and while this is good in many instances, there are others in which it is not the remedy for trouble. Some mixtures behave best in very dry air and with the mixtures fed to the separator while hot to reduce the adsorbed water content. On the other hand, an overdried mixture on coming to equilibrium with more humid air, has been known to take up moisture selectively on one family of particles, as of coal in the presence of slate and clay, and give sharper electrostatic separation. From these observations it is concluded that there is a permissible moisture content for a particle and also for the atmosphere surrounding it, if in equilibrium, at which the particle will have a conductivity or cntact potential2-4 that is ideal for electrostatic separation. This permissible moisture content varies between a wide range of limits for the different materials that are are and with the kind of electrostatic separating process used. Water can be present as a result of adsorption and condensation from the atmosphere, as an accumulation before or during mining, or as a residue from a previous process step. The water may exist as a liquid film or as an adsorbed layer of vapor. If the water exceeds permissible limits it must be removed. Its state determines the method. Drying by evaporation is necessary for adsorbed water, for part of the liquid-film water (that is, up to several percent of the dry weight), and for free water in the internal structure. Large water contents may be removed by drainage Or filtration. At just what point mechanical removal should cease and drying by evaporation begin depends upon the method of mechanical removal and its cost. Particles can also be separated according to their differences in dielectric constant when suspended in a liquid of intermediate dielectric constant. Recovery of this liquid presents a a problem' Permissible Moisture The adsorbed moisture on the outer surface of minerals can be quickly removed or replaced. Accordingly, in speaking of adsorbed moisture contents, either that of the solid or that of the surrounding air may be considered, the two values being connected by a distribution coefficient which varies with the temperature. However, such a condition does not necessarily exist in processes where an initially dry material is suddenly introduced into an atmosphere having a partial pressure of water vapor or where a moist material is suddenly introduced into a dry atmosphere. Here the resultant differences in the

Jan 1, 1949

By W. Lawrence Austin

It has been suggested to me that some data, bearing on the treatment of silver ores in Southern Arizona, would be in accord with the objects of the present meeting. I have, therefore, made a few notes, gathered from practical experience at some of the best known works of that district. Presuming the general arrangement of a silver mill to be familiar to members, the subject having been repeatedly brought to the notice of the Institute, it is my aim in the following description of the modus operandi at the different mills to which I would invite your attention, to give simply such salient points of the apparatus as have a direct bearing upon results, together with the cost of materials, labor, etc. I have gone somewhat deeply into detail in my descriptions of machinery, thinking that possibly some of our members engaged in this branch of the profession might find something of interest among them. In an industry such as silver milling, where the various works are scattered over a vast extent of territory, and the conditions under which results are obtained are subject to the greatest variations, it is essential to go into rather minute details in describing plants, processes, etc., in order to afford a clear idea of the operations. Not only should results be given, but also the means by which such are attained. The milleralogical and chemical constituents of the ore, and its physical properties, throw a flood of light upon the success or failure of a process Figures representing totals I have subdivided as much as possible, so that the cost per ton for labor, castings, chemicals, etc., are apparent. Unless all these Factors are known, no accurate comparison can be drawn, since in this branch of metallurgy, more perhaps than in others, the weakness of any one link in the chain of operations demoralizes the remainder. That it costs $10 to mill in one

Jan 1, 1883

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By W. F. Hower, W. Brown

Large-scale sand consolidation tests were conducted in an effort to determine the reasons for the successes and failures of this method of sand control. Several different consolidating materials were used in treating both clean and bentonitic sands that were packed in a chamber having a capacity of 3.3 cu ft. The results were essentially the same for all of the different consolidating materials, The data show that low-viscosity consolidating materials pumped at a relatively slow rate gave the best results. Where the formation has produced sand, the treating fluids can compress the formation, thus permitting the channeling of fluids to another horizon. Pressure-packing these zones before attempting to consolidate is recommended. Sands containing more than 4 per cent of water-swelling clays are not good candidates for consolidation. It is indicated that loose sand, particularly when it is bentonitic, can be fractured during the placement of the treating fluids. INTRODUCTION Sand production in oil and gas wells has plagued the industry for many years, and numerous cures for this problem have been suggested. Most methods have been successful to a certain degree, but the great variety of well conditions that exist in the different areas has magni- fied the problem and limited the successful use of the various systems. Four review papers1-4 present a wealth of information concerning the degrees of success that have been obtained by the different sand-control methods. The bridging of sand grains by the use of gravel packs and screens has been quite successful. However, these methods do not leave the casing clear for all types of multiple completions, and the cure does not last for the production life of the well in some instance:;. The control of loose sands by sand consolidation with resins has never been as successful as desired. It has always been hoped that such a treatment would eliminate all sand problems for the life of the well, but. initial applications, starting in the middle 1940's, were only moderately successful. Lott, et a1,3 reported a success ratio of approximately 50 per cent and made the following conclusions. The highest percentage of successes were obtained where: a. Consolidation of a zone was made at the time of initial completion or prior to the production of sand. b. The interval treated was less than 12 ft in length. c. Between 30 and 50 gill plastic/ft of producing interval was displaced through the perforations. REASONS FOR SAND CONSOLIDATION FAILURES Our own experiences in the field of sand consolidation point toward the following conditions as the major reasons for the failure of sand consolidation attempts. 1. Mud-plugged perforations and mud invasion of the formation. 2. Sand in the casing covering all or part of the perforations. This sand could be either formation sand or one of the coarser sands used as propping agents in hydraulic fracturing. 3. Holes in the casing. 4. Channels behind the casing. 5. Attempting to treat too long a perforated section. 6. Too high a percentage of water-swelling clays in the formation. 7. Formations that have produced sand. Recent attempts were made to treat perforated sections ranging from 10 to 30 ft, in wells that have produced sand, by using a straddle packer that was raised and lowered through the perforations as the consolidating material was being pumped. In most instances, the pressure required to pump fluid into the formation varied considerably as the tool was raised and lowered. This suggested the possibility that significant differences in permeability were present or that only part of the formation had produced sand. There were times when a sudden break in pressure indicated that a fracture was being formed. Research conducted several years ago concerning the problem of the control of water in air and gas drilling indicated that shale sections could be fractured quite easily. In addition, it was determined that it was easier to pump fluids into shale bodies by fracturing the shale itself, or the interface between the shale and sand, than to pump into a fluid-saturated formation. Formations that produce sand are usually adjacent to shale bodies and frequently have shale streaks of various thicknesses inter-bedded in the sand. Therefore, where shale is exposed to fluid pressure it

By T. D. Jones

MUCH the same story can be told for the lead industry for the year 1945 as for the three previous years. In response to inquiries as to new developments, invariably the answer has been, "No new developments-our men either too busy with the man-power problem or trying to get production out." Time and efforts of industry have been concentrated for the most part on war or readjustment problems. Now that V-E and V-1 day have passed, the lead industry can justly be proud of its record in World War II. As in previous wars, lead played an important role and one of its most spectacular uses was in the production of the atomic bomb. We read that the part lead played was rather obscure, but as a protective agent, lead played a most significant role. "Since the materials in the Pile Plant are intensely radioactive, all storage and handling must be done behind thick concrete walls or lead shields. The material is never seen and all operations are auto matically controlled by a foolproof remote control system especially designed for this purpose." (Chews. & Met., Sept. 1945.) When our armies invaded the European theater of war and made a landing on Normandy beach, gasoline and oil for the motive power were furnished through miles of armored lead pipe. This amaz-

Jan 1, 1946

By Ralph H. Sweetser

IN the recent world-wide deflation of commodity prices the coal industry, including both anthracite and bituminous coal, had reached a level where the actual delivered market prices received by the operators were usually less than the cost of production. Many steel companies and public utilities, operating their own "captive" mines, could have bought coal during the past three years for less money than the true cost of coal produced at their own properties. Competition within the coal industry itself was cruel to the point of profitless operation, and the competition of other forms of fuel was bearing heavily on the coal producers. They were thus forced into methods of production and utilization that they had hitherto ignored; there had been almost complete absence of any appreciation (by the bituminous operators especially) of the necessity of real research work in finding better methods of preparing coal for specific uses, and in finding new and profitable uses for different kinds and grades of coal.

Jan 1, 1933

By Geo. Otis Smith

Twelve years ago, the Director of the United States Geological Survey addressed to the Secretary of the Interior a letter calling attention to the government's need for liquid fuel for naval use and pointing out that the rate of increase in demand was more rapid than the increase in production.' This letter, in a way, inaugurated the policy of public oil-land withdrawals, which was well founded in its primary purpose of protecting the oil industry and highly desirable in its immediate effect of checking the over-development of that day in California. Unfortunately, however, through delays in legislation, this policy may be regarded now as having outlived both its intent and its usefulness. In 1908, the country's production of oil was 178,500,000 bbl., and there was a surplus above consumption of more than 20,000,000 bbl. available to go into storage. In 1918, 10 years later, the oil wells of the United States yielded 356,000,000 bb1.—nearly twice the yield of 1908—but to meet the demands of the increased consumption more than 24,000,000 bbl. had to be drawn from storage. Nor is this all of the brief comparison. In 1918, our excess of imports over exports of crude petroleum was nearly 33,000,000 bbl. whereas in 1908 we exported 3,500,000 bbl., which was net, as we had not begun to import Mexican oil. In this period, the annual fuel-oil consumption of the railroads alone has increased from 16,871,000 to 36,714,000 bbl.; the annual gasoline production from 540,000,000 gal. to 3,500,000,000 gal. This record may be taken not only as justifying the earlier appeal for Federal action, but as warranting deliberate attention to the oil problem of today. Need of Future Supply The position of the United States in regard to oil can best be characterized as precarious. Using more than one-third of a billion barrels a year, we are drawing not only from the underground pools but also from storage, and both of these supplies are limited. In 1918, the contribu-

Jan 1, 1921

By Wallace Pratt

INTRODUCTION IRON-ORE deposits in the Philippine Islands became the subject of official record as early as 1664. Undoubtedly iron ore was known and recognized by the Filipinos long before the earliest Spanish records. It is even possible that the Filipino practice of smelting iron ore is, like the native copper smelting, older than the Spanish conquest of the islands. The first records have to do with the magnetite-hematite ores near the towns of Santa Inez and Bosoboso in Rizal Province, from 15 to 20 miles east of Manila. The magnetite-hematite ores of Bulacan were exploited in 1783. Similar ores near the town of Mambulao in Camarines Province yielded a number of specimens to be exhibited in Spain in 1834. With the exception, then, of the lateritic iron ores on the eastern coast of northern Surigao, the true nature of which was not recognized until 1914, the important iron-ore deposits of the Philippines had all been discovered before the islands came under the dominion of the United States. Indeed, in the Spanish documents relating to the history of iron mining are statements which, if their accuracy be not questioned, leave us in the Philippines today with much less iron ore than the Spaniards found. To quote, for example, a report submitted to the Superior Government in Spain in 1835 by one of its emissaries, Don Lorenzo Calvo: "The Philippine Islands, most excellent Sir, possess iron and exhibit it in nearly every known mineralogical combination, and in such abundance that the cordillera of the island of Luzon, from Montufar Point in San Bernardino Straits to Cape Bojeador, is composed of no other mineral than iron, its ranges, of the third order, being in content and structure totally iron of the best quality, the more valuable in that its combinations are such as to facilitate its fusion and to render its reduction to metal simple."

Jan 2, 1916

By R. J. Murphy, N. J. Grant, J. W. Dowding

A large number of blast furnace slag-metal tests were examined to determine if the manganese reduction could be used as a primary indicator of the degree of oxidation or reduction of the slag and of its desulphurizing power. Slag basicity and temperature were also evaluated. Two laboratory heats were made and sampled prior to reaching equilibrium to check blast furnace data. IN a recent investigation of the factors affecting desulphurization in the blast furnace, is was evident that manganese reduction appeared to parallel the course of desulphurization. Grant, Kalling, and Chipman1 pointed this out in a series of time studies utilizing closely controlled laboratory melts. Fig. 1 is a composite plot of sulphur removal and manganese reduction as a function of time under two slags of different basicity. Manganese reduction appears to approach equilibrium at approximately the same rate as does sulphur. It was also demonstrated that the addition of oxygen to the slag, as manganese oxide, caused a sharp reversal of sulphur from the slag to the metal.' It has been shown that "Excess CaO" was a primary factor in measuring the degree of desulphurization under ideal reducing conditions,1,2 the following reaction being representative of the process: CaO (slag) + S + C (solid) = CaS(slag) + CO (gas) It was also evident that a second reaction could drive the sulphur from the slag into the metal. A suggested reaction was' CaS (slag) + 0 = CaO (slag) + S Any change in the oxidizing power of the system would thus affect both the sulphur and the manganese without causing any change in the calculated basicity of the slag. "Excess CaO," "Excess Base," and other similar basicity values, under such oxidizing conditions, would therefore not be the best measure of desulphurizing power; instead, as was shown by and Chipman" he oxygen content of the slag at low oxygen levels would be the controlling factor. Unfortunately, the extent to which FeO is reduced in the blast furnace makes it difficult to utilize slag FeO as an accurate indicator of the degree of oxidation. By comparison, manganese reduction in the blast furnace proceeds more slowly and is generally only about 40 to 70 pct complete. manganese, which is present in significant amounts and is readily analyzed, offers an opportun-

Jan 1, 1954

By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins' and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer' type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

L. D. Ricketts, New York, N. Y.-In recent years the metallurgical field of the copper industry has expanded greatly, the copper ores have become lean and diverse in character, and we are obliged to treat such ores on a very large scale. On the commercial side, the operating and consulting staffs of ,the great mining companies have been enlarged and organized, and no great capital expenditure is decided upon until it has been investigated and recommended by a highly organized force of specialists as a committee. I believe that in the scientific field and in the most valuable proceedings of our various societies the old idea of one-man point of view and one-man treatment of principle and detail together has been. splendidly developed and should continue, but for the advancement of our art we should deliberately discuss subjects among ourselves in order to do away with the idiosyncrasies of the individual and to gain a composite view representing the best thought of many men. In the development of new ideas leading to the introduction of new methods, the societies could enlarge their present great field of usefulness if such discussion be had, and in my opinion further great good could be done if a number of men of different qualifications and experience would join in preparing a joint book, each dealing with his particular problem, but consulting the other men. In this way individualism would be preserved and various processes would be described, and if properly reviewed the paper would be palpably capable of analysis, and the student would have at his command the associated efforts of a group of qualified engineers.

Jan 4, 1915

By W. R. Ingalls

Jan 1, 1922

By W. R. Ingalls

Jan 1, 1922

By J. H. Jackson, P. D. Frost, C. H. Lorig, L. W. Eastwood, A. C. Loonam

R. S. BUSK*—I wish first to congratulate the authors of this paper both for the work done and the presentation of that work. We have also been working on this type of alloy development, but any technical contribution I might have is better reserved for a separate paper which is planned in the near future. However, I would like to insert a word of caution. The alloys described in this paper are still very much in the laboratory stage. There still remains the quite vexing problem of property stability at slightly elevated temperatures which must be solved before the properties quoted can be effectively utilized. These alloys are extremely interesting and I am confident that the problems can be solved. However, the present existence of those problems must not be overlooked. I have one question with regard to the work-hardening test. If the work harden-ability of magnesium is compared to aluminum using a more standard test such as the Meyer Analysis the magnesium is found to work harden the more rapidly. Is the test developed for this work truly a work-hardening test or a measure of something else ? J. H. JACKSON (authors' reply)—I am sure we appreciate the comments of Mr. Busk and we are pleased that the Dow Chemical Co. has also undertaken work in this field. It is a big field. We, of course, are continuing our research for the Navy Bureau of Aeronautics, since, as clearly shown in the paper, the alloys are not completely developed. With regard to Mr. Busk's comments on the relative work-hardenability of aluminum and magnesium, the comparison we cited in the paper was intended merely to show that the results obtained by our method of testing were independent of the yield strength of the materials. We believe that this test method afforded a rough indication of the work-hardenability of the magnesium-lithium base alloys. It is not known whether this method affords greater or less accuracy than the Meyer Process, which is based upon a hardness-test impression. It is quite possible, since work-hardenability is a function of metal purity, that our results, obtained for commercial aluminum and magnesium, would be different if high-purity metals had been used. A. C. LOONAM—Lithium has some very interesting effects on magnesium. The paper showed that even small percentages increased ductility. These small amounts changed the axial ratio of the hexagonal magnesium from 1.624 in the pure metal to 1.606 in the saturated alpha solution, a value close to that of titanium, which has a ratio of 1.601. You will recall an article in the January, 1949, issue of the Journal of Metals where it was stated that titanium can be cold-rolled over 90 pct without any significant edge cracking. At 4.9 or 5 pct lithium, a change begins in crystal structure—from a hexagonal close packed to body centered cubic. There are two phases over a short range of lithium content, but at 10 pct the structure becomes completely cubic. The melting points of alloys in this range of lithium content are relatively high. Alloys even up to the six ratio have melting points above 500°C; this represents a relatively small reduction in melting point from pure magnesium itself. The magnesium-lithium system has a number of very interesting characteristics. This is only a very small part of the story. J. H. JACKSON—I would like to remind you that Mr. Loonam is one of the authors of this paper, and the fact is that this work is based on many of his ideas. I am sure we appreciate his additional comments in this discussion. R. LEITER*—I am interested in Fig 19 in which Mr. Jackson compares

Jan 1, 1950

By F. W. C. Boswell, R. L. Cunningham, H. M. Weld

Chemical analysis shows the partition of the magnesium addition between the metal and the graphite is independent of whether the graphite is in the form of nodules or flakes. The bright central spot observed in nodular graphite polished sections is shown to be due to the structure of the nodules. DURING the past few years numerous papers have been published on the production1-7 and heat treatment" of nodular cast irons. However, very little information is available on the structure of the nodules and the reason for their formation. It would appear that an explanation of the phenomenon of nodulation must await a detailed knowledge of the nature of the nodule. Disagreement exists among various workers on such a fundamental point as to whether or not a nodule actually contains a microscopically visible, nongraphitic nucleus.9-11 Work was initiated with a view to obtaining definite information on this and other aspects of the problem. Chemical Separation and Analysis Microscopic appearance had indicated9-11 that a nongraphitic core might exist in nodules (Fig. 1). It appeared that a chemical comparison of separated nodules and flake graphite would be profitable, for if the core is nongraphitic a relatively large amount of certain elements would be found in the nodules as compared to the flake. This comparison could best be made by obtaining nodules and flake from the same melt of cast iron, part of which had been in-noculated with a suitable addition reagent for the formation of nodules. A 300 lb melt was produced. About half of this was innoculated in the ladle with an Fe-Si-Mg alloy to produce nodules and cast into keel blocks; the remaining half of the melt had silicon added in an effort to compensate for the silicon in the innoculant used in the other half of the melt and this was cast into similar keel blocks. The analyses of the resultant irons are given in Table I. Nodules and flake were chemically extracted from 2 kg samples of metal as described in the appendix. While this method dissolved the iron and chromium carbides, it did not dissolve the titanium, vanadium, and molybdenum carbides. These latter carbides could have been removed by nitric acid, but in other experiments it was found that it attacked pools of metallic iron entrapped in the nodules which had, until the nitric acid treatment, been protected from the attack of the sulphuric, hydrochloric, and hydrofluoric acids. It will be shown in the next section that entrapped iron exists in nodules but not in flake. On microscopic examination many tiny irregular particles were observed to accompany both the nodules and the flake. These were identified by tabling a sample of nodules from which a sufficient fraction was obtained for X-ray analysis. A good pattern of titanium carbide was obtained indicating that this was the predominant compound present. Since it was not possible to determine how completely the carbides could be removed mechanically and since their removal from flake is much more difficult, it was decided not to resort to any separation as this would render further comparisons more difficult. The samples were ashed in a combustion

Jan 1, 1953

By J. D. Verhoeven

The effectiue distriblltion coefficient has been Measured in a series of vertical, normal freezing experirtzents with large current densities passing through the solid-liquid interface. The results indicate that the effect of the current on solute redistribution is due to electvotransport in the liquid. The high currents produced extensive mixing in the liquid which was considerably reduced by solidifying in small lubing. Analysis of the convection indicates that it probably vesulls from a horizontal temperature gradient produced by the Joule heating- of the electvic crirver~t. Due to the strong dependence of this convection upon the specimen radius, it is conclnded that only for specit~ens with radii of less than somewhere between 1 and 2 mm wilt electric field freezing be getlerally effec-tire at enhancing the purification of zone-melting experittierats in loe-melting alloys. Experiments on 0.8-mm lubes illustrate some interesting potential applications of this techniqne as a means of solute control on smcrll specimens. In a number of papers published within the last few years'-4 it has been found that passage of large dc currents through the solid-liquid interface of a freezing alloy produces a change in the solute redistribution accompanying the solidification. It had been predicted theoretically by Hucke et al.s and by Pfann and Wagner that such an effect would occur as the result of electrotransport within the liquid boundary layer at the solid-liquid interface. These authors independently derived the following relation between the effective distribution coefficient and the variables of the process: Where k0 is the equilibrium distribution coefficient, V is the mobility of the solute relative to the solvent, E is the electric field intensity, D is the solute diffusion coefficient, R is the rate of interface motion, and 6 is the boundary layer thickness. Both groups of authors show that this equation predicts the possibility of extending the purification ability of zone-melting experiments by the addition of an electric current. However, there are other effects in addition to electro-transport which could be produced by the high dc current and might, perhaps, invalidate the applicability of Eq. [I]. For example, high electric current might affect the interface reaction or perhaps the equilibrium distribution which was assumed to exist at the interface. It was the purpose of this work to determine the applicability of Eq. [I] by systematically investigating a simple system for which all of the necessary parameters were known. It was of particular interest for speculating on the potential usefulness of this technique to determine the maximum practical field intensities obtainable, and the effect of these high fields upon convective mixing in the liquid. The initial work in this study was published in a previous paper3 which will be referred to as I. In that work, a current density of 2000 amps per sq cm was used with specimen diameters of 5 mm. The results gave a qualitative confirmation of Eq. [I.], and also showed that a large amount of convective mixing was produced in the liquid by the current. The present study is an extension of that work to smaller specimen diameters and higher current densities. Two points were overlooked in I and will be emphasized here: a) the value of ko has not been well-established in the Sn-Bi system and b) the observed convection could be due to thermal convection produced from the Joule heating. EVALUATION OF k0 To evaluate Eq. [ I.] it is necessary to know the value of the equilibrium distribution coefficient, k,. Tn I the value of k, was taken as 0.3 from a published phase diagram.7 According to ansen' the best data on the phase boundaries of the Sn-Bi system are those of Davidson.5 The data of Davidson give a k, value ranging from 0.21 to 0.25 for the compositions studied in this work, or an average value of around 0.23. In a recent publication, Rigaud and Tougas'10 determined ko by means of a solidification technique. For an alloy of approximately the same composition as that used in this work they obtained a ko value of 0.39. Hence, there is considerable uncertainty in the value of ko and, consequently, a series of experiments were made to determine k, more accurately.

Jan 1, 1968

By G. W. Thomas

A simplified mathematical model of underground conduction heating in a system of limited permeability is presented. The model applies to underground retorting of oil shale, or to reservoirs containing extremely heavy oils. We assume that heat is introduced at a constant rate into a horizontal fracture which communicates between wells. The radial temperature distribution along the fractured surface is approximated by a step-function. Heat transfer away from the fracture is assumed to be by vertical conduction, and all convection effects are neglected. The model also takes into account the possible temperature dependence of thermal conductivity. A general expression for calculating the growth of the step-function temperature distribution with time is derived. The use of this expression and solutions to the one-dimensional heat equation make it possible to construct isotherms. Expressions for calculating .oil recovery, well spacing and heat efficiency are also given. An example calculation is presented for the conduction heating process in oil shale. Finally, the effect of the heat transfer coefficient between the gas and the fracture boundaries is investigated. INTRODUCTION Thermal recovery processes of oil recovery fall into the four general areas of hot fluid injection, forward combustion, reverse combustion and conduction heating. The first three of* these processes have been rather extensively studied in the past decade from both the experimental and theoretical points of view. As a result, it is possible to make reasonable engineering predictions and analyses of these processes. Little attention has been devoted, however, to the conduction heating process other than to note its possible utility.I To a certain extent, conduction heating cannot be divorced from the other regimes cited above, insofar as these provide the source of heat energy. In the conduction heating process, heat is introduced (either by combustion in the forward or reverse mode or by hot fluid injection) into a small fraction of the total reservoir thickness. This fraction may be either a streak of high permeability or an interwell fracture. Heat penetrates by conduction into the adjacent, less permeable regions of the oil-bearing rock, where the direction of conduction is essentially perpendicular to the streak or fracture. The heated product then drains by gravity or is gas driven to production wells. Conduction heating is probably most applicable to systems containing immobile bitumens such as tar sands and oil shale deposits and perhaps to low-permeability reservoirs containing highly viscous crudes. The mechanism also acts in combination with other thermal processes where fingering or overriding of a bed occurs. It seems probable that in at least one field test, conduction heating of this type was very influential.2 In this presentation we give a first approximation to some of the quantitative aspects of conduction heating. Marx and Langenheim3 treated a similar problem where they focused attention upon the injection interval, which spanned the total reservoir thickness. In their model, conduction heat losses to the bounding media imposed a practical limit on the calculated heated area. In the present study, however, we shall confine the injection interval to a small fraction of the reservoir thickness and assume it has no heat capacity. We therefore direct our attention to regions outside the injection interval into which the conduction of heat is beneficial. In particular, we will endeavor to locate specific isotherms in the media bounding the injection interval. Furthermore, we will construct our model to allow the thermal conductivity to vary arbitrarily with temperature. Thus the model will be applicable to underground retorting of shale where variations in thermal conductivity may be important. THEORY We consider the rock matrix to have no or, at best, a very limited permeability; consequently a

Jan 1, 1965