Search Documents

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 John Lamont, Walter Crafts

The principle formulated by Grossmannl for calculating hardenability of steel by multiplying the ideal diameter of "pure" iron-carbon alloys by factors for grain size and alloying elements has been confirmed on many steels and has proved useful in designing substitute alloy steels. Grossmann found that the typical behavior of the multiplying factors was to increase directly in proportion to the amount of the alloy present in a steel. However, the multiplying factor for the effect of silicon on hardenability was found by Grossmann to increase to a lesser degree as the amount of silicon was increased. In view of the increasing use of silicon in heat-treating steels, the effect of silicon on hardenability is becoming more important. Calculation of the hardenability of high-silicon steels made at the Union Carbide and Carbon Research Laboratories, Inc., indicated that the multiplying factor for silicon increased directly in proportion to the amount of silicon present. A more extended study of high-silicon steels covering fairly wide ranges of grain size, carbon, manganese, and aluminum has confirmed that up to 2 per cent silicon the multiplying factor is directly proportional to the silicon content. Manganese and aluminum factors have also been! determined. The results of the study offer strong confirmation of the general validity of Grossmann's multiplying principle. Testing Procedure Steels on which the study of the effect of silicon on hardenability was based were made in high-frequency induction furnaces using Armco iron and standard alloying materials. The ingots were forged to bars, and sections were normalized prior to machining Jominy hardenability test specimens. The Jominy test was carried out under standard conditions.2 The depth of hardness penetration for determination of ideal diameter at "half hardness" was taken at the hardness level indicated in Fig. 29 in Grossmann's paper by the solid line for 50 per cent martensite in plain carbon steel. The depth of penetration of hardness on the Jominy specimen was converted to ideal diameter by the relation given in Fig. 28 of Grossmann's paper. Chemical analysis was determined on a sample taken adjacent to the Jominy specimen. Aluminum was determined as "acid-soluble aluminum" rather than as total aluminum, as it is probably more representative of the aluminum that is effective as an alloying agent. In addition to the elements nominally present in the steels, analyses were made for residual phosphorus, sulphur, nickel, copper, molybdenum and chromium on one heat of those made with the same materials during the same period. Actual grain size was determined by microscopic examination of small samples quenched in water after receiving the same thermal cycle as the Jominy hardenability specimens. Chemical analyses, heat-treatment, grain size, and hardenability are shown in Table I representing three ranges of composition.

Jan 1, 1943

By A. W. Schlechten, W. J. Kroll

As this paper is written, the only method for the commercial production of lithium metal is by the fusion electrolysis of LiCl-KCl mixtures, as first proposed by Guntz.2 The details of the industrial process have not been made public but Osborg8 stated that an efficiency of more than go pct is obtained with a lithium metal recovery above 95 pct and that the metal is 99.5 pct pure. Pletenev9 gave a power consumption of 66 kw-hr per kilogram of lithium metal produced with a salt consumption of 9 kg of LiCl and 0.4 kg of KCI. Pletenev's figures indicate a somewhat lower recovery than that given by Osborg. In a recent report on German lithium plants, Motock7 gives figures that are also less favorable than those reported by Osborg. At the German plants the lithium recovery in electrolysis was only 83.4 pct, with a power consumption of too kw-hr per kilogram of lithium. The metal averaged only 97 pct pure, with sodium and potassium as the chief impurities. The presence of SO2, SO3, Si02, Ba, Ca, and appreciable amounts of Na and Fe2O3 were especially disturbing in the electrolysis, and it was necessary to run the cell for some time to eliminate most of these impurities and condition the bath. It may be noted here that most of these impurities do not interfere with a thermal reduction process. These facts show that the present method of producing lithium is fairly efficient and would suggest that other methods could not compete. However, fusion electrolysis has certain drawbacks, such as the necessity of supplying costly, low-voltage direct current and of collecting and processing the anodic chlorine if it is not to be wasted. An even greater disadvantage is that lithium chloride must be used for an electrolyte. It is one of the most expensive salts of lithium, since it cannot be produced in anhydrous form by precipitation from aqueous solution, as is done with LiF or Li2CO3. The reduction of lithium by a vacuum process similar to the ferrosilicon method for the production of magnesium would have certain advantages. Small units, such as Pidgeon retorts, would give flexibility of production to meet demand, and a small plant would require moderate capital outlay. There is a possibility of using idle Government-owned magnesium plants for such purposes. The raw materials needed for vacuum thermal reduction would not have to be extremely pure, especially with respect to the iron and calcium content. This paper describes a series of experiments to determine the effectiveness of various agents for the reduction of lithium compounds. The investigation is part of a program of vacuum metallurgy con-

Jan 1, 1947

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 G. D. Van Arsdale

THE paper of Mr. Posnjak presents a laboratory confirmation of the well known facts that air ox-idation of pure solutions of ferrous sulfate is slow and difficult and that, like many other similar reactions, the speed, may be greatly accelerated by the presence of other substances, often in very small amounts, the effect of the presence of copper being determined ex-perimentally in this case. However, it should not be. overlooked that copper is always present in heap leach-ing solutions in amounts equal to or greater than those in the experiments described; therefore the paper may be considered as an explanation of present results rather than a possible improve-ment to be added to present practice. It is not practicable and it does not pay to precipitate copper by ce-mentation below a point about 5 lb. per 1000 gal., equivalent to about 0.0005 mol. Cu. per liter, compar-ing with the approxi-mately 0.0009 mol. per liter of curve 2 in the diagrams given of course, also, in the heaps local concentrations are usually very much higher than this, which is also true of the effluent li-quors, so that I feel that it is safe to say that copper is already present in amount sufficient to realize, as large an accelerating effect as is practicable. Too much im-provement or refinement cannot be expected in a method of this kind, due to commercial limitations. It should be remembered that chemically and physically there is no sharp dividing line between leaching in place, heap leaching, and the usual tank leaching practice, practi-cally the same reagents being used in all three. From the viewpoint of extractions, etc., it is not common sense to apply leaching in place to an orebody carrying enough copper to pay for mining; and the same is true of heap leaching, for an ore carrying enough to pay for the crushing, handling, etc., of ordinary leaching. That is to say, leaching in place should properly be consid-ered only for an ore too low-grade to pay for mining, and heap leaching for the next higher grade, still how-ever too low-grade to pay for crushing and other re-finements. There is no advantage in leaching without mining or in heap leaching except lower cost of in-stallation and handling; on the other hand there are very distinct disadvantages which are inherent and which should prohibit their use except where necessity requires. The object of metallurgy is to make money out of the handling of ore, and it is purely a question of money as to how far we can go in "improving" or

Jan 7, 1927

By J. Visman

A simplified method of assessing the characteristics of a cleaning unit, including washability curves, yield figures, ash error, separating gravities, and error curve. FOR more than 25 years evaluations of coal cleaning units have appeared in many publications, and during this time considerable progress has been made in developing the theory and techniques of calculating washery results. A variety of characteristics have been defined over the years, many receiving general recognition during the first post-war Coal Preparation Conference in Paris in 1950. Coal preparation has become a science, and the approach to preparation problems is being revolutionized. Formerly, for example, if a coal operator wanted to know the performance of a given cleaning unit for a particular grade of his run-of-mine, he either shipped a carload to the manufacturer for a test run or relied on a report of a test carried out on a coal similar to the one he intended to clean. In modern practice the expensive, time-consuming test work generally can be avoided if the washability curves of the coal in question and the error curve of the cleaner are known. Normally a guarantee can be given on the strength of this information. General acceptance of modern standards has thus reduced the need for pilot-scale models of existing types of coal cleaners. Needless to say, the method requires exhaustive and accurate information on the cleaning unit and on all the additional circumstances affecting its results, information that ultimately can be secured only from actual tests made in the laboratory or in the washery. It is not the purpose of the present discussion to compare the merits of various characteristics, but to describe the general method of calculation, including a method of obtaining data with a minimum of laboratory work. All data presented here were derived from tests made at the plant with portable field equipment, using small quantities of varsol, carbon tetrachloride, and bromoform. It will be explained later that the use of standard fractional ash contents designated normalized ash contents aids considerably in reducing the routine testing of coal cleaners. Like any other statistical procedure, this method has limitations, and it is not recommended for any work in connection with guarantees. Even a varying commodity such as coal, however, will follow the law of large numbers, which is the basic law of statistics, thus allowing simplification of test work without appreciable loss of accuracy. The characteristics needed for evaluating cleaner performance are normally derived from a float-sink analysis of samples of the clean coal and the refuse, followed by ash determinations of the various fractions. Usually a sample of feed is also collected to find its ash content and to make a single specific gravity cut, both in connection with determination

Jan 1, 1955

By P. Chiotti, G. R. Kilp

IN the study of zinc-zirconium1 and zinc-uranium2 systems, vapor-pressure measurements were made in order to establish the equilibrium phase diagrams for a pressure of 1 atm. In each of these systems, only zinc has an appreciable vapor pressure over the temperature range investigated. The zinc pressure was measured over a sufficiently wide temperature and composition range to permit calculation of the standard free energy, enthalpy, and entropy of formation for the compounds ZrZn, ZrZn2, ZrZn3, ZrZn6, ZrZn14 , and U2Zn17. In these calculations the compounds were treated as line compounds. Although the exact composition range was not determined, metallographic and thermal data indicate that the solubility range for these compounds is small. It is to be noted that the compound initially reported to correspond to the formula UZn9, 2 has been shown by the crystal structure work of Makarov and vinogradov3 to correspond to the formula U2Zn17,. The crystal structure is similar to that for the compounds Th2M17, investigated by Florio,4 et al; here M represents iron, cobalt, or nickel. Therefore, thermodynamic calculations are based on the formpla U2Zn17 EXPERIMENTAL The dew-point method employed to measure the vapor pressure of zinc over uranium-zinc alloys has been described previously.2 The same procedure and apparatus were used in measuring the zinc pressure over zinc-zirconium alloys. In the case of alloys in the two-phase region consisting of a zirconium and the compound ZrZn, the Knudsen effusion method was employed to obtain a few values in the temperature range 600" to 560°C. In most cases, tantalum crucibles were used to contain the zirconium alloys. THERMODYNAMIC PROPERTIES OFU2Zn17 A least-squares treatment of the vapor-pressure data obtained for 35 and 65 wt pct U alloys in the temperature range 650° to 940°C gave lOg10PAtm = 7,713/T + 6.33 Here, as in following equations, T represents degrees kelvin and P represents the zinc vapor pressure in atmospheres. The probable errors for the two constants were calculated to be 60.68 and 0.0563, respectively. This relation represents the equilibrium dissociation pressure for the reaction U2Zn17 (s) - 2U(s) + 17Zn(v) The solubility of zinc in solid uranium is negligible and the only additional information required to calculate the free energy of formation of U2Zn17 is the free energy of vaporization of pure zinc. K. K. Kelley5 gives the relations, AF°= 30,902 + 6.03Tlog T + 0.275 X 10-3T2 - 45.03T

Jan 1, 1961

By J. K. Stanley

IT has been known for many years that the magnetic properties of a ferromagnetic material are very sensitive to internal strain. Any structure-sensitive property such as ferromagnetism, which is a-function of the regularity of the atomic arrangement, and discontinuities such as grain boundaries must show deviations from an equilibrium state when the regularity of the lattice is disturbed. Experience has shown that such distortions have a marked effect on the magnetic properties of a ferromagnetic material. The purpose of this paper is to show the feasibility of using magnetic methods in detecting internal strains. More specifically, it will be shown how such properties as permeability, remanence, and coercive force change on cold- working of aluminum iron and how these magnetic properties change during the annealing below the recrystallization temperatures. This work was conducted for two reasons. One was the desire to see in what manner strains are relieved in aluminum iron at low temperatures-a subject of practical importance in soft magnetic materials-and the other was the feeling that a study of cold-working and strain relief might shed some light honour understanding of what takes place in the deformation of metals DEFINITION IN TERMS It is necessary to define the terminology used in this paper because magnetic nomenclature is usually unfamiliar to the metallurgist, and certain other terms, such as recovery, have been used ambiguously by metallurgists and others. Magnetic terms are best explained by reference to the common hysteresis loop of ferromagnetic materials (Fig. I). In Fig. I the coordinates are magnetic induction, B, (ordinate) and magnetizing force, H, (abscissa). The c.g.s. unit for the magnetic induction is the gauss, the number of flux lines per square centimeter, and the unit for the magnetizing force is the oersted, the number of lines of force per centimeter in air or vacuum. If one starts with a completely de- magnetized specimen and magnetizes it, a typical virgin magnetization curve beginning at the origin is obtained. This curve is also the locus of tips of a family of smaller hysteresis loops. From this curve it is to be noted that the induction is not proportional to the magnetizing force, and that it appears to approach a limiting induction called the saturation value, and does so for values of H of 1000 oersteds. The ratio of the magnetic induction (gauss) to the magnetizing force (oersteds) is called permeability, p. Thus µ = B/H and if the magnetizing force H (oersteds) is specified as 10 or IOO oersteds, the permeability is written as µ10 or µ100. This is the accepted notation, and will be used in this paper. The values of permeability for H = 10 or 100 are chosen as indices for

Jan 1, 1945

By John Lamont, Walter Crafts

The principle formulated by Grossmannl for calculating hardenability of steel by multiplying the ideal diameter of "pure" iron-carbon alloys by factors for grain size and alloying elements has been confirmed on many steels and has proved useful in designing substitute alloy steels. Grossmann found that the typical behavior of the multiplying factors was to increase directly in proportion to the amount of the alloy present in a steel. However, the multiplying factor for the effect of silicon on hardenability was found by Grossmann to increase to a lesser degree as the amount of silicon was increased. In view of the increasing use of silicon in heat-treating steels, the effect of silicon on hardenability is becoming more important. Calculation of the hardenability of high-silicon steels made at the Union Carbide and Carbon Research Laboratories, Inc., indicated that the multiplying factor for silicon increased directly in proportion to the amount of silicon present. A more extended study of high-silicon steels covering fairly wide ranges of grain size, carbon, manganese, and aluminum has confirmed that up to 2 per cent silicon the multiplying factor is directly proportional to the silicon content. Manganese and aluminum factors have also been! determined. The results of the study offer strong confirmation of the general validity of Grossmann's multiplying principle. Testing Procedure Steels on which the study of the effect of silicon on hardenability was based were made in high-frequency induction furnaces using Armco iron and standard alloying materials. The ingots were forged to bars, and sections were normalized prior to machining Jominy hardenability test specimens. The Jominy test was carried out under standard conditions.2 The depth of hardness penetration for determination of ideal diameter at "half hardness" was taken at the hardness level indicated in Fig. 29 in Grossmann's paper by the solid line for 50 per cent martensite in plain carbon steel. The depth of penetration of hardness on the Jominy specimen was converted to ideal diameter by the relation given in Fig. 28 of Grossmann's paper. Chemical analysis was determined on a sample taken adjacent to the Jominy specimen. Aluminum was determined as "acid-soluble aluminum" rather than as total aluminum, as it is probably more representative of the aluminum that is effective as an alloying agent. In addition to the elements nominally present in the steels, analyses were made for residual phosphorus, sulphur, nickel, copper, molybdenum and chromium on one heat of those made with the same materials during the same period. Actual grain size was determined by microscopic examination of small samples quenched in water after receiving the same thermal cycle as the Jominy hardenability specimens. Chemical analyses, heat-treatment, grain size, and hardenability are shown in Table I representing three ranges of composition.

Jan 1, 1943

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 John E. Conley

THE slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5 3/4 million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. USE OF WASTE SLATES FOR MAKING AGGREGATES The lightweight-aggregate industry has been discussed elsewhere4.5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done' on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. REQUIREMENTS FOR RAW MATERIALS As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of any low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig. I illustrates the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By James E. Berryman

A method is presented for calculating the pressure depletion performance of a gas-condensate reservoir from the original reservoir fluid composition using the laboratory determined pressure-production history and retrograde liquid accumulation as guides. Equilibrium vaporization ratios for this calculation were modified from published data until the calculated dew point pressure and retrograde liquid accumulation agreed with the values observed in the laboratory. The calculated results are compared with the produced gas composition determined by low temperature analysis during constant volume laboratory experiments of pressure depletion behavior. This comparison shows that the calculation procedure is adequate for determination of gas phase composition. Data from field separation tests in low temperature separators are presented which verify the applicability of published equilibrium vaporization ratios for a wide range of separator conditions. INTRODUCTION A reliable prediction of the pressure depletion performance of a gas-condensate reservoir is necessary in determining reserves and evaluating field separation methods. The predicted performance is also used in planning future operations and studying the economics of projects for increasing liquid recovery. Because the flow of fluid in a volumetric gas-condensate reservoir is usually single phase flow, the pressure-depletion per-formake is primarily a function of the phase behavior of the reservoir fluid. The properties of a gas-condensate system of major importance are: (1) compressibility factor at reservoir temperature and pressure; (2) dew point pressure; (3) composition changes of the vapor phase with pressure depletion; (4) recovery of original in-place hydrocarbons at any pressure; and (5) retrograde condensate accumulation. These properties are most generally determined by a pressure depletion-type experiment on recombined separator gas and liquid samples in the laboratory. ldeally the pressure-depletion performance can be calculated from the composition of the original reservoir fluid if the reservoir temperature and initial pressure are known.1,2,3 It has been reported "... comparison of such computations with depletion-type ex-periments on recombined samples in the laboratory have yielded results that appeared to be entirely adequate.". The success of such calculations is determined by the equilibrium vaporization ratios chosen, especially those for the higher boiling point hydrocarbons. It is the purpose of this paper to present a method for computing the change in composition of the vapor phase during pressure depletion by production using laboratory determined properties of the system to guide the calculation and to illustrate the use of the method with data from the Cockfield "D" sand of Washington field, St. Landry Parish, La. Results of field tests and laboratory analysis are included. As a result of this reservoir fluid study, a cycling program has been evaluated, the fidd has been unitized, and the cycling started in July, 1956.

Jan 1, 1958

By John L. Lamont, Walter Crafts

THE principle formulated by Grossmann1 for calculating hardenability of steel by multiplying the ideal diameter of "pure" iron-carbon alloys by factors for grain size and alloying elements has been confirmed on many steels and has proved useful in designing substitute alloy steels. Grossmann found that the typical behavior of the multiplying factors was to increase directly in proportion to the amount of the alloy present in a steel. However, the multiplying factor for the effect of silicon on hardenability was found by Grossmann to increase to a lesser degree as the amount of silicon was increased. In view of the in¬creasing use of silicon in heat-treating steels, the effect of silicon on hardenability is becoming more important. Calculation of the hardenability of high-silicon steels made at the Union Carbide and Carbon Research Laboratories, Inc., indicated that the multiplying factor for silicon increased directly in proportion to the amount of silicon present. A more extended study of high-silicon steels covering fairly wide ranges of grain size, carbon, manganese, and aluminum has confirmed that up to 2 per cent silicon the multiplying factor is directly proportional to the silicon content. Manganese and aluminum factors have also been determined. The results of the study offer strong confirmation of the general validity of Grossmann's multiplying principle. TESTING PROCEDURE Steels on which the study of the effect of silicon on hardenability was based were made in high-frequency induction furnaces using Armco iron and standard alloying materials. The ingots were forged to bars, and sections were normalized prior to machining Jominy hardenability test specimens. The Jominy test was carried out under standard conditions.2 The depth of hardness penetration for determination of ideal diameter at "half hardness" was taken at the hardness level indicated in Fig. 20 in Grossmann's paper by the solid line for 50 per cent martensite in plain carbon steel. The depth of penetration of hardness on the Jominy specimen was converted to ideal diameter by the relation given in Fig. 28 of Grossmann's paper. Chemical analysis was determined on a sample taken adjacent to the Jominy specimen. Aluminum was determined as "acid-soluble aluminum" rather than as total aluminum, as it is probably more representative of the aluminum that is effective as an alloying agent. In addition to the elements nominally present in the steels, analyses were made for residual phosphorus, sulphur, nickel, copper, molybdenum and chromium on one heat of those made with the same materials during the same period. Actual grain size was determined by microscopic examination of small samples quenched in water after receiving the same thermal cycle as the Jominy hardenability specimens. Chemical analyses, heat-treatment, grain size, and hardenability are shown in Table I representing three ranges of composition.

Jan 1, 1943

By J. K. Stanley

It has been known for many years that the magnetic properties of a ferromagnetic material are very sensitive to internal strain. Any structure-sensitive property such as ferromagnetism, which is a function of the regularity of the atomic arrangement, and discontinuities such as grain boundaries must show deviations from an equilibrium state when the regularity of the lattice is disturbed. Experience has shown that such distortions have a marked effect on the magnetic properties of a ferromagnetic material. The purpose of this paper is to show the feasibility of using magnetic methods in detecting internal strains. More specifically, it will be shown how such properties as permeability, rema-nence, and coercive force change on cold-working of aluminum iron and how these magnetic properties change during the annealing below the recrystallization temperatures. This work was conducted for two reasons. One was the desire to see in what manner strains are relieved in aluminum iron at low temperatures—a subject of practical importance in soft magnetic materials—and the other was the feeling that a study of cold-working and strain relief might shed some light onour understandingof what takes place in the deformation of metals. Definition of Terms It is necessary to define the terminology used in this Paper because magnetic nomenclature is usually unfamiliar to the metallurgist, and certain other terms, such as recovery, have been used ambiguously by metallurgists and others. Magnetic terms are best explained by reference to the common hysteresis loop of ferromagnetic materials (Fig. I). In Fig. 1 the coordinates are magnetic induction, B, (ordinate) and magnetizing force, H. (abscissa). The c.g.s. unit for the magnetic induction is the gauss, the number of flux lines per square centimeter, and the unit for the magnetizing force is the oersted, the number of lines of force per centimeter in air or vacuum. If one starts with a completely demagnetized specimen and magnetizes it, a typical virgin magnetization curve beginning at the origin is obtained. This curve is also the locus of tips of a family of smaller hysteresis loops. From this curve it is to be noted that the induction is not proportional to the magnetizing force, and that it appears to approach a limiting induction called the saturation value, and does so for values of H of 1000 oersteds. The ratio of the magnetic induction (gauss) to the magnetizing force (oersteds) is called permeability, . Thus u= B/H and if the magnetizing force H (oersteds) is specified as ro or 100 oersteds, the permeability is written as or l00 This is the accepted notation, and will be used in this paper. The values of permeability for H = 10 or I00 are chosen as indices for 106

Jan 1, 1945

By J. E. Chappelear

We are concerned with the problem of calculating the forces produced by passing waves on a submerged object (in particular a drilling barge) located on the ocean floor. We employ the linearized theory of waves (the Airy1 theory), since solutions are generally more easily obtained in such a theory. It will be indicated how an approximate solution to the problem can be obtained for waves of finite height by use of a linear combination of Airy waves. We shall assume the submerged object has an infinite length, thus neglecting diffraction and making the problem two-dimensional. We find that there is not a considerable difference between our solution and the usual engineering solution. The force, as a function of time, is plotted in Figs. 4 and 5, together with the usual solution for easy comparison. So far, no experiments have been found to compare with the results. As will be shown, the calculations can be extended to waves of finite height (Stokes2-Struik3 waves) in an approximate fashion. This can be done by calculating the force produced by each Fourier component of the wave, separately, and omitting the coupling between the various harmonics produced by Bernoulli's theorem. The problem and its boundary conditions will be briefly stated. We seek a function, +, the velocity potential, which is harmonic, ?2?=0...........(1) and which satisfies the boundary conditions ??/?n =0 .......(2) (the normal derivative of + is zero) on the ocean floor and the sides of the barge, and s??/?y = ?..........(3) on the ocean surface, where s = g/w2........(4) The physical reasons for these choices and an interpretation of ? are given by Lamb.' As previously stated, we assume also that the problem is two-dimensional. We set up our coordinates such that x = 0 is the center of the barge and y = 0 is the ocean floor. The coordinates are shown in Fig. 1, together with the location of the barge on the bottom. Our solution may be decomposed into a function which is symmetric about x = 0,?e, and one which is antisymmetric, +,, ? = ? + ?o...........(5) Thus directly above the barge we have as boundary conditions that for x = 0, ?o = 0, ...........(6) and ??e/?x = 0........(7) Now, far from the barge, we have that (for x positive and assuming the waves are incident from the left) ?e ? Ae cosh ky cos k (x + a) , . . . (8) and ?e ? Ao cosh ky cos k (x + ß) . . . . (9) where + means ". .. approaches ... for x large." Let us put Ae, Ao, and k equal to one, and remember that, in accordance with the derivation of Eq. 3, a sinusoidal time factor is to be supplied. Then we may rewrite Eq. 8 for ?e, and we find that

Jan 1, 1958

By John E. Conley

The slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. Use of Waste Slates for Making Aggregates The lightweight-aggregate industry has been discussed elsewhere4,5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. Requirements for Raw Materials As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of ally low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig, I illustratcs the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By M. I. Sherman, J. D. H. Strickland

PRELIMINARY experiments in these laboratories showed that whereas pyrite1 produced only sul-fate the action of aqueous chlorine solutions on most other sulfide ores resulted in the formation of a mixture of sulfate and elemental sulfur, the production of the latter being favored by a very dilute solution of oxidant. The reactions taking place were obviously complex and only a detailed kinetic study could be expected to clarify the position and enable a prediction to be made of conditions leading to the rapid formation of metal salt and the economically desirable elemental form of sulfur. Galena was chosen for the first investigation as it is of widespread occurrence and is representative of a simple cubic lattice sulfide containing the monosulfide unit, S2-. Experimental Procedure The apparatus and general technique used in this work have already been described.' Analyses for chlorine and sulfate were carried out by the same methods as those used for pyrite. The lead in 1 ml aliquots of solution was determined polarographi-cally, after destroying chlorine with hydrazine hy-drochloride and making solutions 0.5 molar with hydrochloric acid. A large sample of Kansas galena, assaying at better than 98 pet PbS, was crushed and wet sieved to give fractions of —10 + 14, —20 + 28, —28 + 35, and —48 + 65 Tyler screen. The particles were almost perfect cubes and the apparent surface Per gram was calculated assuming each particle a cube Of side equal to the mean mesh opening. A volume shape factor, calculated as for pyrite, was exactly unity. The main apparatus was unsuitable for direct visual examination of the ore particles during the reaction. For this purpose a small cell from a Spekker Absorptiometer optical flats 1 cm apart) was l by a greased microscope slide after filling with oxidant solution. One or two ore particles were placed in the cell and the solution was stirred by a glass covered speck of iron wire activated by an external rotating magnet. The surface of an ore particle was examined under a binocular microscope at between 10 and 40 magnifications. Results Experiments were made under a wide variety of conditions, the form of presentation of the data being illustrated by Fig. 1, where the concentrations of chlorine, sulfate, and sulfur are plotted against time. The fictitious concentration of solid sulfur is used for convenience and is the molarity of sulfur which would be recorded if the elementary sulfur formed during the reaction were dissolved in the liquid iii the reaction vessel. As some lead sulfate is occluded with the sulfur on the ore particles the amounts of sulfur and sulfate formed during a reaction cannot be calculated

Jan 1, 1958

By John E. Conley

The slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. Use of Waste Slates for Making Aggregates The lightweight-aggregate industry has been discussed elsewhere4,5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. Requirements for Raw Materials As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of ally low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig, I illustratcs the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Zinc difhsions in gallium arsenide having surface concentrations as low as 5 x 10'' atoms per cu cm have been attained. A multiple-difhsion sequence is employed during which zinc enters the gallium arsenide from a silicon dioxide film in a solid-to-solid diffusion step. The technique is illustrated for the case of a zinc surface concentration of -1 x 1017 atoms per cu cm and a junction depth of 1.2 p. Radiotracer measurements of -0.1-p layers of gallium arsenide are used to delineate the resulting profile. A diffusion coefficient for zinc in pyrolytically deposited silicon dioxide is reported. ZINC is frequently used as an acceptor impurity in gallium arsenide. As examples, p-n junctions are formed using zinc-diffused layers in solar cells, lasers, and varactor diodes. For these purposes surface concentrations of 10'' to over loz0 zinc atoms per cu cm are desired and readily obtained from a vapor source. Diffusion of zinc into gallium arsenide to yield surface concentrations of about 1017 atoms per cu cm, however, is more difficult. For instance, oldstein' reports that large changes in the vapor density of zinc produce only small changes in surface concentration. Such low surface concentrations are necessary in forming the diffused base of a gallium arsenide double-diffused n-p-n transistor in order to obtain an adequate emitter efficiency. An alternative approach to zinc diffusion which can provide reduction in surface concentration of several orders of magnitude is the introduction of the diffusant from a solid source. This can be conveniently accomplished by using oxide films of the type generally employed for selective diffusion masking. Such oxides also serve to prevent the dissociation of the gallium arsenide surface at the high temperatures of diffusion. DIFFUSION PROCEDURE Fig. 1 illustrates the diffusion sequence which is employed for obtaining zinc surface concentrations in the range from 5 x lom to 1 X 10" atoms per cu cm. The description of technique will be given for the instance of -1 x 1017, which is typically utilized in double-diffused gallium arsenide transistor investigations at this laboratory. Tin- or germanium-doped gallium arsenide wafers drawn from crystals grown by horizontal Bridgman or Czochralski techniques are used, with bulk concentrations ranging from 1 to 3 X 10" carrier atoms per cu cm. Each wafer is chemically polished on the (iii) arsenic face using a mixture of five parts concentrated sul-furic acid, one part water, and one part 30 pct hydrogen peroxide at room temperature, followed by rinsing in deionized and quartz-distilled water. Pyrolytic silicon dioxide was chosen as the oxide coating because of the high quality of the films obtainable, the ease of their preparation, and the excellent control over film thickness and uniformity.

Jan 1, 1964

By W. C. Ellis, M. E. Fine

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949