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By M. A. Mayers, J. A. Thompson

In recent years, the problem of damage to coke-oven walls by expanding coal charges undergoing carbonization has engaged great attention on the part of research workers in this field, and has led to the development of many devices for estimating these pressures.l-14 Only in Russell's method" and in the Koppers ovens7 are conditions quite similar to those in commercial ovens. Tests even in these ovens are empirical because no information has been published to permit an evaluation of "scale effects." Owing to the relatively large wall area in these test ovens, the average wall pressure determined may be lower than that existing in localized areas. This factor may be compensated for in part by the testing of coal charged into the test oven at a bulk density that is as high as the highest that is believed to exist in commercial ovens. Both of these lacks might be filled by the development of an adequate gauge for the direct measurement of wall pressure exerted by the charge in commercial coke ovens in normal operation. Previous attempts to elaborate such instruments7,15 have resulted in units which, because they had to be water-cooled, probably produced changes in the conditions of carbonization, and which had to be removed from the oven before carbonization was complete, to avoid their destruction. Late in 1941 the Coal Research Laboratory undertook to develop such a gauge, in which gas pressure was balanced against the charge pressure and which thus would not require water cooling, on a suggestion made in 1937 by one of the present authors and William B. Warren, a former member of the Laboratory staff. The gauge heads themselves were to be simple and cheap enough so that they might be discarded after each run if seriously damaged. This would permit them to be left in place throughout the carbonizing period, when they could be pushed out with the coke. The basis of the design, of which the latest exemplification is shown in Fig. I, was that as the internal gas pressure within a flexible metal envelope was increased, the flexible wall would move away from a stop when the gas pressure just overbalanced the charge pressure. If the stop were an insulated electrical contact, the point of balance could be indicated by the breaking of an electric circuit. It was anticipated that, while the instrument must operate at high temperature, the presence of a strongly reducing atmosphere throughout the carbonizing period would so reduce the danger of scaling that mild steel could be used for the gauge. This expectation has been justified. Danger of attack on silica oven walls by the steel gauge body can be eliminated by cementing asbestos paper or an alundum or silica plate to the back of the gauge body. The gauge head itself has a relatively heavy mild-steel body, A, into which standard ¼-in. pipe B is screwed to conduct gas and electrical leads. The body is closed by a single bellows C, consisting of two annuli of 0.011-in. (o.a8-mm.) cold-rolled shim-steel spot-welded together at their outside edges. The lower one is

Jan 1, 1944

By J. A. Thompson, M. A. Mayers

In recent years, the problem of damage to coke-oven walls by expanding coal charges undergoing carbonization has engaged great attention on the part of research workers in this field, and has led to the development of many devices for estimating these pressures.l-14 Only in Russell's method" and in the Koppers ovens7 are conditions quite similar to those in commercial ovens. Tests even in these ovens are empirical because no information has been published to permit an evaluation of "scale effects." Owing to the relatively large wall area in these test ovens, the average wall pressure determined may be lower than that existing in localized areas. This factor may be compensated for in part by the testing of coal charged into the test oven at a bulk density that is as high as the highest that is believed to exist in commercial ovens. Both of these lacks might be filled by the development of an adequate gauge for the direct measurement of wall pressure exerted by the charge in commercial coke ovens in normal operation. Previous attempts to elaborate such instruments7,15 have resulted in units which, because they had to be water-cooled, probably produced changes in the conditions of carbonization, and which had to be removed from the oven before carbonization was complete, to avoid their destruction. Late in 1941 the Coal Research Laboratory undertook to develop such a gauge, in which gas pressure was balanced against the charge pressure and which thus would not require water cooling, on a suggestion made in 1937 by one of the present authors and William B. Warren, a former member of the Laboratory staff. The gauge heads themselves were to be simple and cheap enough so that they might be discarded after each run if seriously damaged. This would permit them to be left in place throughout the carbonizing period, when they could be pushed out with the coke. The basis of the design, of which the latest exemplification is shown in Fig. I, was that as the internal gas pressure within a flexible metal envelope was increased, the flexible wall would move away from a stop when the gas pressure just overbalanced the charge pressure. If the stop were an insulated electrical contact, the point of balance could be indicated by the breaking of an electric circuit. It was anticipated that, while the instrument must operate at high temperature, the presence of a strongly reducing atmosphere throughout the carbonizing period would so reduce the danger of scaling that mild steel could be used for the gauge. This expectation has been justified. Danger of attack on silica oven walls by the steel gauge body can be eliminated by cementing asbestos paper or an alundum or silica plate to the back of the gauge body. The gauge head itself has a relatively heavy mild-steel body, A, into which standard ¼-in. pipe B is screwed to conduct gas and electrical leads. The body is closed by a single bellows C, consisting of two annuli of 0.011-in. (o.a8-mm.) cold-rolled shim-steel spot-welded together at their outside edges. The lower one is

Jan 1, 1944

By J. A. Thompson, M. A. Mayers

IN recent years, the problem of damage to coke-oven walls by expanding coal charges undergoing carbonization has engaged great attention on the part of research workers in this field, and has led to the development of many devices for estimating these pressures.1-14 Only in Russell's method11 and in the Koppers ovens7 are conditions quite similar to those in commercial ovens. Tests even in these ovens are empirical because no information has been published to permit an evaluation of "scale effects." Owing to the relatively large wall area in these test ovens, the average wall pressure determined may be lower than that existing in localized areas. This factor may be compensated for in part by the testing of coal charged into the test oven at a bulk density that is as high as the highest that is believed to exist in commercial ovens. Both of these lacks might be filled by the development of an adequate gauge for the direct measurement of wall pressure exerted by the charge in commercial coke ovens in normal operation. Previous attempts to elaborate such instruments7,15 have resulted in units which, because they had to be water-cooled, probably produced changes in the conditions of carbonization, and which had to be removed from the oven before carbonization was complete, to avoid their destruction. Late in 1941 the Coal Research Laboratory undertook to develop such a gauge, in which gas pressure was balanced against the charge pressure and which thus would not require water cooling, on a suggestion made in 1937 by one of the present authors and William B. Warren, a former member of the Laboratory staff. The gauge heads themselves were to be simple and cheap enough so that they might be discarded after each run if seriously damaged. This would permit them to be left in place throughout the carbonizing period, when they could be pushed out with the coke. The basis of the design, of which the latest exemplification is shown in Fig. I, was that as the internal gas pressure within a flexible metal envelope was increased, the flexible wall would move away from a stop when the gas pressure just overbalanced the charge pressure. If the stop were an insulated electrical contact, the point of balance could be indicated by the breaking of an electric circuit. It was anticipated that, while the instrument must operate at high temperature, the presence of a strongly reducing atmosphere throughout the carbonizing period would so reduce-the danger of scaling that mild steel could be used for the gauge. This expectation has been justified. Danger of attack on silica oven walls by the steel gauge body can be eliminated by cementing asbestos paper or an alundum or silica plate to the back of the gauge body. The gauge head itself has a relatively heavy mild-steel body, A, into which standard ¼ in. pipe B is screwed to conduct gas and electrical leads. The body is closed by a single bellows C. consisting of two annuli of 0.011-in. (0.28-mm.) cold-rolled shim-steel spot-welded together at their outside edges. The lower one is

Jan 1, 1944

By Franklin J. Hill, Theodore D. Tiemann

Sized fractions of Wisconsin Gogebic taconite were reduced with hydrogen over the temperature range from 600° to 1000°C. In general, the degree and rate of reduction increase with temperature. Particle size has no observable effect except in the smaller fractions at 900°C and above, where reduction is impeded, possibly due to the siliceous nature of the ore. Gaseous diffusion appears to be significant as a rate controlling factor at certain stages. THE depletion of high grade iron ore reserves in the United States has established the need to utilize all available iron ore deposits, both in long range planning and from the viewpoint of national emergency. This has led to extensive research and development in this field. The beneficiation of Wisconsin Gogebic taconite ore has been previously studied by investigators at the University of Wiscconsin, 1 the United States Bureau of Mines,, Battelle Memorial Institute, 3 and others. Methods investigated have included concentration by flotation processes, magnetic and gravity separation, magnetic roasting and various combinations of them. The foregoing studies have been concerned with the production of an enriched ore suitable for blast furnace use. If the ore could first be reduced to metallic iron and then beneficiated, the product could be used directly in the open hearth or electric steel-making furnace. The by-passing of the blast furnace should enhance the economic feasibility of the beneficiating process. The work reported here,4 was undertaken to establish data on the hydrogen reduction of Wisconsin taconite that would eventually lead to the development of an economic direct reduction process for this and perhaps other low grade siliceous ores. The volume of work on direct reduction can be judged by the fact that 240 direct reduction processes were patented in the United States alone up to 1951, 5 and numerous additional processes have since been developed. Some of the factors contributing to direct reduction development are: 1) The increasing capital cost of the blast furnace and its accessory equipment. 2) The decreasing availability of high grade domestic ore. 3) The high cost of steel scrap for use in the open hearth and electric furnaces. In general, direct reduction processes can be divided into two types; those using a solid reductant (coal, peat, lignite) usually carried out in a kiln, and those using a gaseous reductant (H2, CO) in a shaft furnace or a fluidized bed retort. As there is no low cost coal readily available in northern Wisconsin but natural gas could be quite easily obtained, it is believed a gaseous reductant process would offer the greater feasibility for use on Wisconsin taconite. It is hoped that this preliminary work will beof interest to other investigators in this increasingly important field. TACONITE ORE The ore used in the investigation was obtained originally from the U. S. Bureau of Mines, and consisted of a representative composite made up from trench samples of the Norrie, Pabst, Plymouth, Pence, and Yale members of the Wisconsin Gogebic range iron formation. Chemically, the ore contains approximately 52 pct SiO, and 30 pct Fe. X-ray diffraction and other studies indicate the principal minerals to be quartz (SiO2), hematite (Fe2O3), and goethite (Fe2O3. H2O). Minor amounts of iron containing silicates, siderite (FecO3), and magnetite (FeO-Fe2O3) are present. The iron minerals and quartz are so finely disseminated that the ore requires grinding to less than 200 mesh (74 µ) for essential liberation.l,2 The iron content of each of the several size fractions studied is shown in Table I. EXPERIMENTAL METHOD The method used throughout the investigation was based on that developed by the U. S. Bureau of Mines in Minneaopolis6,7 in which the course of reduction is followed by the loss in weight of the ore sample. More specifically, a 100-g sample of the size frac-

Jan 1, 1962

By Milton E. Wadsworth, W. Martin Fassell, William H. Dresher

A study of the rate of dissolution of molybdenite (MoS2) in alkaline solution was carried out under carefully controlled conditions. Effects of temperature, oxygen over-pressure, and KOH concentration were evaluated. Studies were made in the temperature range 100°C to 175°C and in the pressure range 0 to 700 psia of oxygen. Under these conditions molybdenite was found to leach according to a linear mechanism. Both oxygen over-pressure and KOH concentration were found to control the rate of leaching. The mechanism has been explained in terms of adsorption of oxygen at the molybdenite surface followed by configurational rearrangement of the adsorbed molecules. The hydroxyl ion dependency is believed to be diffusion-controlled. Laboratory batch studies have shown that molybdenite can be readily dissolved in alkaline solutions under moderate conditions of temperature and pressure. Commercial application of this process to the production of ferro-molybdenum and molybdenum chemicals is promising in view of the ease of dissolution of molybdenite and the relatively noncorrosive conditions involved in the process. HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.' The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.' National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 phalerite,4 galena,5 and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,8 who found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo+ + in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit's construction and operation have been discussed elsewhere,7 Only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

By R. J. Bethancourt, D. M. Collingwood

The use: of a pilot waterflood is very desirable where all of the pertinent data necessary to initiate a full scale waterflood are not. available. This paper attempts to take a specific case and .show the step by step process of starting with a pilot waterflood and progressing to a full wale flood as results are obtained. INTRODUCTION Many of the older fields of Soutlwest Texas are approaching depletion by primary produrtion methods. As primary protlllc:inp operations on individual properties approach their economic limit. conflicting considerations face management: cm the one hand. plugging and abandonment of wells for equipment salvage; on the other hand, further investment in secondary recovery installtions, equilent, and well workovers in the interests of conservation anal additional oil reserves. In main instances, where primary production by pressure depletion and gas solution drive has been comparatively good, there still exists the possibility of an economic secondary recovery by waterflood. This is not necessarily true to the same degrre of all such fields. nor all portions of large fields. To properly evaluate the economics of a prospective water-11ot1cI requires a considerable amount of precise geological. statitical. and physical data Such information on the older field.; is often very limited. and in the case of the property discussed in this paper was considered inadequate to justify investment in an overall waterflood. Primary production was estimated at :39 per cent of the original oil in place, yet sand conditions of permeability and homogeneity, and position in the field appeared to be favorable for a limited margin of profit from a carefully controlled waterflood. Thus a pilot waterflood, with its minimum initial financial risk, followed by extension as favorable results were obtained, seemed to be the answer for the Sun Oil Co L. Wiederkehr lease in the Nortl Government Wells Field, Duval County. Texas DESCRIPTION OF RESERVOIR Approxinately 8,200 wells have been drilled in Duval County. As of March 1, 1952, there were 3,350 producing oil wells in 92 different fields, with very few flowing wells (Fig. 1.) Sun Oil Co. operates the I.. Wiederkehr lease located in the North Government Wells Field in Duval Countv. 85 mile. west of Corpus Chriti and 100 miles south of San Antonio. The lease has been subjected in part to a controlled five spot waterflood. The North Government Wells Field is roughly 7 miles long and 3 miles wide, with numerous overlapping producing zones. The L. Wiederkehr lease of 3.085 acres. Has seven producing zones from 700 to 7.500 ft. The lease is in the northern section of the field where it is widest, and has 710 acres productive from the North Government Wells .and. (Fig. 2.) The North Government Wells sand, Jackson group. Eocene age, at an average depth of 2.250 ft (minus 1.750 subsea). has a thickness range of 25 ft on the east side of the L. Wiederkehr lease to 4 ft on the west side. It has a slight overall dip to the North and East of some 33 ft to the mile.

Jan 1, 1953

By K. E. Brown, G. H. Fancher

An 8,000-ft experimental field well was utilized to conduct flowing pressure gradient tests under conditions of continuous, multiphase flow through 2 3/8-in. OD tubing. The well was equipped with 10 gas-lift valves and 10 Maihak electronic pressure recorders, as well as instruments to accurately measure the surface pressure, temperature, volume of injected gas and fluid production. These tests were conducted for flow rates ranging from 75 to 936 B/D at various gas-liquid ratios from 105 to 9,433 scf/bbl. An expanding-orifice gas-lift valve allowed each flow rate to be produced with a range of controlled gas-liquid ratios. From these data an accurate pressure traverse has been constructed for various flow rates and for various gas-liquid ratios. A comparison of these tests to Poettmann and Carpenter's correlation indicates that deviations occur for certain ranges of flow rates and gas-liquid ratios. Numerous curves are presented illustrating the comparison of this correlation with the field data. Poettmann and Carpenter's correlation deviates some for low flow rates and, in particular, for gas-liquid ratios in excess of 3,000 scf/bbl. These deviations me believed to be mainly due to the friction-factor correlation. However, Poettmann and Carpenter's correlation gives excellent agreement in those ranges of higher density. This was as expected and predicted by Poettmann. He pointed out that their method was not intended to be extended to those ranges of low densities whereby an extreme reversal in curvature occurs.l As a result of these experimental tests, correlations using Poettmann and Carpenter's method were established between the friction factors and mass flow rates which are applicable for all gas-liquid ratios and flow rates. Definite changing flow patterns do not allow any one correlation to be accurate for all ranges of flow. INTRODUCTION The ability to analytically predict the pressure at any point in a flow string is essential in determining optimum production string dimensions and in the design of gas-lift installations. This information is also invaluable in predicting bottom-hole pressures in flowing wells. Although this problem is not new to industry, it has by no means been solved completely for all types of flow conditions. Versluys,2 Uren, et al, 3 Gosline,4 May,5 and Moore, et al,6,7 were all early investigators of multiphase flow through vertical conduits. However, all of these investigations and proposed methods were very limited as to their range of application. Likewise, many are extremely complicated and therefore not very useful in the field. Only in the last decade have any significant methods been proposed which are generally applicable. The most widely accepted procedure in industry at the present time is a semi-empirical method developed from an energy balance, proposed by Poettmann and Carpenter8 in 1952. Their correlation is based on actual pressure measurements from field wells. Accurate predictions from this correlation are limited to high flow rates and low gas-liquid ratios. Although this method will be discussed in detail later, it should be pointed out that two important parameters, namely the gas-liquid ratio and the viscosity, were omitted in their correlation. The viscosity was justifiably omitted since their data was in the highly turbulent flow region for both phases, and most wells fall in this category. The gas-liquid ratio was incorporated to some extent in the gas-density term. In 1954, Gilbert9 presented numerous pressure gradient curves obtained from field data for various flow rates and gas-liquid ratios for the determination of optimum flow strings. However, no method is presented for predicting pressure gradients except by comparison to these curves. Baxendell, et al,10 proposed a method based on Poettmann and Carpenter's procedure

By G. R. Speich, S. A. Kulin

The isothermal formation of martensite at subzero temperatures has been studied in an austenitic stainless steel. The amount of martensite formed isothermally in a given time was found to follow a C-curve behavior with decreasing temperature. Since isothermal rnartensitic transformation occurs at temperatures above the true M. temperature of the olloy, the observed M. temperature is dependent on the cooling rate. It is believed that a general martensite theory must include the basic concepts of the strain embryo theory, and also the important role of thermal fluctuations. UNTIL recently the isothermal component of the martensitic transformation had been considered as a trivial effect in theoretical considerations of this type of transformation. One of the postulates used in defining a martensitic transformation was that the reaction was temperature dependent but not time dependent. Cohen and his associates1'2 were the first to report the isothermal formation of mar-tensite. They obsel-ved the time dependency of the martensite reaction at room temperature in plain carbon steels and certain tool steels. They found that a small amount of additional transformation occurred after the specimen reached the quenching temperature and that the rate of this isothermal transformation decreased rapidly with time. These authors considered this phenomenon to be a "tailing-off" of the main athermal reaction. Kurdjumov and MaksimovaL 5 studied the isothermal formation of martensite at subatmospheric temperatures in steels containing 0.6 pct C-6 pct Mn, 1.6 pct C, and in an iron-base alloy containing 23 pct Ni and 3.4 pct Mn. In each case it was found that both the initial rate and the total amount of isothermal transformation exhibited sharp maxima with decreasing temperature. They stated that it was possible to completely suppress the martensitic transformation in the 0.6 pct C-6 pct Mn steel by drastic quenching in liquid nitrogen. They interpreted their results in terms of a thermally activated process. The maximum in the rate of nucleation vs. temperature curve was assumed to be a result of the temperature dependence of the rate of growth of the martensite plates. It has been demonstrated," however, that martensite plates can form with great rapidity even at temperatures approaching absolute zero. In addition," attempts to confirm the reported suppression of the martensitic transformation by rapid cooling of a 0.6 pct C-6 pct Mn steel have proved unsuccessful. On this basis, and on other theoretical grounds, the validity of some of Kurd-jumov's results and conclusions is open to serious question. Cohen, Machlin, and Paranjpe' have proposed a theory of martensite formation based on the nucleation of strain embryos and a growth mechanism involving cooperative atomic displacements. According to this theory thermal fluctuations can make a strain embryo supercritical and thereby produce martensite isothermally. Das Gupta and Lement' have investigated the isothermal formation of martensite in a 17 pct Cr-0.7 pct C steel at temperatures below the ambient. They found that partial suppression of the martensitic reaction occurred on quenching into liquid nitrogen. That part of the reaction which can be suppressed is taken to correspond to the isothermal rather than the athermal part of the rnartensitic transformation. The initial rate of isothermal transformation for this steel was found to go through a maximum with decreasing temperature. This is in conformity with the findings of Kurdjumov and Maksimova for the steels used in their investigation. Das Gupta and Lement conclude that isothermal martensite formation occurs by the nucleation of new plates and is always preceded by some athermal transformation. An iron-base alloy containing 14 pct Cr-9 pct Ni was used in this investigation to study further the kinetics of the austenite to martensite transforma-

Jan 1, 1953

By R. F. Steigerwald

The effects of heat transfer on the corrosion behavior of type 304 stainless steel in boiling water have been studied. Heat transfer conditions increase the tendencies of the stainless steel toward stress-corrosion mucking when the water is contaminated with Cl-. Surface preparation is the most important variable in determining the severity of the stress-corrosion problem in water with a given Cl- content. Heat treatment, chemical cleaning, and degree of wet film boiling also affect the corrosion of stainless steels used as heat transfer surfaces in boiling water. An up-paratus for corrosion testing under controlled heat transfer conditions is described. THE principal objective of this investigation was to study the corrosion behavior of AISI Type 304 stainless steel in boiling high-purity water under conditions of heat transfer. The principal variables in the study were: a) boiling conditions: limited boil, agitated boil; b) metallurgical structure: annealed or sensitized; c) surface condition: rolled, pickled, or ground. The results of the study should elucidate the role of heat transfer in the corrosion of stainless steel in boiling high-purity water and provide a base line from which to assess the severity of this type of corrosion. Although there has been an investigation of the effect of heat transfer on the corrosion behavior of stainless steels in alkaline waters,' work on the corrosion of stainless steels under heat transfer has been largely confined to various acid solutions.'-4 Furthermore, the study of the corrosion of stainless steels in high-purity water has been generally restricted to auto-clave and instream testing in superheated (e.g., 300°C) water and steam.5'6 Cooling water problems led to this study of the corrosion behavior of type 304 stainless steel in high-purity water at its atmospheric boiling point. In addition to the effects of heat transfer, this study also considered the influences of the type of boiling,7 metallurgical structure, and surface condition on the corrosion behavior of stainless steel in high-purity water. Two boiling conditions were investigated in this study: a) limiting boiling, i.e., when the heat-transfer surface had just reached the boiling point and boiling nucleated randomly over the specimen surface and b) agitated boiling, i.e., when a mild degree of superheat had been achieved on the specimen surface and boiling occurred generally over the specimen surface. Both boiling conditions are broadly classified as wet-film boiling. Originally, this program included the study of a third type of boiling, dry-film conditions. At dry-film boiling the temperature of the heat transfer surface is high enough so that it is covered with a continuous film of steam. Experimental difficulties made it impossible to study this kind of boiling with the available apparatus. Since surface condition affects heat transfer rates, three typical surfaces were chosen for study: a) as-rolled, the 2B finish received from the supplier, b) as-pickled, 30 min in 8 pct HNO3-1 pct HF, and c) as-ground on 120 grit paper. In order to evaluate the effect of improper heat treatment or welding on hot wall corrosion, both annealed and sensitized mi-crostructure were included in this study. EXPERIMENTAL Test Apparatus. The particular problems of interest in this investigation required a knowledge of the thermal gradient through the test specimen. From this gradient, the heat flux to the surface and the surface temperature could be determined. In order to satisfy this need, an apparatus similar to the boiling-disk apparatus of Fisher and whitney2 was designed. The solution is contained in a thermally-insulated, steel pipe lined with TEFLON resin. A stainless steel _______;________________________________________

Jan 1, 1970

By R. F. Blakely, P. E. Potter

Any stratigraphic section or bedding sequence can be synthesized if there is a transition procedure from one lithology or bedding type to another, and if thickness distributions of the different lithologies are known. Stratigraphic sections of a fluvial sandstone body were synthesized with five bedding types: cross-bedding, massive beds, parting lineation, ripple mark and mudstone. The transition procedure from one bedding type to another used dependent, Markovian random processes which have a memory that extends one step backward in the depositional process. As observed in nature, median grain size and sand wave thickness (cross-bedding and ripple mark) decline upward in the synthesized sections as proportions of the different bedding types change. Grain size and permeability were also incorporated into the sections. By changing the transition procedures, bed thickness distributions, rate of upward decline or sand wave height and length, different types of sections can be synthesized, thus making it possible to model many different sedimentation problems. INTRODUCTION This paper describes a general method for synthesizing stratigraphic sections and bedding sequences of sedimentary, metamorphic or igneous origin. Synthetic generation is of interest for several reasons. Close correspondence between real and synthetic sections suggests that the factors used in the synthesizing model may indeed be the correct ones, thus giving the investigator a check on his assumptions. Rapid, inexpensive simulation of many stratigraphic sections permits one to synthesize a rock body (sandstone or carbonate reservoir) or, on a larger scale, the fill of a sedimentary basin. Harbaughl gives an example of mathematical simulation of a carbonate basin. He simulated the basin in the hope that improved prediction would follow better understanding of the depositional processes. From the petroleum engineer's viewpoint it seems reasonable to believe that the synthetic generation of rock properties and their distribution in a reservoir should be relevant in the study of reservoirs. Any stratigraphic section or bedding sequence can be generated provided there is a transition procedure from one lithology or bedding type to another, and provided the thickness distributions of the different units are known. The transition procedure involves random processes that are either independent or dependent. If the depositional process is independent, previous deposition will have no influence on present deposition. However, if it is dependent, past deposition will influence either present or future deposition. Such a dependent depositional process can be thought of as having a memory that extends backward in time through one or more pulses of deposition. A process with a memory can be described by a Markov process. Because the concept of memory or dependence appears to be in accord with our understanding of many depositional processes, Markov processes were used to synthesize the bedding sequences of this study (see Appendix). The above methods are perfectly general and are appropriate for any stratigraphic section or bedding sequence: bedding types in a beach deposit, an evolving carbonate bank or the changing lithologic fill of a thick geosyncline sequence. We chose to synthesize a vertical profile of a fluvial sandstone body because its characteristics were well documented, much was known about fluvial processes and fluvial-deltaic sandstone bodies constitute an important class of petroleum reservoirs. CHARACTERISTICS AND ORIGIN OF FLUVIAL CYCLE The fluvial cycle has been well documented in recent years by Bersier,2 Allen3-5and Visher.6,7 Deposits from fluvial cycles range from 10 to 150 ft or more in thickness and are characterized by a "fining upwards": coarse sandstones with occasional conglomerates grade upward into medium- to fine-grained sandstone, and hence into siltstone and mudstone. The dominant sedimentary structure is inclined bedding: thick cross-beds in the lower half

By J. Husson, R. Iffly, M. Gondouin

A systematic variation of well deliverability, as reflected from isochronal back-pressure tests performed at regular intervals, has been observed in some gas condensate wells producing at high rates. The same effects have been obtained using a numerical model of gas and condensate flow which takes into account secondary gasoline deposited in the pore space as a result of pressure reduction, and non - Darcy flow of gas in the vicinity of the wells. Matching calculated values with previous test results has been possible, and future predictions have been obtained. An application of this method to the Hassi Er R'Mel gas-condensate field in Algeria is tentatively shown. INTRODUCTION Flow capacity of gas wells is generally derived from an analysis of back-pressure tests. The empirical equation q = C (?p2)n used by Rawlins and Schellhardtl can be derived rigorously assuming that steady-state radial flow of a dry gas of constant viscosity and compressibility is established during each flow period of the well tests. Furthermore, when Darcy's law applies in the entire flow region, the theory predicts that the exponent n is equal to 1. In low-permeability reservoirs, it was soon discovered that the time required to reach a stabilized flow often exceeded the duration of the flow periods normally available for testing wells. Consequently, transient gas flow had to be considered instead of the steady-state assumption previously used. This led to the isochronal testing procedure established by Cullender2 which has largely replaced conventional back-pressure testing. For dry gas fields, this method yields definite values of C and n equivalent to those of the empirical equation. These values should remain constant for each well as long as the permeability of the formation and the characteristics of the gas (viscosity and compressibility) do not change appreciably. This is the case when reservoir pressure remains -close to the original value and when the formation near the wellbore remains free of plugging. Under those conditions, stabilized flow potential curves of gas wells can be established from a single sequence of isochronal flow and shut-in periods. An analysis of a pressure build-up following a longer production period provides additional data on the transmissivity (k h/ u) of the reservoir, and eventually on the 'drainage radius rd of the well, which can be related to the value of C so that future performance of the well can be predicted using the concepts developed by A. Houpeurt.3 At high flow rates, Darcy's law no longer applies in the vicinity of the wellbore, and inertial effects in the high velocity gas flow introduce additional pressure drops. As a consequence, exponent n of the backpressure tests becomes smaller than 1, and a slight curvature of the log-log plot of ?p2 vs q can be predicted when going from very low to high rates of flow (Elenbaas and Katz).5 The effects of variations of viscosity and compressibility with pressure on the radial flow of dry gas in an infinite reservoir were taken into account by Jenkins and Aronofsky.7 Numerical solutions of the transient flow of an ideal gas in finite radial reservoirs were presented by Bruce, Peaceman, Rachford and Rice.8 In the case of gas condensate wells, however, the presence of gasoline in the pore space as soon as reservoir pressure is reduced below the dewpoint pressure further complicates the interpretation of flow tests so that the prediction of stabilized well performance becomes very difficult. Field observation shows that both C and n derived from isochronal tests vary in time, even when reservoir pressure has not changed appreciably. Such a variation cannot be attributed to any change of the gas characteristics, and must result from the effect of a gasoline saturation on the gas flow.

By L. A. Wood, A. G. Winslow

Subsidence has occurred in several areas of the upper Gulf Coast region of Texas, although in most cases this is not evident without precise instrumental leveling. As referred to in this report, the region comprises about 7200 sq miles of the Gulf Coastal Plain and includes all or parts of the following counties: Harris, Fort Bend, Waller, Brazoria, Galveston, Liberty, Chambers, Orange, and Jefferson (Fig. 1). Topographic relief is low, ranging from sea level at the Gulf of Mexico to 300 ft or more in northwestern Harris County. In this upper Gulf Coast region, which embraces the most heavily populated and industrialized parts of Texas, industrial and municipal water supply is obtained chiefly from wells. Largest center of ground-water withdrawal is the Houston-Baytown area, where about 200 million gallons per day was pumped in 1956 for municipal and industrial use. Other large centers of ground-water withdrawal include the Alta Loma sector and the heavily industrialized Texas City area in Galveston County, where about 23 mgd was pumped in 1956. In the Freeport area in Brazoria County about 6 mgd was pumped in 1956 for city and industrial supply. In addition to withdrawals in metropolitan districts, great quantities of ground water are supplied by irrigation wells to thousands of acres of rice. These wells are widely dispersed over many miles, principally in Harris, Waller, Fort Bend, Brazoria, and Liberty counties, and effects of pumping are not so readily noticed as in the industrial and metropolitan sectors. Subsidence: Starting with the 1905-1906 line from Smithville, Tex., to Galveston, the U. S. Coast and Geodetic Survey has extended a network of first and second-order level lines throughout the upper Gulf Coast region. In 1918, when a line was run from Sinton, Tex., to New Orleans, La., a tie was made to the 1905 leveling at Houston. In 1932-1933 a line was run from Palestine, Tex., to Houston, and a good deal of leveling was carried out in the vicinity of Houston. At this time the entire network was adjusted to the Sea Level Datum of 1929. In 1935-1936 and 1942-1943 several new lines were run and considerable releveling was performed. Supplementary adjustments were made after both the 1936 and 1943 levelings in order to reduce the elevations to the Sea Level Datum of 1929. These adjustments probably masked some of the subsidence that had occurred up to that time, although a certain amount of subsidence was noticed in the 1943 leveling. When several lines in the vicinity of Houston and Galveston were releveled in 1951, the regional nature of the subsidence became apparent.' Direct comparison with the 1943 leveling was possible because the datum was not changed. Comparisons with prior leveling were unreliable because of differences in the early and subsequent datums. In 1953-1954 many lines in the region were re-leveled and in 1957 the entire network, including the elevations previously determined, was readjusted to determine the changes in elevations as indicated by various levelings between 1905 and 1953-1954. In this instance the adjusted elevations were held fixed near the boundaries of the region where the bench marks seem to have remained stable. The only sea-level connection held fixed was the connection of the 1905 leveling to the 1903-1906 tidal series at Galveston. Almost the entire region has been at least slightly affected by the subsidence, some areas to a great extent. The profiles of subsidence (Fig. 2) and the map showing the contours (Fig. 3) illustrate both regional and local changes. A large area of subsidence is centered in the Houston-Baytown district, where the maximum recorded is about 2.7 ft between 1905 and 1954. This probably falls short of the actual maximum, since land surface subsided as much as 2.5 ft in the industrial section alone between 1943 and 1954. Sub-

Jan 1, 1960

By H. M. Manasevit, R. L. Nolder, L. A. Moudy

The observation that silicon-on-sapphire crystallo-graphic relationships exist which are unrelated to one another implies that there are regions of sapphire orientations containing these relationships which are separated by boundaries. The presence of these boundaries is demonstrated, initially on rounded cylindrical surfaces md more definitively on flat sapphire substrates with orientations along primary crystallograPhic zones. By means of reflection electron and X-ray diffraction techniques the crystallographic relationships have been studied. Two new relationships have been found, viz., (111) Si (1014) sapphire and (001)Si (1012) sapphire. Also found were multicrystalline relationships. The approximated boundaries between the crystallographic regions for each relationship are shown by means of a stereo-graphic projection. These studies also clarify discrepancies in the literature concerning the silicon-sapphire relationships on the (1120) sapphire substrate. SINCE the first report of the deposition of single-crystal silicon on sapphire in 1963' this epitaxial system has been the object of study by many semiconductor laboratories. In particular, there has been strong interest in the crystallographic relationships between the two materials. In 19652,3 we demonstrated that at least four distinct modes of orientation relationships can occur, namely, (100)Si (0112) sapphire, (111)Si 11 (1124) sapphire, (111)Si (1120) sapphire, and (111)Si (0001) sapphire. Each relationship could be obtained when the substrate plane was at the particular orientation indicated. Other workers as well as our laboratory concurred in general with the initial results. However, two discrepancies were observed. First it was observed by Joyce et a1.4 that on a (1120) substrate a (110) silicon deposit could be obtained. This was actually consistent with the (111)Si (1124) sapphire mode. Second, two other laboratories,5,6 as well as our own,7 have found a deposition on the basal plane which is different than our initial findings. Even though a (111)Si deposit was obtained, the crystallographic relationships were not identical to those previously found. Subsequent work in our laboratories has confirmed that the form found in these later investigations of the basal plane is by far the more predominant, and the original finding was an anomaly. The relationships which have been previously estab1.ished are summarized in Table I. It is seen that at present a rather small number of possible substrate orientations has been investigated. Therefore, it seemed appropriate that a systematic investigation of silicon epitaxy on various sapphire substrate orientations would be of value. It was expected that the answers to three questions could be obtained from such an investigation. These are as follows: 1) Since we know of at least four distinct modes of orientation relationships, over what range of substrate orientation do these modes occur and what is the form of the boundary expected between the different regions in which each mode occurs? 2) Are there other modes which occur on substrate orientations not previously investigated? 3) What is the explanation for the discrepancy between our laboratory's findings and those results reported by Joyce et al.4 concerning the relationships occurring on (1120) substrates? APPROACHES AND EXPERIMENTAL METHODS Two different approaches were used. Initially, depositions were carried out on rounded cylindrical surfaces which lay perpendicular to the (0112) plane.* By this means the presence of boundaries and their approximate positions could be determined. Finally and more definitively, depositions on flat sapphire substrates with a variety of orientations, mostly along primary crystallographic zones and about the (1120) plane, were studied by means of reflection electron diffraction and X-ray diffraction (using back-reflection Laue patterns and full circle goniometer techniques) in order to determine crystallographic relationships. The sapphire orientations investigated by these means

Jan 1, 1969

By A. W. Schlechten, C. M. Hsiao

The apparent vapor pressures of a number of metal sulphides were determined by measuring their rate of weight loss when they were heated under vacuum. The calculated pressures are due in some instances to the volatility of the sulphide and in others to the decomposition pressure. FIE direct reduction of metallic sulphides, as in the precipitation method for lead or antimony, is not a widely used process today. However, it might be employed for the production of a number of metals if the operation were carried out under reduced pressures. Two general procedures are possible; the reducing agent could form a stable nonvolatile sulphide from which the valuable metal could be removed by volatilization or liquation. The other approach would be to choose a reducing agent which would form a sulphide that could be volatilized away from the valuable metal. A vacuum operation would serve to protect the sulphides and metals from oxidation and would increase the evaporation rates. A related process is the separation of metallic sulphides by selective volatilization either at atmospheric pressure or under vacuum. This procedure is already used commercially for the elimination of lead and cadmium as PbS and CdS from zinc calcines; it might well have other applications. To predict such processes it is necessary to know the relative volatilities of the metallic sulphides and to know whether they volatilize as sulphides or whether the predominant weight loss is due to decomposition. Such data would also be of value in studying problems such as the use of sulphides for refractories, as described by Brewer,] or in the evaluation of the theory of ore deposition from the vapor state, as proposed by Brown.' Qualitative statements concerning the volatility of metallic sulphides can be found frequently in the literature and are well summarized by Mellor, but accurate determinations of rates of evaporation or vapor pressures are very scarce. Kelly" lists vapor pressure data only for PbS; his reference being to the work of Schenck and Albers,4 who measured the vapor pressure of PbS by a dynamic method between 850" and 995°C. More recently Veselovskii5 has determined the vapor pressures of the sulphides of antimony, lead, cadmium, and zinc at temperatures ranging from 360" to 1000°C using Knudsen's method. A second Russian worker, Pogorelyi,6 determined the vapor pressures of CdS and ZnS at temperatures from 900" to 1250°C. The results obtained by these workers are shown in subsequent graphs in comparison with the data of this paper. Brewer and coworkers1 have studied some of the metallic sulphides to determine their suitability as refractories in vacuum. Veselovskii's determinations on PbS checked well with those of Schenck and Albers, and his determinations of CdS check almost exactly with Pogo-relyi. For the vapor pressure of ZnS the data of Veselovskii and that of Pogorelyi are in fair agreement, as shown in Fig. 1, but it should be pointed out that Lumsden7 has discovered that the equation given by Veselovskii for the vapor pressure of ZnS: - 14,200 log P9.495 is in error by a factor of ten when compared to the experimental data. In contrast with the scarcity of data on vapor pressures, the decomposition pressures of many metal sulphides have been determined and are summarized by Smithells.8 Theoretical Considerations The experiments described in this paper consisted of determinations of the rate of weight loss of certain metallic sulphides under very low pressures at different temperatures. These data plus observation and analyses of the products reveal the mechanism of the weight loss and also provide a basis for the calculation of the vapor pressure or apparent vapor pressures of the sulphides.

Jan 1, 1953

By Milo W. Krejci

The plant and quarries of the Inland Portland Cement Co. are located at Metaline Palls, Wash., about 128 miles north of Spokane, on the Pend Oreille river, and within 10 miles of the Canadian border. The plant is one of a chain of cement plants controlled by the Lehigh Portland Cement Co., of Allentown, Pa. Work on this plant was commenced in June, 1910, and was completed in April, 1911, but on account of some delays in the construction of the power plant, the works were not put into operation until August, 1911. Since then it has been in continuous operation and has furnished the Inland Empire with a high grade of cement. Fig. 1 is a view and Fig. 2 is a plan of the works. Water Power Development.—The source of the water supply for the hydro-electric plant of the Inland Portland Cement Co. is Sullivan lake, a body of water approximately 5.5 miles long and' 0.5 mile wide, situated in the Kaniksu Forest Reserve. A wooden crib dam was installed so as to raise the elevation of the lake 25 ft., and the additional storage capacity was taken up by the diversion of Sullivan creek into the lake by means of a wooden flume, 0.25 mile long, 6 by 8 ft. in cross-section, and a ditch 1,200 ft. long. The water from the lake follows the natural water course to an intermediate storage reservoir, which was created by the construction of an earthen dam. This pond was used in connection with the saw mill which was installed at this point. Besides the earth dam, there was also built a crib, at the point shown in the sketch map, Fig. 3. This crib dam is 35 ft. high. From this point the excess water follows the natural course of Sullivan creek to the Pend Oreille river. The water is taken from this intermediage storage by means of a 6 by 8 ft. wooden flume approximately 13,000 ft. long. This flume is built up on the side hill, piling being driven most of the way on

Jan 1, 1914

By A. P. Svenningsen

IN the early stages of design it was not considered necessary that separate crushing plants be built for the new sulphide concentrator and smelter until sometime in the future. The plan was to use the existing crushing facilities for both oxide and sulphide ore. A few additions were contemplated for the existing plants, such as increased bin capacity, and possibly two new secondary crushing units. The more the problem was studied and discussed with the plant operators, the more it became evident that it was complex. It involved the classification of different kinds of ore from the open pit mine -sulphide, oxide and mixed-and how best to separate them so that each kind of ore was given the proper processing and treatment. It also involved the problem of keeping the different ores from being contaminated in bins, hoppers and chutes. Added to these, transportation became complicated and would involve additional handling and loading of ore from crushing plants to conveyors, to bins, and finally to railroad cars which were to be hauled to the concentrator and dumped into the fine ore bin. General In the early part of 1951 it was decided that the concentrator be constructed with ten grinding units instead of seven as originally authorized. The smelter was to be increased proportionally and naturally also the overall tonnages of ore to be handled by the new sulphide plant. Due to this increase in plant capacity and the larger tonnages involved, the difficulties which would arise by using the existing crushing plants were increased to a point where it became evident that the building of new crushing plants for sulphide ore exclusively was technically, as well as economically, advantageous. Authorization was, therefore, given by the company to construct new crushing plants to handle 30,000 tons of ore per day, and capable of reducing the run-of-open-pit ore to the proper size feed for the 10x14-ft rod mills in the concentrator. The ore, mined in the open pit, sometimes comes in pieces as large as 6 to 7 ft diam. The rod mills may call for ore crushed to 3/4 in. The large .size of ore delivered from the open pit determined that a 60-in. gyratory crusher be used as primary breaker. Such a crusher will have a capacity considerably in excess of 30,000 tons per day. The crusher will be a single discharge unit driven by a 500-hp electric motor through a tear coupling and a floating shaft. This type of drive has proven successful at a number of other crusher installations which our company has operating in the United States, Mexico and South America. The tear coupling will protect both the crusher and motor against damage in case of overload. No new features are incorporated in the design of the crusher itself, except that the, discharge chute is made the full width of the crusher with parallel sides instead of the usual converging sides. This change in detail should eliminate, a feature which has been a bottleneck in some of the operating plants and has caused loss of production due to ore hanging up and blocking the chute. The secondary crushing plants will have three 7-ft standard Symons cone crushers and six 7-ft short head Symons crushers. Between the primary and secondary crushing plants a coarse ore bin will be constructed with a nominal draw-off capacity of 30,000 tons of ore. The standard Symons and the short head Symons will be in separate buildings. All the crushing plants and the coarse ore bin are interconnected with conveyor belts for transporting the ore to the crushers at the tonnage rate desired. The final product of the new crushing plants is produced by the short head crushers. It will be delivered onto a conveyor belt leading to the top of the fines ore bin in the concentrator. A separate conveyor belt running the full length of the fines ore bin and provided with a movable tripper of rugged design will discharge the sulphide ore into the bin. The concentrator bin is planned and designed so that the installation of this additional conveyor will not interfere with the operation of the two railroad tracks on which crushed ore is brought from the existing oxide plant. Thus when completed the bin can be filled simultaneously by ore from the new crushing plant and by ore from the existing leaching plant.

Jan 1, 1952

By George Krauss, Morris Cohen

NUMEROUS investigators1-4 have shown that one of the most conspicuous effects of the reverse marten-sitic transformation in Fe-Ni alloys is the stabilization of the austenite which forms on reversal. However, the present authors5 found a virtual absence of stabilization in a recent study of this subject. The purpose of this note is to account for the discrepancy.

Jan 1, 1963

By D. R. Mitchell

MEETING for the thirteenth time in New York as part of the five-ring circus known as the Annual Meeting A.I.M.E., the Coal Division experienced a wartime boom in attendance. Technical sessions were crowded and whereas 65 seats were set up for the annual luncheon meeting of the Division over 100 members showed up, many of whom had to be fed elsewhere. Possibly the Coal Division should adopt "13" as its lucky number. Discussions at technical sessions, formal and informal, were lively. Those papers containing material directly concerned with the war, or containing information that might be usable for war industries, were enthusiastically received. Some criticism was made in regard to the present method of handling discussions and it was suggested that better success would be had in getting discussions in the record by the use of hired reporters. This is being considered by the executive committee of the Coal Division.

Jan 1, 1943

Jan 1, 1879

By K. G. Davis

Dilute alloys of silzer in tilz haz been solidzjzed a1 controlled rules, in lzorizontal tubes 2 mrz and 0.5 rn in diam. Radioactive; tracer techniques we?-e used to study solute distvihutions along llze specimens and irmpurity substructures, as functions of the conditions growth. The results have heen mzalyzed using Burton, Prim, and Slichter's tnodel for the solute disty-ihution in the liquid ahead of an advancing solid-liquid interface. DECANTING techniques have been used to establish criteria for the formation of impurity substructure during solidification in several alloy systems An analysis equating the appearance of impurity substructure with the incidence of constitutional supercooling was developed,= in which diffusion was assumed to be the predominant mode of solute mixing in the liquid. Substitution of experimental data into the equations derived from the diffusion analysis gave reasonable values for solute diffusivity in the liquid. However, in these investigations solidification rates of 10 cm per hr and over were used, to minimize the effect of natural conection, whereas for crystals of high perfection lower solidification rates are needed, usually between 1 and 5 cm per hr. A knowledge of the conditions under which impurity substructures will be formed at low growth rates, and the degree of segregation to be expected, is therefore of interest. In the present investigation, radioactive-tracer techniques have been used to study the effect of growth rate, initial solute concentration, and size of specimen on the formation of substructure in uni- directionally solidified rods of dilute silver in tin alloys, over a range of growth rate between 0.5 and 10 cm per hr. Criteria for the formation of substructure were established by auto radiography. This was believed preferable to the decanting technique, for the relationship of the structure on a decanted interface with that of the freezing interface is not clear, since a layer of liquid is left on the surface following decanting.' The effect of substructure on the distribution of solute along the rods was also investigated. EXPERIMENTAL The procedure for sample preparation has been described in detail by einber. Alloys were prepared from tin of 99.999 pct purity and silver of 99.99 pct purity. A"', an emitter of both y and 0 radiation, was used as tracer. Samples of the alloys were drawn up into silica tubes with inside diameters 0.5 or 2 mm, remelted in a horizontal furnace, and solidified at controlled rates. A few centimeters of the samples were left unmelted for a measure of the initial concentration. Total sample length was approximately 20 cm. The temperature gradient in the furnace was kept constant at 36°C per cm in the region corresponding to the melting point for tin. To find how well this corresponded to the actual temperature gradient in the melt, a thermocouple of 38-gage wire was electrically insulated with a thin layer of Sauereisen cement and placed within one of the 2-mm-diam tubes, which was then filled with tin. The maximum diameter of the coated wire was 0.5 mm, the bead of the thermocouple junction being no larger than the diameter of the wire. A plot of temperature vs distance traveled by the furnace is given in Fig. 1 for a rate of furnace travel of 1 cm per hr. The temperature gradient in the liquid

Jan 1, 1967