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By F. V. Shallcross

Physical properties of thin films of CdS and CdSe formed by vacuum deposition onto glass sibstrates have been studied as a function of deposition and processing conditions. The crystallinity and surface features of CdS films were examined using electron microscopy and electron and X-ray diffraction techniques. The films were poly crystalline; the preferred orientation and crystallite size increased with film thickness, substrate temperature, and deposition time. The CdS films consisted primarily of hexagonal-phase material, in contrast to similarly prepared CdSe films which have previously been observed to contain mixtures of cubic and hexagonal phases. As-deposited CdS films showed no major dependence of Hall mobility on crystallite size or degree of preferred orientation. Hall mobility and carrier concentration in CdS and CdSe .films were measured at various temperatures; both parameters increased with temperature and yielded activation energies which depended on fabrication conditions. Surface-desorption phenomena and overcoating of the semiconductor with SiO affected the observed electrical properties significantly. THIN films of cadmium sulfide1,2 and cadmium sele-nide3,4 have been employed by various workers as semiconductors in the insulated-gate thin-film field-effect transistor, known as the TFT. These devices are most commonly made by vacuum deposition of all materials onto an amorphous substrate such as glass. A knowledge of the microstructure and electrical properties of semiconductor layers used in the thin-film transistor is essential in order to form a realistic model for the device and to improve its performance, reproducibility, and reliability. This paper will describe studies of the physical properties of vacuum-deposited CdS and CdSe films prepared under various conditions. Structural characteristics examined in- cluded phases present, crystallite size, nature of preferred orientation of crystallites, surface roughness, and structural homogeneity throughout the film thickness. Electrical properties measured were Hall mobility and conductivity and their dependence on temperature and ambient. Thin-film properties are affected by many fabrication parameters including purity and physical form of evaporant, deposition rate, film thickness, design and temperature of the evaporation crucible, geometry of the deposition chamber, nature of the residual atmosphere, composition and temperature of the substrate, and details of postdeposition processing. PREPARATION OF FILMS In this work the semiconductor films were deposited in a conventional oil-diffusion-pumped system with pressures in the 10-8 torr range. The CdS evaporant was obtained from the Eagle-Picher Co. as a high-purity coarse-grained crystalline powder; the CdSe was a high-purity sintered powder supplied by the Harshaw Chemical Co. The evaporation crucible was a resistance-heated molybdenum-wire basket coated with aluminum oxide and filled with a quartz wool plug at the top. The source to substrate distance was usually 10 cm. This region was enclosed by a Pyrex inner cylinder. The substrate was heated with an overlying Pyrex plate coated with tin oxide. The substrate temperature was controlled using a thermocouple attached to the lower side of the heater. This thermocouple was calibrated against another thermocouple attached to a dummy substrate and by observation of melting points of various metal films deposited in the system. The substrates were polished borosilicate glass plates and conventional glass microscope slides. Substrate preparation included cleaning with an ultrasonically agitated detergent bath followed by isopropanol-vapor de-greasing. Film thickness was measured interferomet-rically during and after deposition. STRUCTURE OF CdS FILMS Structural studies were performed on CdS films using electron diffraction, electron microscopy, and

Jan 1, 1967

By W. H. Andrews

THE constantly increasing consumption of Portland cement in the State makes the above subject of partlcular interest at this time. The increasing demand is due to the rapid settling of the country and the fact that new uses are being found frequently for the above named commercial article. The industry is one that is bound to grow as the population increases, and this being the case, it may be well ,it this time to consider briefly- the matter of the chemical and physical com-position of proper raw materials. A cement mixture is one that contains approximately 75 per cent. carbonate of lime, 15 per cent. Silica, and 5 to 7 per cent. alumina, and iron oxides; the other elements being magnesium carbonate and small quantities of the rarer elements general associated with limestone deposits. It call be readily seen from the above composition that it is possible to build up this mixture from a number of different materials. First.-A rock high in carbonate of lime can be mixed with clay or shale in such proportions as to bring about the desired composition ; the chief difficulty in the building up of such a mixture is that it is hard to find a clay or shale in which the silica-alumina, ratio lies .between 4 to 1 and 3 to 1 and at the same time shows physical characteristics which will make certain its adaptability to the practical manufacture of Portland cement. Very often clays or shales are found which are right chemically but contain large quantities of grit or free silica. Such clays or shale must be ground to extreme fineness in the mixture in order to make the silica and alumina combine with the lime when the mixture is burned. On the other hand, clays or shales are often found that have the proper physical characteristics but in which the amount of alumina, is too great.

Jan 9, 1913

By Fred C. Bond

THEM is acute need for a method that will measure the size distribution of finely divided materials, particularly when the particle sizes are smaller than the openings of the finest screen cloth regularly available for testing. Several methods and types of apparatus are in common use, but none are entirely satisfactory for all purposes. The commonest methods are microscopic grain counts, elutriation by liquids or air, and sedimentation. Valuable results have been secured by air elutriating devices, typified by the Haultain Infra-Sizer and the Pearson Air Analyzer. These are especially useful in obtaining sized fractions that can be examined and analyzed separately. They are particularly advantageous because the sizes of the samples produced are adequate for a considerable amount of subsequent manipulation and testing. The sedimentation methods, such as the Wagner and Klein turbidimeters, and the sedimentation balance, do not deliver sized fractions, but they do provide a means for reasonably rapid comparative determinations of fineness and surface area, which are important in many industries. The sedimentation balance consists essentially of a balance pan suspended in a liquid that contains falling particles. These are weighed as they settle onto the pan, and the time rate of settling is determined. The size distribution is computed from the settling rate. The balance appears to be inherently more accurate than any of the other methods, and it has served a useful purpose in the study of numerous problems, but there have been limitations which have restricted its scope of application. Because of the essential simplicity of the method, it was felt that intensive investigation might lead to modifications that would make it a valuable tool for the operators in industries that require precise information regarding the results secured from grinding equipment. A large number of size-distribution determinations below 200 mesh were required in connection with a particular research problem in fine grinding. The sedimentation balance was used in this investigation, and a technique was gradually developed that ultimately gave good results. A serious difficulty appeared early in the work. It was discovered that less material always settled on the sedimentation pan and more on the bottom of the containing jar than could be accounted for by calculation, and also that the material that settled to the bottom of the jar outside the edges of the pan was considerably finer than that on the pan. This segregation was so great that the distribution obtained for the finer sizes was obviously very much in error; material ground to about the degree of comminution of cement might have only 60 per cent of the calculated weight actually settling on the pan, and the error increased with the fine-

Jan 1, 1939

By AIME AIME

AT A meeting of the Boston Local Section of the Institute, on Oct. 3, approval was voted to the work done by its representatives on the Committee opposing the passage of a bill by the, Massachusetts Legislature to license engineers. The report is as follows: The Joint Committee on Licensing of Engineers, which included a Committee of the Boston Society of Civil Engineers and representatives of seven other societies,* submitted to the members of the respective societies, on Jan. 8, 1921, a report in which it was stated that on Jan. 4, 1921, a petition was filed in the Legislature of Massachusetts by the Boston Chapter of the American Association of Engineers accompanied by a bill to provide for the registration of professional engineers and land surveyors. This report also stated that at a meeting of this committee, held on Jan. 7, 1921, it was voted:

Jan 1, 1921

By Gerald Edmunds

THE liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the com- position of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. APPARATUS By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 1 ¾ in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 18 ½ in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By G. W. Healy, W. D. Forgeng, N. R. Griffing

The liquidus surface of the C-Cr-Fe system to 1900°C has been mapped from carbon solubility and freezing point measurements, metallographic observations, and published data. In the graphite field, the surface drops precipitously to meet a slope descending from the Cr3C2-C join through the mixed carbide fields to a meandering eutectic valley; this flows from the Cr-C to the Fe-C edge. On the low-cavbon side of the valley, the surface rises to the chromium corner. 1 HE purpose of this inquiry was to gain a more complete knowledge of the C-Cr-Fe liquidus surface. This required an extensive study of carbon and chromium-rich alloys which, in the past, have received the least attention. Sanbongi el al.1 measured the solubility of carbon in liquid alloys containing up to 25 wt pct Cr at temperatures of 1460" and 1545°C and found that it increased with chromium content and temperature. Lucas and wentrup2 also made solubility experiments in graphite crucibles, but at higher chromium contents in the range of 38 to 80 pct and at temperatures of 1550" to 1700°C; however, their experiments were relatively few, and the effect of temperature was not consistent. The present investigation included compsitions ranging from 0 to 94 pct Cr and 1.4 to 11.7 pct C at temperatures up to 1800°C. Saturation experiments in graphite crucibles, thermal analyses during freezing, and metallographic and X-ray diffraction studies were employed to obtain desired information which, together with published data from other investigations about the binary edges and the ternary system at lower carbon levels, made possible the construction of a comprehensive C-Cr-Fe liquidus surface. C-CR-FE LIQUIDUS SURFACE The derived ternary liquidus surface is shown in Fig. 1 where the solid curves are liquidus isotherms. The dashed curves and the binary edges are the liquidus field boundaries of the primary crystals, the arrows along these boundaries indicating their direction with decreasing temperature. Each intersection of three internal boundaries is the composition of liquid involved in four-phase isothermal equilibrium with the three primary crystals whose liquidus fields touch there. It may be observed that a total of six four-phase equilibria occur at melt temperatures. The general topography of the liquidus surface consists of a eutectic valley sloping down from the Cr-C edge at 3.2 pct C to the Fe-C edge at 4.25 pct C. The liquidus surface rises in two directions from the valley, one hillside terminating at the Cr-Fe edge while the opposing hillside rises toward the carbon corner out beyond the top edge of Fig. 1. Both hillsides are interrupted by intersections of surfaces or joints representing the liquid colmpositions of various three-phase equilibria. Seven primary crystals occur, namely a(bcc), ?(fcc), graphite, (Fe, Cr)3C capable of dissolving as much as 15 pct Cr, and three different chromium carbides in which iron is partially soluble by substitution for chromium. The composition ranges of the primary l~hases at melt temperatures are shown

Jan 1, 1962

By J. B. Morrow

WITH numerous plans under consideration for coal classification, and with the advent of the Bituminous Coal Code, the intelligent sam-pling of coal has become increasingly important. To us it is rather significant that there have been very few fundamental studies of coal sampling in American technical literature since those of E. G. Bailey, which appeared in the Journal of Industrial and Engineering Chemistry in March, 1909. He covered the subject up to that time so thoroughly and in such an excellent manner that perhaps many other later students have felt that they could add very little to his findings. The recent studies of the British Engineering Standards Association have indicated the possibility of a somewhat different interpretation of Bailey's results, permitting the taking of smaller samples, and perhaps it will now be helpful to reopen this question. C. W. H. Holmes, in an informative series of articles on coal sampling recently published in Colliery Engineering, makes two rather interesting statements, as follows: It is scarcely surprising to find a lack of interest and knowledge regarding the sampling of coal not only in the mining industry itself but also among consumers of industrial fuel: at its best coal sampling is a dirty business, regarded as a nuisance and an expense by the commercial man, and usually as a nuisance and nothing else by the chemist. The writer can conceive only two classes of people who have never experienced any difficulty in obtaining representative samples of coal from wagons; those who have never tried to, and those who have never had the necessity or desire to check the accuracy of their work. The primary purpose of this paper is to present some tabulated data of the more significant results of a sampling investigation undertaken during the last four years to obtain certain fundamental data on the variables connected with coal sampling and to point out that often assumptions have been made that are not in accordance with the facts. One of the standard sampling methods states:

Jan 1, 1935

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is neccssary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important cornponents of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transFormation are dealt with in a highly detailed and descriptive manner in. the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilib-rium conditions of thermal treatment. The Guilletl diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts: At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase's in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. Reference may be made at this point to the efforts of Marsh5 to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encountered in traversing the nickel-steel nickel-cast-iron range under what might be called ordinary departures from equilibrium. ExperimentaT. Conditions Since the intent has been to establish structures developed under arbitrary conditions, experimental details have perhaps more than usual importance. Three of these conditions should particularly be noticed: (I) the material was cast and not subjected

Jan 1, 1942

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is neccssary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important cornponents of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transFormation are dealt with in a highly detailed and descriptive manner in. the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilib-rium conditions of thermal treatment. The Guilletl diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts: At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase's in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. Reference may be made at this point to the efforts of Marsh5 to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encountered in traversing the nickel-steel nickel-cast-iron range under what might be called ordinary departures from equilibrium. ExperimentaT. Conditions Since the intent has been to establish structures developed under arbitrary conditions, experimental details have perhaps more than usual importance. Three of these conditions should particularly be noticed: (I) the material was cast and not subjected

Jan 1, 1942

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is necessary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important components of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transformation are dealt with in a highly detailed and descriptive manner in the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilibrium conditions of thermal treatment. The Guillet1 diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts. At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase's in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. [ ] Reference may be made at this point to the efforts of Marshy to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encoun-

Jan 1, 1942

By G. B. Gould

FROM the very inception of the price-control experiment in the bituminous-coal industry, the problem of price differentials was of major importance. In fact, assuming that there will be no legal or Govern- mental obstacles to price control, the successful maintenance of the present or any other method designed to control bituminous-coal prices will depend upon the discovery of some satisfactory way to determine these differentials in price, among: individual mines and groups of mines. Being of organic origin, bituminous coal is a commodity that presents an almost infinite variety of qualities. It is inevitable, therefore, that a work- able price-control system must attempt

Jan 1, 1935

By Wilson Lundy

THE history of the production of sulfur from salt domes in Louisiana and Texas originated with the operations of the Union Sulphur Co. at Sulphur, La., followed by the Freeport Sulphur Co. at Bryanmound, Tex. Including the present development of Grande Ecaille by the Free-port Sulphur Co., which constitutes the tenth dome to be equipped for the production of sulfur in the Gulf Coast, less than 10 per cent of all the known domes have proved to contain sulfur in commercial quantities. The Grande Ecaille salt dome is in the tidal marsh of the Mississippi River delta in Plaquemines Parish, Louisiana. It is 10 miles southwest of the right descending bank of the river approximately 45 miles below the city of New Orleans and is within 4 miles of the shore line of the Gulf of Mexico.

Jan 1, 1934

By H.E. Brauer

Among the zinc base alloys used for casting in metal moulds, pnrticularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortncss which facilitate ca,sting. Objection to the use of these alloys may be raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intererystalline corrosion. In all cases which have come to our kno~vlcdge where the conditionsof service were known, failure has occurred upon cxposurc to moisture and heat varying from a hot moist atmosphere to lligh pressure steam. RIoreover, the alloys described in all such roses contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intererystalline oxid:~t'ion in zinc-aluminurn alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Baucr2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the must part, and Rawdon's3 examinations were madc on an alloy containing 0.1 per cent. lead also exyosctl to thc Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to det'ermine the exact nature of this phenonienon and the effect of other metals present as impurities or intentional additions in accelerating or retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation. At the time this work was undertaken the best available equilibrium *Investigator, Metal Section, Research Division, The New Jersey Zinc Company. 'H. W. Williams—Jour. Am. Inst. of AIet,als, Vol. 11, p. 221 (1917). 2o. Bauer—ZeiL, fiir i'vletall Kunde, Vol. 12, .No. 7, pp. 129-31 (1920). 3H. S. Rawdon—Trans. Am. Elcctrochcmic.al Society (1921).

Jan 1, 1923

By H. E. Brauer

Among the zinc base alloys used for casting in metal moulds, pnrticularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortncss which facilitate ca,sting. Objection to the use of these alloys may be raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intererystalline corrosion. In all cases which have come to our kno~vlcdge where the conditionsof service were known, failure has occurred upon cxposurc to moisture and heat varying from a hot moist atmosphere to lligh pressure steam. RIoreover, the alloys described in all such roses contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intererystalline oxid:~t'ion in zinc-aluminurn alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Baucr2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the must part, and Rawdon's3 examinations were madc on an alloy containing 0.1 per cent. lead also exyosctl to thc Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to det'ermine the exact nature of this phenonienon and the effect of other metals present as impurities or intentional additions in accelerating or retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation. At the time this work was undertaken the best available equilibrium *Investigator, Metal Section, Research Division, The New Jersey Zinc Company. 'H. W. Williams—Jour. Am. Inst. of AIet,als, Vol. 11, p. 221 (1917). 2o. Bauer—ZeiL, fiir i'vletall Kunde, Vol. 12, .No. 7, pp. 129-31 (1920). 3H. S. Rawdon—Trans. Am. Elcctrochcmic.al Society (1921).

Jan 1, 1923

To THE BOARD OF DIRECTORS AND MEMBERS OF THE AMERICAN INSTITUTE OF MINING AND METALLURGICAL ENGINEERS. GENTLEMEN Like every other significant activity in the United States today, the work of the Institute has been affected by and adjusted to the prosecution of war against Germany, .Japan and their satellites. As the elaborate engines and materiel of modern mobile warfare are made, for the most part, of metals and other minerals; and are powered by mineral fuels, the industries -represented by the A.I.M.E. are of primary and vital importance. Of some 29 critical materials officially listed by the War Production Board, 24 are minerals. An alternate for one of the others, rated as a nonmineral, is to be made principally from petroleum. This alludes, of course, to rubber. The procurement of tremendous quantities of such raw materials and the effective processing, fabrication, and utilization of them depend on members of those branches of the engineering profession represented by the A.I.M.E.

Jan 1, 1943

By C. D. Hall

This paper may be divided into two main parts: (1) analysis and data to show that Eq. 6 adequately correlates the authors' experimental data, and (2) the assertion that Eq. 20 "should permit scale-up with data taken from one pipe diameter for Newtonian, inelastic non-Newtonian, and viscoelastic fluids, such as dilute polymer fracturing fluids, which produce considerable pressure reductions." The authors might well recommend that this broad grouping of fluid types could be correlated by using Eq. 6 (requiring data from at least two pipe diameters). On the other hand, Eq. 20 is only shown to be adequate for conditions within the range of the present data set. Specifically, predictions by Eq. 20 for diameter scale-up to casing sizes would give larger deviations than implied in Table 2, and scale-up for some other fluids that give large drag reduction could be grossly in error. The description of a class of fluids "which produce a diameter family of straight parallel lines on a log (d?p/4L) vs log (8 v/d) plot. . ." defines a necessary condition for using Eq. 6; i.e., that s shall be constant for each fluid. The proposal that Eq. 20 is applicable to turbulent flow of such fluids is equivalent to saying that the spacing of these parallel lines, with A being constant, will be found to correspond to m = -1.20 for all such fluids. Table 1 shows the values of m derived from data on 16 non-Newtonian fluids. The key statement of this paper is that the diameter exponents "do not vary significantly from . . . -1.20." In statistical terms, this says that the m value for each fluid, which was obtained from all the measurements made on that fluid. has not been shown to be different from the arithmetic mean of the m values for the 16 fluids tested. This implies that the group mean, -1.20, is a more reliable value to use for an individual fluid than is the m value derived from the data on that fluid alone. No statistical test is described to support the key statement that the diameter exponents do not vary significantly from -1.20. Such a test would have to take into account that each individual m value is shown to correlate the pressure gradients for its fluid, with only about 3 percent standard deviation over the diameter range covered. That is, the m value is not the result of a single independent measurement. Thus, it would not be sufficient, or valid, to compare the deviation of one of the m values with the variance of the 16 values of m about their mean. An alternative interpretation of the key statement is that the diameter exponents do not vary appreciably from -1.20; i.e., that using -1.20 does not cause serious inaccuracy. Table 2 seems to be offered in support of such an assertion. However, such a statistical treatment (1) is unnecessary and (2) cannot lead to any valid scale-up generalization. The amount of error introduced by using a 1"wrong" value of diameter exponent — i.e., -1.20 instead of m — is determined by Eq. 6. The ratio of the pressures predicted by Eqs. 6 and 20 for scale-up from ds in small pipe to d, in casing is The pressure for 30-percent calcium carbonate slurry (m = -1.112) in 10-in. ID pipe would be predicted 30 percent higher by Eq. 6 than by Eq. 20, if based on tests in 0.5-in. ID pipe. The data set tested in Table 2 represents only a limited sample of pipe diameters (ratio of about 4:l) out of the population of diameters that would

Jan 1, 1970

Elected Died 1895 *ABBOTT, AI ATTHUR 1908 1882 *ABBOTT, ARTHUR V 1906 1905 * ABE, MASAYOSHI 1909 1903 * ADAMS, CHARLES C. 1905 1905 * ADAMS, WILLAMS 1909 1903 * ADAMS, W. EDWARDS 1910 1884 *ADDY, MATTHEW 1896 1889 * AKERS, WILLIAMS 1906 1894 *ALLEN R B 1896 1905 * ALLEN, R. SCOTT 1906 1874 *AMIOT, H 1892 1886 *AMSLER, CARL 1894 1895 *ÅNGSTROM, CARL 1901 1887 * ARCHBALD, JAMES 1910 1900 * ARLETT, GEORGE H 1906 1895 *ARMSTRONG, JOHN F 1898 1882 *ARNOLDS, HUGO 1886 1875 *ASHBURNER, CHARLES A 1889 1872 *ASIIBURNER, WILLIAM 1887 1883 *ATKINS, C M , JR 1885 1905 * AUSTEN, PETER T 1907

Jan 1, 1917

Elected Died 1895 *ABBOTT, AI ATTHUR 1908 1882 *ABBOTT, ARTHUR V 1906 1903 * ADAMS, CHARLES C. 1905 1884 *ADDY, MATTHEW 1896 1889 * AKERS, WILLIAMS 1906 1894 *ALLEN R B 1896 1905 * ALLEN, R. SCOTT 1906 1874 *AMIOT, H 1892 1886 *AMSLER, CARL 1894 1895 *ÅNGSTROM, CARL 1901 1900 * ARLETT, GEORGE H 1906 1895 *ARMSTRONG, JOHN F 1898 1882 *ARNOLDS, HUGO 1886 1875 *ASHBURNER, CHARLES A 1889 1872 *ASIIBURNER, WILLIAM 1887 1883 *ATKINS, C M , JR 1885 1905 * AUDTIN, PETER T 1907 1897 *AYERS, WILLIAM 1898 1885 *BABCOCK, GEO H 1893 1884 *BAILEY, EDWARD 1889 1880 *BAILEY, JACKSON 1887 1900 *BALLOU, FRANKLIN 1903

Jan 1, 1910

By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

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Jan 1, 1940