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By J. C. Martin

A theoretical analysis of steam stimulation is presented for single sands. The analysis includes the effect of steam production and most of the effects of heat conduction. The results show the effects of a number of important variables on the performance of an idealized well under steam stimulation. Calculated responses are presented which indicate the effects of steam production, amount of steam injected, water production, formation thickness and formation damage. Results indicate that steam production can cause large reductions in the heat contained in the formation. This effect can be eliminated by drawdown control. Water production reduces the amount of oil produced during stimulation. The optimum amount of steam to inject depends on economic factors as well as the well response. In many cases, the increased temperature resulting from stimulation reduces oil viscosity near the well sufficiently to overcome the effects of formation damage even if the damage is not removed during steam injection. Calculated responses for thin sands are more favorable than anticipated. INTRODUCTION Little has been published on the theory of steam stimulation'-' despite the interest it has created and the wide variation in well responses. The results of the present analysis provide an insight into steam stimulation, and the methods employed provide a foundation for future work. Analyses presented in Refs. 1 and 2 are very limited and apply to gravity drainage conditions. Ref. 3 contains an analysis similar to the one presented here. The idealized models used and the assumptions made in Ref. 3 are different from those used in this paper. The analysis assumes that after steam injection has heated a small portion of the volume within the radius of drainage of a single uniform sand, a shut-in soaking period is allowed before returning the well to production. The effects of gravity, capillarity, transient pressure and water-sensitive sands are neglected. The injection and soaking times are assumed short compared to the stimulated production time. The initial temperature is assumed uniform; thus, the results apply primarily to first-cycle stimulation. The effects of gas production other than steam are neglected, and the water-oil ratio during production is assumed constant. Steam stimulation involves the simultaneous variation of the temperature, pressure and saturations. General mathematical equations for these variations are complicated and can be very difficult to solve. Simplified equations based on idealized models are used to reduce the mathematics sufficiently to allow approximate solutions to be obtained. DISCUSSION INJECTION An idealized model for which heat conduction is neglected is used to represent the behavior of a well during steam injection. The mathematics for this model is presented in Appendix A which also contains an approximate solution for the behavior of the no-conduction model. SOAKING During soaking, the well is shut in. Only the temperature, pressure and saturation distributions at the end of soaking are needed in the analysis. During soaking the heat is considered to be conducted in a uniform medium from an initially uniformly-heated circular cylinder confined to the producing interval. At the end of soaking the saturations and pressures are assumed to correspond to the cold zone. Analysis of the heat flow during soaking is included in the next section. The radius of the heated cylinder is calculated from the following heat balance (for constant quality steam injection). At the end of the soaking period it is assumed that little or no free gas is present near the well, and that the soaking period has been sufficiently long that the steam zone has had time to expand and the steam has condensed. The condition where there is no soaking is considered in the next section. PRODUCTION In this section, an approximate method is presented for solving the equations of heat and fluid flow associated with the production of oil and water during steam stimulation. Where initial pressure drawdowns are sufficient to cause steam to flow into the wellbore, steam production is assumed to occur within a short initial adjustment period (Appendix B). The production practices followed soon after the well is returned to production can have a large influence on the amount of oil produced during the stimulation cycle. Under most conditions, there is a period of time in which some or all of the water in the heated zone is converted into steam and produced. This flashing of hot water is caused by the pressure in the heated zone dropping below

By M. D. Cooper

Production of both anthracite and bituminous coal in 1954 was about 16 pct below 1953. Estimates on Dec. 1, 1954, indicated 27 million tons of anthracite and 385 million tons of bituminous. Decline in production was due principally to lower demand by the steel industry and the railroads, although competition from other fuels also affected coal. The year was notable for vigorous effort by the coal industry to promote the use of its product. A Cabinet Committee on Energy Supplies and Resources Policy and an Interdepartmental Committee on the Soft Coal Industry were set up by the Administration in Washington. A Governors' Fuel Conference was also organized.

Jan 3, 1955

By Walter S. Weeks

The process of cooling air by allowing it to expand and do work in an engine is well known, but the theory of obtaining cold air by free expansion without the aid of an engine operating with cutoff has been little discussed. Case I If compressed air is allowed to expand to the atmospheric pressure through an orifice in an air line that is supplied by a running compressor, no cooling results except the negligible one due to the JouleThompson effect, which will not be considered in this discussion. The effect of moisture will also be neglected. Symbols P1 Absolute pressure in pipe line, lb. per sq. ft. P3 Atmospheric pressure, lb. per sq. ft. V1 Volume occupied by 1 lb. air in pipe. V3 Volume occupied by 1 lb. air at P3. C, Specific heat of air at constant volume, B.t.u. per lb. per deg. F. C, Specific heat at constant pressure, B.t.u. per lb, per deg. F. T1 Absolute temperature of air in pipe, deg. F. T8 Absolute temperature of air outside after expansion and mixing and coming to rest. j Mechanical equivalent of heat (778 ft. lb.) R Gas constant for air, ft-lb. per deg. F. = 53.3. Formulas Consider 1 lb. of air moving out of a pipe. The air behind it does work on it to the extent of P1V1 ft-lb. This work is really done by the thrust of the piston of the compressor and does not come from any energy that exists in the air in the pipe. The pound of air contains

Jan 1, 1937

By H. D. Wilde

At the Sugarland and Raccoon Bend fields in the Gulf Coast area, all wells are drilled with rotary tools and the casing is always set in cement that is placed by the circulation method. After the cement is set, the rotary mud that fills the hole is not withdrawn or bailed out; consequently, it is not customary to give the cementing job a direct test either by putting pressure on the hole to see whether the cement will hold or by observing whether an effective water shut-off is secured. About three years ago, this company started the practice of coring the cement left in the bottom of the casing and examining the core thus secured. If the core was hard and strong, the cementing job was judged a success but if the core was incoherent, soft, and crumbly, the job was considered a failure. Of course, there were intermediate types of cores and it was not always a simple matter from this examination to decide whether the job was a success or failure. After about two years, a summary of the core examinations that had been made indicated that of cementing jobs made at depths of 1000 ft. or less, 60 per cent.. were failures; of those between 1000 and 2000 ft., 80 per cent. were failures, and of those between 3000 to 6200 ft., 100 per cent. were failures. This sta,rtling table emphasized the need of the study of the conditions under which the wells were cemented and of adopting means to reduce the percentage of failures. In addition to these core tests, two wells gave direct evidence that the cementing jobs were not always successful. In one, a four-year-old well at Goose Creek, the casing was perforated, and when fluid was circulated some of the old cement wss brought to the surface. Most of it was powdery and the few chunks that were brought up were soft and crumbly. The other was a well at Raccoon Bend which during a blow-out brought a number of chalky, soft and crumbly pieces of cement to the surface. Suggested Explanations of Cementing Failures Efforts were made at once to explain the causes of these cementing failures. As all of the cements used were of a high grade and gave

Jan 1, 1930

During the past year the Committee on Coal and Coke has been collecting data concerning various phases of the bituminous industry about which considerable misinformation has been circulated even, in some cases, through the coal trade papers. The data here presented have been compiled by various members, from the most authentic sources available and, where possible, cover the period 1913-1924. They will enable comparisons to be made within the industry, and of this and other industries, and will explain some of the differences between conditions existing now and in the prewar period. Capacity and Over-development The capacity of bituminous mines is frequently stated at figures ranging between 800,000,000 to 1,400,000,000 tons per year. Table 1 shows statistics for the industry, mainly from U. S. Geological Survey sources but partly from U. S. Coal Commission reports. Column 3 gives the mine capacity with equipment and labor as of given date, as estimated from the data published by the U. S. Geological Survey. This is calculated for each State by obtaining the total man days worked as reported by the operators (multiplying average men employed by total days worked at each mine) and dividing this figure into the total production, getting the production per man day; this figure times number of men employed times 308 (a theoretical full working year) equals estimated full-time capacity. Two major objections are made to this method—one that the total number of men employed is used, instead of the number actually working, and the other that the number of days used only deducts Sundays and five holidays. The first objection is answered by the fact that the same number of men is used in estimating capacity as is used in actual production, and while this number is always from 12 to 20 per cent. more than are actually working, this condition exists at all times, although it is worse at times of maximum output. Few coal men will agree with the conclusion that the use of 308 days is correct, as it is practically impossible to keep any mine working full time at the same daily rate of production as when it is working part time, and the opinion is

Jan 1, 1927

Jan 1, 1924

By McHenry Mosier

SUMMARY MERCURY is one of the strategic metals of which the supply has been raised from critical uncertainty to more than enough for essential demands. Work by the Bureau of Mines has contributed substantially to increased production of mercury in the United States and to consequent accumulation of Government stocks. Other contributing factors have been higher prices for mercury and Government loans to operators. The Bureau has undertaken 13 exploration projects, 10 of which have been completed. This work has comprised 28,376 ft. of several types of drilling and 23,798 lin. ft. of surface trenching, and has indicated commercial ore containing 34,800 flasks of mercury and marginal ore containing 26,200 flasks, a total of 61,000 flasks; equivalent, respectively, to domestic production for 8 months, 6 months, and 14 months. As Government stocks are now adequate, domestic production (currently at the rate of 50,000 flasks per year) is gradually being curtailed through Government control of labor and operating supplies.

Jan 1, 1944

By H. B. Fuqua, B. E. Thompson

The area discussed in this paper, commonly known as the West Texas district, is easily divisible into three geologic provinces, the Midland Basin to the east, the Delaware Basin to the west and the West Texas structural platform separating these two. Production in Garza, Scurry, Mitchell, Howard, Glasscock, Irion, Reagan and central Crockett counties is associated with the east flank of the Midland Basin. That in Loving and Reeves counties is associated with the Delaware Basin. All other production and developments discussed in this paper belong to the province of the West Texas structural platform. Because of certain developments that have occurred during the past year, it has been found necessary to slightly revise one of the fields as grouped by Mr. Reith in last year's paper1. The Scarborough-Leck field has been broken down as follows (Table 1): The Leck field is shown separately because it is producing from dolomite; while the Scarborough area, producing from sand, is regrouped and designated as " Scarborough-Kermit-Halley," which includes the producing sand belt across Winkler County from Ward County to New Mexico. It is believed that this is a more logical division of Winkler County and that considerable future work will be avoided by making this change before further production figures have accumulated under the present set-up. A number of new fields are listed in Table 1, some of which may represent extensions of other produeing arras. The authors, however, are inclined to believe that they represent new fields. In either event, less work is involved ill adding two areas together, if they later prove to be one, than in attempting to separate a maze of production data into two fields after they have been erroneously carried as one for a number of years. The Howard-Glasscock field is designated in this review as the Chalk-Roberts field and the Denman production on the Howard-Mitchell County line is included in the Iatan field. Development during 1934 Development in West Texas during the year 1934 showed a marked increase over the previous year both in exploration and ill exploitation

Jan 1, 1935

By T. Sterry Hunt

THIS remarkable mine, to which attention has lately been drawn, is situated not far from the New River, in Ashe County, North Carolina, on a spur of the Blue Ridge which lies between the main crest of this name and the so-called Iron Mountain, a part of the Unaka or Smoky Mountain range. It is on a true fissure-lode, which cuts the strata of gneiss and mica-schist of the region. These, which have the lithological characters of what I have called the Montalban or White Mountain series, have here a dip of about forty-five degrees to the southeast, while the lode is vertical, with a course north 60° east. Both the country-rock and the lode, as is usual in this region, are decomposed to considerable depths ; and the latter exhibits a cap of hydrous peroxide of iron or gossan, blocks of which, left by the denudation of the softer inclosing rock, are scattered over the surface, and first called attention to the locality as a source of iron ore. In sinking upon this lode, it was found that the porous gossan at a certain depth became charged with carbonate and red oxide of copper, and lower down was replaced by sulphuretted ores of this metal of remarkable richness. This deposit was worked for copper, in an irregular manner, before the late civil war, but was afterwards abandoned, and only reopened during the present year, by Messrs. S. S. & J. E. Clayton, of Baltimore. The outcrop has been traced for 1900 feet, and the sulphuretted copper ores have been met with in five shafts in a distance of 661 feet, a drift having moreover been carried for the above distance through the solid ore. The breadth of the lode, so far as opened, varies from six to eight feet to fourteen feet in places, and that of the outcrop of gossan is, in some parts, twenty feet. After comparing this deposit with the copper mines of Ducktown, Polk County, Tennessee, and those of Carroll County, Virginia, it is evident that we have, at Ore Knob, to do with the same kind of black ores as were met with in these mines, and will be noticed further on. Beneath the gossan, at Ore Knob, is found, in some parts, an iron-black, friable, drusy, crystalline, sulphuretted ore, inclosing grains of quartz, garnet, and magnetite, besides a black non-magnetic mineral, not attacked by nitric acid. This ore contains about 36 per cent. of copper, and portions have the mineralogical charac-

Jan 1, 1874

Jan 1, 1938

For the benefit of those of our members who are considerable holders of securities, but owing to their isolated situations are not in-close touch with the metropolitan market and current quotations, we are publishing two very interesting graphs, showing the course of the bond and stock markets in New York over a long period. These graphs are furnished through the courtesy of the financial department of the New York Tribune.

Jan 5, 1919

By E. J. Freeh, W. E. Horst, R. C. Kellner

A technique useful in the important area of process-model building is described. The procedure is illustrated in the development of a mathematical model to describe the unsteady-state process of batch ball-mill grinding. The influence of certain assumptions relative to model structure are quantitatively evaluated and reviewed.

Jan 1, 1969

Merritt: Karl, you are a native New Englander, having been born in St. Albans, Vermont, in 1885. How did you decide on becoming a mining engineer? Twitchell: While I was attending St. Albans High School, my uncle, who had been the American Consul in Kingston, Ontario, for many years, told me of the excellent mining school there. He also introduced me to a Canadian mining engineer who sparked my interest in mining by noting the possibility of achieving personal success without always being under salary. Well, that appealed to me, so I applied to the Kingston School of Mines at Queen's University.

Jan 9, 1965

By John Nelson

AN OUTLINE survey of the economic outlook for the United States export trade in petroleum products resolves itself broadly into two general divisions; first, a consideration of our present position in this trade, and second, a discussion of the visible factors which promise to affect appreciable changes in the immediate future in that trade. The UNITED STATES PETROLEUM EXPORTS OF MAJOR PETROLEUM PRODUCTS 1925, 1926 and 1927 Gasoline, Naphtha, and Other Light Products 1925 1926 1927* Quantity (gal.) 1,286,787,796 1,784,154,802 1,851,494,190 Value $197,491,588 $263,199,938 $214,721,652 'Illuminating Oil, Kerosene 1925 1926 1927* Quantity (gal.) 885;136,041 924,680,979 827,162,280 Value $84,699,724 $100,352,877 $80,358,082 Gas and Fuel Oil 1925 1926 I 1927 Quantity (gal.) 1,365,358,988 1,449,688,394 1,815,130,464 Value.... ? $49,040,024 $45,354,108. .. $50,343,031 Lubricating. Oil 1925... ....1926 .. 1927 Quantity .(gal.) 402,572,584 388,767,055 403,369,512 Value $90,596,671 $86,414,621 $88,926,815

Jan 1, 1928

By H. Scott

SINCE Böhler discovered, in 1903, on cooling certain alloy steels, the phenomenon of a new and lower temperature transformation than the usual Ar3_2_1 obtained by increasing the maximum temperature to which the material was heated, much has been published' connecting this phenomenon with a large number of dissimilar steels of high alloy content. From the fact that the transformation divides itself, taking place at two widely separated temperatures, it has been called a "split transformation." The, significant facts established by recent investigators' are: that when the' transformation occurs at the higher temperature Ar', troostite or a decomposition product is formed, and that when the transformation occurs at the lower temperature Ar", the resulting structure is martensite. The terminology Ar' and Ar" adopted here is that of Portevin.3

Jan 2, 1919

By M. J. Coolbaugh

Mining potash at depths of 3000 ft or more beneath thick water-bearing sediments in Saskatchewan presented a unique challenge to the North American mining industry. Potash is known to flow under pressure, but the knowledge of its flow characteristics at great depths was inadequate for safe design of mine workings and for assured protection from water above the salt formations. At the 3000-ft. depth of the Canadian mines, the potash is stressed beyond its elastic limit, and therefore mining design must deal primarily with its behavior as a plastic material. Recognizing that careful study would be required in order to assure safety and stability of mine workings in deep potash, IMC initiated an extensive rock mechanics investigation of structural properties of potash and salt under high-stress conditions. This presentation consists of a brief review of the development of some methods of testing potash in the laboratory and in the field; some of the rock mechanics concepts and principles derived; and their application to potash mine design. The mining of potash more than 3000 ft beneath the water-bearing sediments in Saskatchewan presented the unique challenge of designing stable mine workings and assuring protection from overhead water in a material that was believed to flow plastically, but whose behavior as a plastic material was not sufficiently known. Under the stress conditions ordinarily encountered in mining, most rocks behave as elastic materials; that is, they compress slightly under pressure, and rebound when the pressure is released. Salt and potash, however, are different. Even under the relatively low pressures encountered at shallow depths, these materials become slightly plastic and yield to stress by flowing.* The plastic properties become more pronounced at greater depth and pressure, and the question arises as to whether or not the plastic flow will be rapid enough and exert enough pressure to destroy underground structures or interrupt the mining process. It was found, however, that not only was there an insufficiency of information about the behavior of potash and salt, but conventional methods of testing these materials, such as determining the modulus of elasticity, Poisson's ratio, and uniaxial compressive strength, were inapplicable because of the high stress conditions prevailing at the 3000-ft depth. Potash under high pressure, for example, has practically no modulus of elasticity, its stress-strain relationship varies with time, and its compressive strength depends upon the degree of confinement. Elasticity and Stress/Strain Relationship: Fig. 1 shows a standard stress/strain chart for potash as made by the Department of Mines in Canada. Typically, when stress is applied to a hard-rock specimen, the specimen contracts, then expands to its original shape when the stress is withdrawn. This chart illustrates, however, that potash under stress yields to the stress by flowing, and does not expand when the stress is withdrawn. When the applied stress was held constant for 30 min, beginning at points A and C, the strain continued to increase and the potash flowed to points B and D, respectively. Points B, D, F, and H show that the potash did not return to its original shape when the stress was released. Thus it can be observed that potash has practically no elasticity and that the amount of strain depends upon the length of time that the stress is applied. Compressive Strength: The conventional method of determining the compressive strength of hard material is to find the maximum pressure that long slender specimens of the material can withstand without failing. As illustrated in Fig. 2,* line B, a standard 2-in. cube of potash subjected to a conventional type of uniaxial compressive test will exhibit a strength of about 5000 psi. However, the compressive strength exhibited can be made to change by changing the conditions under which the test is made. For example, if teflon plates lubricated with graphite are inserted between the press and the specimen, thus minimizing end constraint, the compressive strength is only about 2500 psi, shown in line A. If a specimen is cut in half, changing the width-to-height ratio to 2 : 1 instead of 1:1, and then tested without lubri-

Jan 1, 1968

Jan 1, 1962

By W. T. Lankford, Edward Saibel

During the course of an investigation of the plastic flow of aluminum aircraft sheet under combined loads, several problems arose in which analyses of the conditions leading to unstable plastic flow were needed. In order to provide these analyses, and in the hope of attaining a better understanding of the general problem of unstable plastic flow, the present study was undertaken. It is well known that unstable plastic flow is associated with a form of mechanical instabi!ity frequently observed during the plastic deformation of ductile metals. This instability is characterized by the fact that, at its onset, plastic straining mill proceed at a constant magnitude of the externally applied forces. It is further typical that the resulting unstable flow is generally accompanied by the formation of a neck, a local bulging, or some other form of heterogcneous deformation. Perhaps the most familiar example of unstable plastic flow to the metallurgist is the formation of the neck in the ordinary tension test. It is well known that in this test most metals exhibit a maximum in the externally applied load, followed by the process commonly referred to as "necking down." Instability in the simple tension test has been frequently discussed and numerous investigators1'2'3'12 have derived the criterion for instability in terms of a critical rate of strain hardening. It is the purpose of the present study to extend the criterion for unstable flow to the more general case where the body undergoing flow is subjected to combined loads. It is hoped that the problems considered will provide a more consistent picture of the general features of this important form of mechanical instability. The most practical implications of instability in plastic flow arise in connection with sheet metal forming operations. In the formation of a great many sheet metal parts, the deformations are produced primarily by stretching. If the conditions which lead to unstable flow are fulfilled in such a formation, and if the resultant instability leads to a pronounced localization of flow, then the useful limit of ductility of the material will have been reached. It i; also essential that the effects of instability be taken into consideration in any study of the plastic flow and rupture of metals under combined stresses. In general, when unstable plastic flow is initiated, straining becomes localized, the geometry of the test splecimen changes, and the state of stress in that portion of the specimen undergoing plastic flow is no longer under external control. In many past studies of the effects of combinetl Metals On flow and rupture) account has not been taken of the fact that, although a given test may be started under constant

Jan 1, 1947

By Edward Saibel, W. T. Lankford

During the course of an investigation of the plastic flow of aluminum aircraft sheet under combined loads, several problems arose in which analyses of the conditions leading to unstable plastic flow were needed. In order to provide these analyses, and in the hope of attaining a better understanding of the general problem of unstable plastic flow, the present study was undertaken. It is well known that unstable plastic flow is associated with a form of mechanical instabi!ity frequently observed during the plastic deformation of ductile metals. This instability is characterized by the fact that, at its onset, plastic straining mill proceed at a constant magnitude of the externally applied forces. It is further typical that the resulting unstable flow is generally accompanied by the formation of a neck, a local bulging, or some other form of heterogcneous deformation. Perhaps the most familiar example of unstable plastic flow to the metallurgist is the formation of the neck in the ordinary tension test. It is well known that in this test most metals exhibit a maximum in the externally applied load, followed by the process commonly referred to as "necking down." Instability in the simple tension test has been frequently discussed and numerous investigators1'2'3'12 have derived the criterion for instability in terms of a critical rate of strain hardening. It is the purpose of the present study to extend the criterion for unstable flow to the more general case where the body undergoing flow is subjected to combined loads. It is hoped that the problems considered will provide a more consistent picture of the general features of this important form of mechanical instability. The most practical implications of instability in plastic flow arise in connection with sheet metal forming operations. In the formation of a great many sheet metal parts, the deformations are produced primarily by stretching. If the conditions which lead to unstable flow are fulfilled in such a formation, and if the resultant instability leads to a pronounced localization of flow, then the useful limit of ductility of the material will have been reached. It i; also essential that the effects of instability be taken into consideration in any study of the plastic flow and rupture of metals under combined stresses. In general, when unstable plastic flow is initiated, straining becomes localized, the geometry of the test splecimen changes, and the state of stress in that portion of the specimen undergoing plastic flow is no longer under external control. In many past studies of the effects of combinetl Metals On flow and rupture) account has not been taken of the fact that, although a given test may be started under constant

Jan 1, 1947

By E. J. Rapperport, J. P. Pemsler

The thermodynamic activities of zinc in six solid solution Cu-Zn alloys ranging from 5 to 35 at. pct Zn were determined experimentally in the temperature range 400° to 600°C. This low temperature investigation was canducted in order to evaluate techniques developed to utilize the inherently high sensitivity of atomic absorption flocesses in the measurement of thermodynamic activities. Analytical expressions ,for the activity and actizlity coeflcient are given for the six alloys in the temperature ranges investigated. RELATIVELY few experimental methods are available for investigation of thermodynamic activities of alloys, especially in the solid state. The techniques most frequently used have been the electrochemical potential and the effusion methods, both of which have severe limitations in many instances. It is therefore desirable to expand the ability to perform such measurements in order to obtain new information as well as to provide an additional independent verification capability. In this work, we present a significant improvement in the spectrophotometric method for sensing small vapor pressures in static absorption cells. Similar techniques have been used previously;1"5 however, applications had been limited to relatively high pressures, often greater than 1 torr. Prior investigators have, for the most part, used broad spectral sources such as xenon or mercury lamps, and high intensity arcs. Hollow cathode sources were first suggested in 1956 6 and were used soon afterwards.4'5 These sources offer significant improvements in sensitivity and freedom from interfering spectral lines.'-' EXPERIMENTAL High purity zinc was obtained from Cominco Products, Inc., and copper from American Smelting and Refining Co. Both elements were of 99.999 pct purity. Copper-zinc alloys were vacuum melted in a high fired carbon crucible with each alloy pulled from the melt as a 4 -in. diam bar. The bars were swaged to -1/4 in. rods and vacuum annealed for 160 hr at 800° + 1°C. Samples for gross chemical analysis were taken at intervals along the length of the rods to ascertain the axial zinc gradient. Electron microprobe analysis of homogenized specimens indicated that the alloys had uniform compositions over their cross sections on a macro (200 p) and micro (1 u) scale to better than *1 pct (20) of the gross composition. This tolerance was determined by counting statistics, rather than assured composition fluctuations. All SiO 2 windows were high-ultraviolet-transmission grade to minimize intensity losses. Silica absorption cells were scrupulously cleaned consecutively in organic solvents, dilute HF, and distilled water before use. The empty cells were then flamed while under a dynamic vacuum, cooled, and removed to an argon-filled glove bag. Alloy pieces were cut and filed in the glove bag to produce fresh surfaces, and then loaded into the cells. The loaded cells were temporarily sealed, removed from the glove bag, reevacuated to 10-5 torr or better, and permanently sealed. The instrument used is schematically shown in Fig. 1. The spectral emission from a commercially made hollow cathode lamp (A) of a selected element is focused through an absorption cell (B) inside a well-controlled furnace (C). The intensity of the transmitted beam is measured using the spectrometer* (D) 'Techtron model AA4 atomic absorption spectrometer. which contains a grating (E) that disperses the light prior to impingement on the photomultiplier (F). The monochromator grating is adjusted so that only the wavelength of interest is measured. The power supply delivered an interrupted voltage to the lamp, causing a chopped radiation output to be transmitted. The detector read only the intermittent component of radiation incident upon it, so that all continuous noise signals (furnace radiation, and so forth) were eliminated. Three recording thermocouples contained in the muffle furnace were positioned along the length of the absorption cell: one at each end and one at the center. An effort was made to keep the ends of the cell several degrees hotter than the center to avoid window condensate. Appropriate thermal corrections were then necessary to relate cell pressure to radiation attenuation. Water-cooled heat shields, as shown in Fig. 1, were found to aid signal stability by protecting the hollow cathode and the photomultiplier from furnace radiation. The furnace had a 2-in. diam muffle, Kan-thal wound, with SiO 2 windows at its ends to minimize convective effects. The hollow cathode radiation was masked and focused to form a conic beam that was a maximum of { in. diam within the furnace. Thus, the 1.5 in. diam absorption cell easily contained the entire beam. The furnace was mounted on ball-bearing slides with positive positioning detents. This arrangement allowed the removal of the entire furnace assembly from the radiation path, position [I], Fig. 1, so that frequent sampling of the unattenuated beam intensity could be obtained. In all cases the beam intensity was kept constant to 0.1 pct as judged by readings taken immediately before and immediately after data collection. Only data for absorptions of less than 80 pct were utilized, as systematic deviations from linearity were found for greater absorptions.

Jan 1, 1970