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By G. H. Alani, H. T. Kennedy

One of the major difficulties in predicting the performance of oil reservoirs from their early pressure history lies in the uncertainty of estimating the volume of the liquid hydrocarbons contained in them. As a first step in filling this need, an equation was developed to determine the Inolal liquid volume of pure hydrocarbons over a wide range of temperature and pressure. The second step consisted of adapting the equation to apply to mixtures, with the heary hydrocarbons expressed as c The equatious are similar in form to van der Waals equation. hut the constants a and b tire considered as furnctions of temperature. In addition to the gas constant R, there are four constants characteristic of each hydro- When comptired with experimental values jound in the literal the. the average absolute deviation in the calculated molal volumes is found to be a Maximum of 0.33 per -cem for any of the pure liquid hydrocarbons studied. This maximum deviation was that found when comparing the calculated and observed values over a temperature range of 86° to 482°F and a pressure range from the bubbl-point ro 10,000 psis. The equations expressing the correlation for. mixrurrc were developed from 647 experimental measure-rilents of volume on 47 bouom-hole samples covering ; temperature range of 72" to 250°F and a pressure znge from bubble-point ro 5,000 psig. The average absotute deviation was found to he 1.6 per cent with the maximum for any measurement of 4.9 per cent. INTRODUCTION Accuratc information of the pressure-volume-temper-iiture behavior of hydrocarbon liquids is of considerable importance in the field of both applied and theoretical science and, especially, in the solution of petroleum reservoir engineering problems. These PVT relationships can be expressed graphically, in tabular form or as equations of state. Equations of state for gases have been developed based on the ratio of pressure, temperature and volume to the pressure, temperature and volume at the critical points of the hydrocarbons. These equations have been successful in yielding values fairly accurate for reservoir engineering purposes. For liquids, however, relations of this type are more complex and have not yielded useful results. The composition of reservoir liquids is normally expressed in terms of the moles of hydrocarbons C,? C,. C,. elc, per mole of mixture. The composition must include the fraction of a mixture such as C,,, which cannot be separated with reasonable time and effort into specific hydrocarbons. Although there are several equations of state having variable degrees of accuracy applicable to pure liquid hydrocarbons, none includes a means for estimating the volume of mixtures as a function of temperature. pressure and composition expressed in this manner.

By John R. Green

Rotary kilns, varying in construction, are used in a variety of processes. Products differ and operating conditions vary accorcling to economic requirements. All of these variables influence the degree of instrumentation and type of control necessary or profitable to install. Products fired in rotary kilns are the results of combined temperature and time treatment and the interrelation of these two factors should be kept constantly in mind in the perusal of this paper. Measurements of Kiln Temperature The securing of proper temperatures within the rotary kiln, either of the charge or of the kiln lining in the high fire zone, are basic objectives of kiln operation; therefore the measurement of these high-temperature conditions merits first consideration. For these measurements, radiation pyrometers, properly designed and protected, have proved adequate, particularly where records ox automatic control are desired, while Optica1 pyometers may serve as portable indicators. Light-sensitive devices or photoelectric cells in this service are capable of producing records as well as certain forms of automatic control. High-temperature measuring devices for rotary-kiln work should have the measuring unit protected from dust, as a continued accumulation of deposit would lower the readings. Fig. 1 shows a typical application of radiation equipment to a rotary kiln, mounted far enough away from the sighting hole through the kiln hood to be protected From puffs or stingouts and with a sighting tube having a series of settling chambers, to prevent dust from reaching the lens. Although dust conditions inside the kiln itself usually fluctuate considerably and have their effect upon the readings at that moment, such effects are not cumulative and show as a continuous fluctuation in the temperature indicated, provided the radiation unit and recorder are responsive to such slight and rapid temperature fluctuations. The ambient temperature to which a measuring unit is subjected fluctuates from possibly 0" to over zoo°F., therefore these changes should have no effect upon the final reading or upon the life of the measuring unit. A very narrow sighting angle is desirable, so that measurement of temperature may be made as far as possible into the high fire zone without effect of the flame temperature. There should some sighting means on the measuring unit, so that the proper field may be viewed. Measurement of wall temperature taken at a point where the charge has just left the wall is less affected by dusting conditions than when taken elsewhere. Factors influencing Temperature Table I gives an outline of the factors that produce kiln temperatures and comments on the possibility of measurement and control. Of greater number and of varied influence are the factors that control when, where and how the heat is delivered to the kiln, the type of flame and the rate of

Jan 1, 1942

By John R. Green

Rotary kilns, varying in construction, are used in a variety of processes. Products differ and operating conditions vary accorcling to economic requirements. All of these variables influence the degree of instrumentation and type of control necessary or profitable to install. Products fired in rotary kilns are the results of combined temperature and time treatment and the interrelation of these two factors should be kept constantly in mind in the perusal of this paper. Measurements of Kiln Temperature The securing of proper temperatures within the rotary kiln, either of the charge or of the kiln lining in the high fire zone, are basic objectives of kiln operation; therefore the measurement of these high-temperature conditions merits first consideration. For these measurements, radiation pyrometers, properly designed and protected, have proved adequate, particularly where records ox automatic control are desired, while Optica1 pyometers may serve as portable indicators. Light-sensitive devices or photoelectric cells in this service are capable of producing records as well as certain forms of automatic control. High-temperature measuring devices for rotary-kiln work should have the measuring unit protected from dust, as a continued accumulation of deposit would lower the readings. Fig. 1 shows a typical application of radiation equipment to a rotary kiln, mounted far enough away from the sighting hole through the kiln hood to be protected From puffs or stingouts and with a sighting tube having a series of settling chambers, to prevent dust from reaching the lens. Although dust conditions inside the kiln itself usually fluctuate considerably and have their effect upon the readings at that moment, such effects are not cumulative and show as a continuous fluctuation in the temperature indicated, provided the radiation unit and recorder are responsive to such slight and rapid temperature fluctuations. The ambient temperature to which a measuring unit is subjected fluctuates from possibly 0" to over zoo°F., therefore these changes should have no effect upon the final reading or upon the life of the measuring unit. A very narrow sighting angle is desirable, so that measurement of temperature may be made as far as possible into the high fire zone without effect of the flame temperature. There should some sighting means on the measuring unit, so that the proper field may be viewed. Measurement of wall temperature taken at a point where the charge has just left the wall is less affected by dusting conditions than when taken elsewhere. Factors influencing Temperature Table I gives an outline of the factors that produce kiln temperatures and comments on the possibility of measurement and control. Of greater number and of varied influence are the factors that control when, where and how the heat is delivered to the kiln, the type of flame and the rate of

Jan 1, 1942

By A. G. Preban, R. J. De Angelis, J. B. Cohen, P. Gordon, D. C. Brillhart

Changes in stored energy, resistivity, density, X-ray line broadening, and dislocation arrangements (from transmission electron microscopy) have been mensured on copper specimens shock-loaded at 75 to 435 kbars. The stored energy in shock-loaded copper and changes in density and resistivity are larger than those after conventional deformation. A high density of twins makes an appreciable contribution to all the measured quantities. Dislocation densities rise to values of 1011 lines per sq cm at the highest pressure. The resistivity, density, and X-ray In a study of the effects of shock loading on copper, changes in stored energy, resistivity, density, hardness, lattice parameter, line broadening, and dislocation structure have been examined after subsequent annealing of specimens shocked to various pressures. This paper presents certain aspects of the data, taken by two groups, one at the Illinois Institute of Technology, and the other at Northwestern University, and compares the changes in these properties, and what they indicate about the effects of shock deformation. measurements yield dislocation densities in substantial agreement at all pressures, after correcting for the effects due to the twins. At the higher pressures, electron microscopy yields dislocation densities that are lower by a factor of about 5 to 10. Dislocation densities from stored -energy measurements are high; this finding can be rationalized by the consideration that the deformation twin boundaries present are largely incoherent. There is no evidence for homogeneous dislocation nucleation during shock loading. Shock loading any metal or alloy, such as copper, causes a large increase in yield strength, with dimensional changes of the order of only a few percent."' Other properties have not been extensively studied, but this result clearly indicates the importance of examining the substructure. Previous studies of the substructure of conventionally deformed specimens have been made using electron microscopy,3-6 X-ray diffraction,7,8 and etch pitting.9,10 The dislocation density can reach values of about 10" per sq cm; and the dislocations are arranged in cells approximately 0.15 in size. The substructure varies widely, however, from point to point in the specimen. The substructure of explosively loaded copper consists of cells of about the same dimensions6,11 but their size is more uniform.6 Profuse twinning occurs12,13 and the twins are often too small to be detected optically.6,13 The boundaries outlining these twins appear to be incoherent.14 There is now ample evidence 13-15 that twinning is a strengthening mechanism in fcc metals but this is only part of the strengthening effect in shock-loaded copper.* From the twinning systems which operate in shock-loaded single crystals,13 and from changes in texture on shock loading,17 it has been shown that both the

Jan 1, 1968

By C. V. Millikan

Temperature measurement in wells is an old practice and geothermal gradients have been of interest to geologists for many years.le2 Their application to the operation of oil wells is a more recent practice. It has long been recognized that temperature anomalies occur in drilling and producing wells but thermometers that could obtain a satisfactory record of the anomalies were not available. The normal geothermal gradient is con-sidered as being about one degree Fahren-heit for each 60 ft. of depth.4 This "nor-mal " gradient varies in different areas, but whatever it may be in an area there is little variation from the surface to as deep as the : drill penetrates. The normal gradient is appreciably changed by gas expanding ; from the reservoir into the borehole or by the movement of fluid through a borehole : while drilling, producing, or circulating. It is the resulting anomalies and abnormal gradients from which conditions in wells can be interpreted. Some of the applications of such interpretations are locating the position of oil or gas sands, permeable strata in a reservoir zone, gas-oil contact, source of water, casing leaks, and the top of cement behind casing. Thermometers A thermometer for use in wells must be sensitive and have a low thermal lag. The sensitivity should permit recording 0.2OF. or less for differential temperatures although the actual temperature need not be more accurate than 1°F. The thermal lag should be as low as rugged construction will permit in order to allow surveys to be made in a minimum of time. Of the several kinds of thermometers, these requirements are most easily obtained with the vapor-pressure, expansion, and electric-resistance types. Thermometers for use in wells may be self-contained—that is, the complete instrument is lowered into the well and a record made of the temperature—or the thermal element only may be lowered into the well and the temperature recorded at the surface. The vapor-pressure and expansion types are more adaptable for a self-contained instrument while the electric-resistance thermometer is more suitable for surface recording of temperatures. The self-contained instrument can be run against high pressure on a single wire line with only one operator required. The instrument and its hoisting equipment is easily portable and can be mounted on a small car. The disadvantages are a somewhat greater thermal lag and the necessity of completing a run before any temperature or temperature anomaly is known. A surface-recording thermometer has the advantage of being somewhat more sensitive and of having a lower thermal lag. The Operator can see what anomalies are encountered and can immediately change the running conditions of the instrument or the well conditions in order to obtain the most

Jan 1, 1941

By C. V. Millikan

Temperature measurement in wells is an old practice and geothermal gradients have been of interest to geologists for many years.le2 Their application to the operation of oil wells is a more recent practice. It has long been recognized that temperature anomalies occur in drilling and producing wells but thermometers that could obtain a satisfactory record of the anomalies were not available. The normal geothermal gradient is con-sidered as being about one degree Fahren-heit for each 60 ft. of depth.4 This "nor-mal " gradient varies in different areas, but whatever it may be in an area there is little variation from the surface to as deep as the : drill penetrates. The normal gradient is appreciably changed by gas expanding ; from the reservoir into the borehole or by the movement of fluid through a borehole : while drilling, producing, or circulating. It is the resulting anomalies and abnormal gradients from which conditions in wells can be interpreted. Some of the applications of such interpretations are locating the position of oil or gas sands, permeable strata in a reservoir zone, gas-oil contact, source of water, casing leaks, and the top of cement behind casing. Thermometers A thermometer for use in wells must be sensitive and have a low thermal lag. The sensitivity should permit recording 0.2OF. or less for differential temperatures although the actual temperature need not be more accurate than 1°F. The thermal lag should be as low as rugged construction will permit in order to allow surveys to be made in a minimum of time. Of the several kinds of thermometers, these requirements are most easily obtained with the vapor-pressure, expansion, and electric-resistance types. Thermometers for use in wells may be self-contained—that is, the complete instrument is lowered into the well and a record made of the temperature—or the thermal element only may be lowered into the well and the temperature recorded at the surface. The vapor-pressure and expansion types are more adaptable for a self-contained instrument while the electric-resistance thermometer is more suitable for surface recording of temperatures. The self-contained instrument can be run against high pressure on a single wire line with only one operator required. The instrument and its hoisting equipment is easily portable and can be mounted on a small car. The disadvantages are a somewhat greater thermal lag and the necessity of completing a run before any temperature or temperature anomaly is known. A surface-recording thermometer has the advantage of being somewhat more sensitive and of having a lower thermal lag. The Operator can see what anomalies are encountered and can immediately change the running conditions of the instrument or the well conditions in order to obtain the most

Jan 1, 1941

By Walter Crafts, C. M. Offenhauer

IN a previous study' of the carbide phase of chromium steels, it was shown that chromium carbide (Cr7C3) is a more stable carbide than cementite (Fe3C) at tempering temperatures above about 500°C. in quenched steels containing from about r1to 7.5 per cent chromium. Below this temperature the carbide phase was found to consist of cementite in all of the steels examined. In the present investigation it was found that a similar change in the carbide phase takes place in molybdenum and in chromium-molybdenum steels at approximately the same tempering temperatures. The approximate ranges of occurrence of the alloy carbides Cr7C3, Cr4C, and Mo2C have been determined in steels containing up to 5 per cent chromium, 1 per cent molybdenum and 0.60 per cent carbon. The experimental steels were made in small high-frequency furnaces from Armco ingot iron, low-carbon ferrochromium and calcium molybdate and were poured into 2-in. ingots, which were forged to 1-in. round bars. Sections of the bars were heated to the carbide-solution temperature and cooled rapidly to induce austenite transformation at relatively low temperatures. The steels were subject to some segregation, therefore comparatively high temperatures were necessary to dissolve all of the carbides. The microstructure of the quenched specimens was examined to verify the belief that the carbides had been dissolved, and also to determine the nature of the nonmartensitic structure of incompletely hardened steels. Ferrite and pseudomartensite were present in some of the specimens, but all specimens were quenched at such a rate that pearlite was not formed, in order to ensure the formation of the carbides at temperatures lower than about 500°C. It had been found previously' that in chromium steels the chromium carbide could be produced by transformation of austenite in the pearlite range above 500°C., and, in order to start the tempering treatment with the carbide present as cementite, the absence of pearlite was considered to be essential. The specimens were tempered for 64 hr. to permit the formation of the stable carbide. After tempering, the specimens were submitted to microscopic and X-ray examination. The carbides were separated either electrolytically in a 5 per cent HCl electrolyte or with an acidified copper-potassium chloride solution. The crystal structure of the carbide phases was determined by the Debye-Scherrer type of X-ray patterns. The X-ray patterns obtained from specimens near the boundaries between two types of carbides were generally weak and diffuse as compared with the other patterns. For this reason, and because the more soluble components may be masked, the boundaries between the phases could not be determined precisely. However, the X-ray analysis of electrolytically separated carbides has given consistently reproducible results

Jan 1, 1943

By B. W. Levinger

THE lattice parameter of the ß form of pure titanium has been measured at elevated temperature.', ' No attempt was made, however, to correct the parameter obtained to room temperature. In the course of phase diagram studies at Armour Research Foundation and elsewhere, the variation of ß-phase lattice parameter with composition has been established in a number of binary and ternary systems involving titanium. It was possible to extrapolate in these instances to 100 pct Ti to find the apparent lattice parameter of ß titanium at room temperature. Table I lists the results thus obtained. The suggested value for the lattice parameter of ß titanium is the average of the extrapolated values 3.276 ±0.003 kX. This suggested value gives an interatomic distance in ± titanium of 2.837 kX and hence a Goldschmidt atomic diameter (coordination number 12) of 2.925 kX. The latter agrees closely with the value of 2.93 given by Hume-Rothery." From the data of Adenstedt and coworkers' it was possible to determine by extrapolation the mean coefficient of linear expansion for /3 titanium in the range from room temperature to 1000°C. This value, 10.1x10-8 per degree C, compares with about 11x10-8 for a titanium in a similar range." It was thus possible to calculate the parameter at 900 °C. The value of 3.305 kX agrees well with 3.3065 given by Eppel-sheimer.' The majority of values reported in the literature7-', ' were given as Angstroms. In at least one case, ref. 8, it was shown that they actually represented kX units. The source of this confusion appears to be that a large number of tables of X-ray emission spectra list wavelengths as Angstroms and give values in kX units. The accepted conversion factor for kX units to Angstroms (10.' cm) is 1.00202. Thus the parameter of ß titanium suggested corresponds to 3.282A. References J. H. de Boer, W. G. Burgers, and J. D. Fast: Proc. Acad. Amsterdam (1936) 39, p. 515. 2D. S. Eppelsheimer and R. R. Penman: Nature (Dec. 2, 1950) 166, p. 960. 3 W. Hume-Rothery: The Structure of Metals and Alloys (1945) London. Inst. Metals. 4 H. K. Adenstedt, J. R. Pequignot, and J. M. Raymer: Trans. ASM (1952) 44, p. 990. 5 Gmelins Handbuch der Anorganischen Chemie. Titan, Verlag Chemie, Weinhein (1951). 8 P. Pietrokowsky and P. Duwez: Trans. AIME (1952) 194, p. 627; Journal of Metals (June 1952). 7 P. Duwez and J. L. Taylor: Trans. ASM (1952) 44. D. 495. 8 M. Hansen, E. L. Kamen, H. D. Kessler, and D. J. McPherson: Trans. AIME (1951) 191, p, 881; Journal of Metals (October 1951). 8 Unpublished Research, Armour Research Foundation.

Jan 1, 1954

By Harmon D. Nine

DISCONTINUITIES in the strain vs cycles to failure (S-N) fatigue curves have been reported for polycrystalline materials by Porter and Levy for copper,&apos; by Benham and Ford for mild steel,&apos; and by Williams and Stevens for 18/5 stainless steel.3 However, the considerable scatter of the points for polycrystalline materials have made a statistical analysis of the data necessary to confirm the discontinuities. By using oriented single crystals of high-purity material and low grown-in dislocation content, the reproducibility has been improved to a degree which makes statistical analysis unnecessary and clearly shows discontinuities in the S-N curves. A recent publication4 reports an abrupt change of slope in the S-N curve for ( 100) axially oriented copper single crystals fatigued in torsion. The reported discontinuities in the S-N curve, along with a different mode of failure in the two branches of the curve, have been interpreted as being due to two different amplitude-dependent mechanisms. Further work on copper single crystals of (111) axial orientation has now been completed which supports the existence of an amplitude-dependent change in the mechanism of fatigue. In the present study torsional-fatigue experiments were performed at room temperature in air on (111) axially oriented single crystals. The crystals were grown and prepared as reported in Ref. 4. Two different methods of growing the crystals also discussed in Ref. 4 produced crystals of two different perfections: Type I with dislocation density of >l06 per sq cm and Type I1 with dislocation density of <l05 per sq cm. In accordance with the accepted hypothesis that crystal flaws are primarily responsible for the scatter of fatigue lifetimes, particularly at low amplitudes, the values for the three lowest amplitudes for Type I crystal are believed to be uncertain. They are marked in braces in Fig. 1. On the other hand, at amplitudes above a surface shear strain (SSS) of *0.003, the data for both types of crystals are in agreement. Most remarkably the S-N curve for torsional fatigue of (111)-oriented single crystals is composed of three segments separated by rather large discontinuities, Fig. 1. Metallographic and X-ray measurements indicate that the lower branch corresponds to the low-amplitude (F) region of the (100) copper single-crystal results as discussed in Ref. 4, and the two upper branches correspond to the high-amplitude (H) region. The lower discontinuity in the (111) S-N curve and metallographic evidence give further support to the hypothesis that different mechanisms of failure operate for high and low strain amplitudes. Reference to the resolved shear stress diagram, Fig. 2, shows that the highest stressed systems in

Jan 1, 1965

By C. P. Proctor, E. D. Hummer, J. A. Younkins

COMPARATIVELY little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission of any effluent of high solid content to be replaced by clean water in order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the purpose of this paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settling and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." GENERAL ARRANGEMENT OF WATER SYSTEM So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers.1.2 The washer, which handles 0 to 4-in. raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. r) consists of twin 48-in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10 ½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By J. L. Taylor, P. Duwez

PARTIAL phase diagrams of titanium with iron, cobalt, and nickel have been established by previous investigators.1-3 These diagrams seem to be reliable, at least for concentrations of titanium ranging from 0 to about 50 at. pct. More recently, Long and his collaborators have presented a tentative titanium-nickel diagram covering the titanium-rich side.&apos; These various studies indicate that in each system three intermediate phases exist and correspond to the compositions Tia, TiX, and TiX2 (or TiX3). The purpose of this paper is to review the available information on the crystal structure of these phases and to give the results of additional X-ray diffraction studies. Previous Work A summary of the work of Wallbaum and his collaborators"-&apos; is presented in table I. The first intermediate phase on the titanium-rich side of the three systems, with iron, cobalt, and nickel, is of the Ti2X type and has a face-centered cubic structure. Although it is stated that the unit cell contains 96 atoms: no lattice parameters are given. The second phase is centered around the compositions TiX for the three systems. The crystal structure of this phase is mentioned in a short note" as being body-centered cubic (CsCl type), but no parameters are given. The analogy between the three systems, which is perfect as far as the two phases of the type Ti2X and TiX are concerned, disappears at the titanium-poor end of the diagrams. In the system titanium- iron, TiFe2 has an hexagonal (MgZn2 type) struc-ture with the parameters given in table I. The existence of TiFe3 has also been reported8 (table I) but was questioned by other investigators2 and is also refuted by the present study. In the system titanium-cobalt, a phase corre-sponding to the composition TiCo2 has been investi-gated by Wallbaum and Witte6 who claim that the structure is cubic (MgCu2 type) for alloys slightly deficient in cobalt and hexagonal (MgNi2 type) for alloys slightly deficient in titanium. The parameters of the two phases are given in table I. In the system titanium-nickel, the nickel-rich phase corresponds to the composition TiNi3 and has been described as hexagonal7 with the parameters given in table I. The present investigation was initiated for the purpose of filling in the gaps in the knowledge con-cerning the structure of the various phases sum-marized in table I. Since the titanium used by Wallbaum and his collaborators was only 95 pct pure,&apos; it was found desirable to redetermine the lattice parameters of the alloys prepared with a

Jan 1, 1951

By R. T. Webber, R. B. Owen

The vapor phase deposition of molybdenum and tungsten from the hexacar-bonyls has been thoroughly investigated by Lander and Germerl, and shown to yield well-bonded coatings on a variety of hot metallic surfaces. They also demonstrated that chromium coatings2&apos;3 could be similarly deposited, but did not investigate this metal extensively. Recently, conditions have been described by which this compound can be prepared in quantities sufficient for laboratory scale plating experiments, and it is the purpose of the present communication to outline the results of preliminary experiments upon the plating of chromium from its carbonyl. Apparatus and Technique The apparatus used in these experiments is shown in Fig I. At one end, connected by a short length of rubber tubing, is a Cenco Hypervac 20 pumping continuously. At the opposite end is a needle valve which allows a small stream of purified hydrogen to flow through the apparatus. Connected in series are a trap T1, maintained at the temperature of dry ice and acetone, the plating chamber, and two traps T² and T3 containing crystals of the carbonyl. T² is kept in a constant temperature bath (not shown), while T³ is at room temperature. Stopcock S6 allows the hydrogen flow to by-pass the carbonyl traps. A McLeod gauge is connected so that it can measure the pressure at the pump through Se, or the pressure at the plating chamber through S9 and S6. The standard (12 liter) volume connected by Sb is used to determine the volume included by S4, S6, SB, Slot the needle valve and the McLeod gauge. Knowledge of this volume allows calibration of the flow of hydrogen. The apparatus* is built entirely of pyrex, except for the needle valve, the rubber connection to the Hypervac, and the cover of the plating chamber. The plating chamber is water-jacketed, with a large brass top allowing insertion of the specimen to be plated. Set into the brass top is a ground glass stopper through which thermocouple leads are sealed. The thermocouple wires (pure Pt, and 87 pct Pt-13 pct Rh) serve the double purpose of measuring the specimen temperature and suspending it in the chamber. Surrounding the chamber is the coil of an induction heater, H. The apparatus is designed to allow variation of the following conditions: (I) the specimen temperature, from room temperature to about 1000°C, (2) the carbonyl vapor pressure, from 40 to 220 microns, and (3) the hydrogen flow. In several runs, 0.8 to 1.8 PCt of hydrogen sulfide was introuced through a needle valve that replaced S4. The vapor pressure of the carbonyl is

Jan 1, 1949

By R. T. Webber, B. B. Owen

THE vapor phase deposition of molybdenum and tungsten from the hexacarbonyls has been thoroughly investigated by Lander and Germer1 and shown to yield well-bonded coatings on a variety of hot metallic surfaces. They also demonstrated that chromium coatings2.3 could be similarly deposited, but did not investigate this metal extensively. Recently,4 conditions have been described by which this compound can be prepared in quantities sufficient for laboratory scale plating experiments, and it is the purpose of the present communication to outline the results of preliminary experiments upon the plating of chromium from its carbonyl. APPARATUS AND TECHNIQUE The apparatus used in these experiments is shown in Fig I. At one end, connected by a short length of rubber tubing, is a Cenco Hypervac 20 pumping continuously. At the opposite end is a needle valve which allows a small stream of purified hydrogen to flow through the apparatus. Connected in series are a trap T1, maintained at the temperature of dry ice and acetone, the plating chamber, and two traps T2 and T3 containing crystals of the carbonyl. T2 is kept in a constant temperature bath (not shown), while T3 is at room temperature. Stopcock S6 allows the hydrogen flow to by-pass the carbonyl traps. A McLeod gauge is connected so that it can measure the pressure at the pump through Ss, or the pressure at the plating chamber through S9 and S6. The standard (12 liter) volume connected by S5 is used to determine the volume included by S4, S6, Se, S10, the needle valve and the McLeod gauge. Knowledge of this volume allows calibration of the flow of hydrogen. The apparatus* is built entirely of pyrex, except for the needle valve, the rubber connection to the Hypervac, and the cover of the plating chamber. The plating chamber is water-jacketed, with a large brass top allowing insertion of the specimen to be plated. Set into the brass top is a ground glass stopper through which thermocouple leads are sealed. The thermocouple wires (pure Pt, and 87 pct Pt-13 pct Rh) serve the double purpose of measuring the specimen temperature and suspending it in the chamber. Surrounding the chamber is the coil of an induction heater, H. The apparatus is designed to allow variation of the following conditions: I, the specimen temperature, from room temperature to about 1000°C, 2, the carbonyl vapor pressure, from 40 to 220 microns, and 3, the hydrogen flow. In several runs, 0.8 to 1.8 pct of hydrogen sulfide was introduced through a needle valve that replaced S4. The vapor pressure of the carbonyl is

Jan 1, 1948

By Glen R. Neighbors, Sylvan Cromer

HIGH subsurface temperatures and pressures are making cementing operations more difficult as deeper producing horizons are being sought. Recorded bottom-hole temperatures above 200°F. and pressures in excess of 12,000 Ib. per sq. in., obtained by combining hydrostatic and pump pressures, are not uncommon. Insufficient time is available for proper placement of standard Portland cement, because of the shortened setting time produced by these excessive temperatures and pressures, therefore special types of cements have been developed to overcome these difficulties. From the standpoint of placement, the ideal slurry would be one that would remain fluid long enough to be placed, then harden rapidly, so that there would be a limited amount of contamination and the well could be placed on production in a minimum of time. It is highly desirable, therefore, that some method be devised to measure accurately the time that any slurry will remain in a fluid state while being pumped into the well. To study the effect of elevated temperature and pressure on fluidity, the authors have developed the pressure-type consistometer (Figs. I and 2) described below, and are presenting data obtained with it, using slurries of both quick-setting and slow-setting cements. Studies were made over a temperature range from 110° to 270°F., and a pressure range from atmospheric to 3000 lb. per sq. inch. APPARATUS The fluidity of cement slurries at atmospheric pressure is usually determined with the Halliburton consistometer1 or the Thickening Time Tester.2 These instruments are similar, in many respects, to an ordinary ice-cream freezer. The slurry to be tested is placed in a container that is rotated at a constant speed with an electric motor. Constant temperature is maintained by surrounding the container with a thermostatically controlled bath. The torque on the paddles, which is proportional to the force needed to shear the slurry, is indicated on a scale. The Halliburton instrument is calibrated from 0 to 100 poises against fluids of known viscosity. To permit direct correlation of observed elevated pressure data with those published at atmospheric pressure, the authors&apos; designs of the slurry container, paddle, and torque indicator closely resemble those used on the Halliburton instrument. Duplicate results may be obtained at atmospheric pressure in either instrument. Instead of the atmospheric constant-temperature bath, one was built from a high-pressure steel bull plug. A Uni-Bolt union equipped with a blanking plug serves as the top, permiting the instrument to be opened or closed in less than one minute. The slurry container is built from Shelby steel tubing. A wrench socket welded to the bottom of the container engages a hexagonal nut on the top of the steel shaft that rotates it. This acts as a universal

Jan 1, 1941

By J. E. Gould, H. J. Hand

MANY independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types In maintaining quality control at the National Tube Company&apos;s plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final deoxidation In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding over-deoxidation to minimize the amount of inclusions present and to make as sound a steel as possible For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or long FeO values The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishing the state of oxidation at a given time Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors Data obtained are from actual furnace operations, the metal test being of the spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States Steel Corporation This method of taking open-hearth metal temperature was invented by Collins and Oseland,1 and was developed into its present form by L 0 Sordahl,2 of the Research Laboratory The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications 3,4,5 Slag components were obtained by chemical analysis Data were taken from four 165-net-ton furnaces during the working period of the heat Recognizing that additions of ore affect the

Jan 1, 1942

By John R. Green

ROTARY kilns, varying in construction, are used in a variety of processes. Products differ and operating conditions vary according to economic requirements. All of these variables influence the degree of instrumentation and type of control necessary or profitable to install. Products fired in rotary kilns are the results of combined temperature and time treatment and the interrelation of these two factors should be kept constantly in mind in the perusal of this paper. MEASUREMENTS OF KILN TEMPERATURE The securing of proper temperatures within the rotary kiln, either of the charge or of the kiln lining in the high fire zone, are basic objectives of kiln operation; therefore the measurement of these high-temperature conditions merits first consideration. For these measurements, radiation pyrometers, properly designed and protected, have proved adequate, particularly where records or automatic control are desired, while optical pyrometers may serve as portable indicators. Light-sensitive devices or photoelectric cells in this service are capable of producing records as well as certain forms of automatic control. High-temperature measuring devices for rotary-kiln work should have the measuring unit protected from dust, as a continued accumulation of deposit would lower the readings. Fig. I shows a typical application of radiation equipment to a rotary kiln, mounted far enough away from the sighting hole through the kiln hood to be protected from puffs or stingouts and with a sighting tube having a series of settling chambers, to prevent dust from reaching the lens. Although dust conditions inside the kiln itself usually fluctuate considerably and have their effect upon the readings at that moment, such effects are not cumulative and show as a continuous fluctuation in the temperature indicated, provided the radiation unit and recorder are responsive to such slight and rapid temperature fluctuations. The ambient temperature to which a measuring unit is subjected fluctuates from possibly 0° to over 200°F., therefore these changes should have no effect upon the final reading or upon the life of the measuring unit. A very narrow sighting angle is desirable, so that measurement of temperature may be made as far as possible into the high fire zone without effect of the flame temperature. There should be some sighting means on the measuring unit, so that the proper field may be viewed. Measurement of wall temperature taken at a point where the charge has just left the wall is less affected by dusting conditions than when taken elsewhere. Factors Influencing Temperature Table I gives an outline of the factors that produce kiln temperatures and comments on the possibility of measurement and control. Of greater number and of varied influence are the factors that control when, where and how the heat is delivered to the kiln, the type of flame and the rate of

Jan 1, 1941

By C. S. Matthews, H. C. Lefkovits

The performance of depletion-type reservoirs at the stage in which the gas is at such low pressure that gravity is essentially the sole driving force has been investigated both theoretically and by use of scaled models. A simple theory is developed which completely explains the scaled model experiments. It also agrees with some field data. When the range of production rates to be considered is less than 25, the theory predicts that the production rate decline curve for homogeneous reservoirs in which there is a free surface will be of the hyperbolic type with n = 2: The theory gives a physical significance to the parameter y. INTRODUCTION This investigation was undertaken to determine a method for prediction of performance of reservoirs where gravity is the sole driving agent. Depletion-type reservoirs fall into this category after the pressure has fallen to some low value. Some examples of this type are found at Healdton (&apos;Oklahoma), Oklahoma City (Oklahoma), Midway-Sunset (California), and East Coalinga (California). Generally the production rate per unit thickness is quite low in such reservoirs, with the conse- quence that this stage is sometimes called the stripper stage. However, per well production rates may be of the order of 50 B/D because of the considerable sand thickness open in some of the reservoirs. In the past, predictions of behavior of such reservoirs have been based on empirical extrapolation of the rate of production to the economic limit. Difficulties arise when new wells are drilled in the field or when production is artificially curtailed, since in such cases the decline rate of individual wells or leases changes and no clear trend can be detected. It was hoped that the present study would lead to improved methods for evaluation of such reservoirs. The study was initiated by building a scaled model for a particular field and by running a number of experiments on this model. Later a simple theory was developed which explained the laboratory results completely. The theory led, as shown below, to a hyperbolic-type decline equation which had been used previously&apos; in a completely empirical manner. THEORY The General Case The problem to be treated here is the following: We are given a homogeneous cylindrical porous reservoir with exterior radius r, wellbore radius r., and height h,, containing, from the bottom up to a height hit oil, some gas, and interstitial water (see Fig. 1 A). The portion of the reservoir between K, and h, is filled with gas at low pressure, with residual oil, and with interstitial water. If at a time t = 0, the level of the oil in the wellbore is lowered to a height h,, what is the production rate from the reservoir at a time to The configuration within the reservoir at some instant

Jan 1, 1957

By J. M. Seeman, R. A. Dodd

If some solution-quenched supersaturated aluminum solid solutions, e.g.., Al(Cu), are plastically deformed at room temperature and then aged at 200oC, the hardness may first decrease before increasing in the usual manner &apos; A similar transient softening is observed, even in the absence of plastic deformation, when a thin foil or small-diameter wire Al(Cu) specimen is rapidly quenched from the solution-treatment temperature and then aged.&apos; Also, some solution-quenched and neutron-irradiated alloys undergo an initial hardness decrease during subsequent aging.3 The usual explanation of the transient softening in the above examples involves the effect of vacancies introduced by plastic deformation, rapid quenching, and neutron irradiation, respectively However, the mechanism of softening is not unequivo-cably established. In the first-noted case, Gane and parkins&apos; observed that the softening was approximately proportional to the difference in the atomic diameters of solute and solvent, and it was argued that, if a large relative difference in atomic diameter promoted vacancy-assisted room-temperature solute diffusion to dislocations, dislocation climb occurring during subsequent aging at 200°C could cause transient softening. Some substantiation of this theory was offered by the additional observation that discontinuous yielding of solution-quenched polycrystalline Al(Cu) tensile specimens was suppressed by interrupting the test for a short aging treatment at 200°C. Of course, reversion (resolution of GPI) at 200°C would also cause softening, and Sil-cock4 expressed the opinion that the softening in the case of Al(Cu) must be partly associated with reversion. Also, Hirsch5 commented on the possibility that, if jogs cause hardening, an anneal at 200°C should straighten the jogged dislocations and result in softening. However, parkins&apos; has re-expressed his belief that these mechanisms are not entirely consistent with the observed serrated stress-strain curves. Experimental. New data has now been obtained for Al(Cu), Al(Ge), Al(Mg), and Al(Zn) primary solid-solution alloys. These alloys were prepared from metals exceeding 99.99 pct purity, and specimens 4 by 4 in. diam were solution-treated, quenched, deformed 10 pct in compression at room temperature, and aged at 200&apos;C in a cottonseed oil bath for various times. Generally, these operations could not be carried out in rapid succession, so the alloys were stored in a freezer between treatments to minimize aging. The variation in hardness with aging time, Figs. 1 to 4, was determined by microhardness testing with a 3.0-kg load. At least five readings were averaged to obtain each data point, and all measurements were taken about the center circumference of each cylinder (region of maximum deformation). Each specimen was used to obtain only one data point, i.e., specimens were not replaced in the aging bath after measurements were made. In

Jan 1, 1968

By Ralph Hultgren, David W. Mitchell

Magnesium alloys usually are superheated before casting in order to ensure fineness of grain. Superheat temperatures in common use range from 1600" to r 7o0°F.; the casting temperature, which depends upon the mold shape, is usually 200° to 300°F. lower. The process of superhcating requires considerable time and seriously shortens the life of the iron pots used. Recently it has been reported1 that if acetylene, carbon dioxide or natural gas is bubbled through molten electrolytic A.S.T.M. No. 4 alloy at 1400°F. for 5 min., grain refinement equivalent to that of superheating will take place. Addition of certain solids such as graphite or aluminum carbide accomplishes the same results? As will be shown in this paper, it is possible to achieve grain refinement in magnesium casting alloys at low temperatures by mechanical stirring of the molten metal for a short time. This process was developed in the course of research work, supervised by the War Metallurgy Committee under the "Restricted&apos; project NRC-550, for the Office of Production Research and Development of the War Production Board. This paper, based on that work, has been released for publication by the O.P.R.D. Materials and Methods The alloys studied were the most common American sand-casting alloys designated as No. 4 and No. 17 by the American Society for Testing Materials. The magnesiun used in these alloys was of both carbothermic3 and electrolytic&apos; origin. Chemical analyses supplied by the producers are shown in Table I. Each heat consisted of approximately 5 lb. of alloy melted in a Tercod crucible. It was refined by fluxing with Permanente No. 7* refining flux at 1300° to 1350°F. After cooling to 1200° to 1250°F., portions of approximately one pound each, were ladled into iron crucibles contained in an electric furnace at about 1250°F. The molten metal was covered with Permanente No. 21 † covering flux and then heated to the temperature to be investigated. Normally each of the four portions was given a different treatment. In a typical case one portion was stirred vigorously for 5 min., acetylene gas was passed through a second portion for 5 min., a third portion was superheated to 1600°F. for 15 min., then . cooled to casting temperature, and the fourth was held for 5 min. at the temperature of stirring or gassing without other treatment. Each portion was then cast into one-inch diameter cylinders in three "nonturbulent" molds of identical shape. One mold was made of cast iron and the other two of baked sand. The cast-iron mold and one of the baked sand molds were heated to 360°F., the other baked sand mold was at room temperature. The freezing times in these molds were

Jan 1, 1945

By Robert L. Hoss

The application of Muskat&apos;s differential equations for predicting the performance of a solution gas-drive reservoir to the Fullerton field indicates that a recovery may be expected of 14,030 bbl per acre under primary depletion, and 15,910 and I7,190 bbl per acre, respectively, under the two pressure-maintenance programs analyzed. In this analysis it is assumed that fluid properties are the same throughout the reservoir, that the core data used are typical of the Clear Fork limestone in the locality, and that injected gas is completely diffused through the pay zones. The economic study of the three recovery programs considered indicates that the one in which 60 pct of the produced gas is returned to the formation is the most profitable. Introduction The purpose of this paper is to consider the effect of pressure maintenance by gas injection on the ultimate recovery of oil from a solution gas-drive reservoir. This prediction of reservoir behavior is the result of calculations based on the equations presented by M. Muskat in the Journal of Applied Physics, March 1945. Reservoir The reservoir analyzed is the Fullerton field in Andrews County, West Texas. It is situated on a broad anticlinal structure with approximately 330 ft of closure, and extends approximately eight miles north and south and five miles east and west. The areal extent is taken as 16,642 acres. The producing horizon is the Lower Clear Fork limestone of Permian age, occurring at depths from 6650 to 7350 ft. It is divided into four zones. For the purposes of this study, the fluid characteristics in all zones are assumed to be the same. Therefore an equivalent zone is assumed of thickness equal to the sum of the thicknesses of the four zones, or an average of 216 ft. The reservoir contains 3,586,991 acre feet of producing limestone, with an initial volume of stock tank oil in place of 918,-403,100 bbl. The average connate water saturation is 24.0 pct. The permeability ranges from 6.7 md. to 12.6 md., and the porosity ranges from 7.7 pct to 11.4 pct, except for occasional cavernous streaks. Based on these values, the limestone may be considered intergranu1ar.l Production histories and material-balance studies have indicated that the driving mechanism is solution gas. Water levels have been established. Theory It is possible to express mathematically the change in residual oil saturation with pressure decline in a solution gas-drive reservoir as being equal to the change in the physical properties of the fluids present in the reservoir as this pressure decline occurs. Essentially these equations, in differential form as presented by M. Muskat,2 express quantitatively the instantaneous net effect

Jan 1, 1948