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By R. W. Gurry

In the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and III0°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon conteDt of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched, The mean result of concordant ments-—taeats-is-^that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C .(i755°F.) and 1.89 per cent at III0°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutec-toid temperature (738°C. or I360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature II35°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. Experimental Procedure The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.' In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (I6°F.) but at a given location the temperature remained within +o.5°C. (o.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (I760°F.) and III0°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with toluene; this quickly produced on the

Jan 1, 1942

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By R. W. Gurry

When a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. Experimental Procedure Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;' it suffices to state here that the carburization lasted about I40 hr. at 760°C. (1760°F.) and 44 hr. at iiio°C. (2030°F.), these periods being long enough-—on the basis of the calculations presented later—to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By Robert A. Colten, Frederick C. Hull, Robert F. Mehl

It is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.l,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in I939.3 Two types of process were described: (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. I);2,4 the former, occurring near the knee of the S-curve, has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ael, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenabil-ity; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels." Previous Data on Rate of nucleation and rate of Growth Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Meh1,l and by Dorn, De Garmo and Flanigan.2, It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given. Except for the approximations of Mehl and the work of Dorn, austenite grain size was disregarded, though it is well known

Jan 1, 1942

By G. V. Smith, R. F. Mehl

The decomposition of austenite in steels, because of its immerse practical importance, has been subjected to extensive study in recent years from the point of view of the mechanism of the process.1"3 Although much information has been acquired, a number of questions, principally of theoretical interest, remain. One is that of the atomic-crystallographic mechanism by which each of the various reaction products forms. The isothermal reaction products of the eutectoid decomposition in plain carbon steels (to which this study is restricted) have conveniently been classified in three general groupings—pearlite, bainite, and martensite. Of these several products, pearlite and martensite have been studied extensively, but bainite has received only scant attention. -As a result, the mechanism of the formation of pearlite and that of martensite are now fairly well understood while a great deal of uncertainty exists regarding bainite. Pearlite Pearlite forms from austenite by the precipitation of alternate platelets of cementite and ferrite, which grow into the austenite matrix.2--5 The rate of reaction may be described in terms of a rate of nucleation and a rate of growth.2.3 Mehl and Smith6 have attempted to determine the lattice relationships existing between the ferrite in pearlite and the' parent austenite. Using a pole-figure method of analysis, it was found that a limited number of ferrite orientations resulted from the decomposition of a single grain of austenite; it was not possible, however, to decide between two assumed ideal relationships, both of which appeared to account for the experimentally determined pole figure. It was definitely shown, however, that the relationship obtaining was quite different from that determined for the proeutectoid separation of ferrite.7 No attempt was made to determine the habit plane (matrix plane to which the precipitate lies parallel) of the pearlite lamellae. Belaiew8 earlier had stated that the number of directions assumed by the pearlite lamellae in a single grain of austenite was 12 (no details were given) and concluded wrong!:!, as Mehl and Smith6 have pointed out, that the lamellae delineate the {2I0} planes of ferrite.* Martensite It is known that martensite is a transiti0nal constituent of body-centered tetragonal lattice,' and that it forms suddenly

Jan 1, 1942

By M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

By J. K. Stanley, R. F. Meel

The recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are emp1oyed.l Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystal- lization is not a heterogeneous reaction within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress. 4,5 The theory of recrystallization is not in advanced state; if recrystallization data were obtained in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed.27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert mcasurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now available for the case of three-dimensional recrystallization (recrystallization of

Jan 1, 1942

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By Blake M. Loring

Recently the S-curves for 30 to 40 alloy steels have been pub1ished.l.2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.29 per cent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr, at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1¼ by ½ by ? in. Wires attached to the samples were used for handling. instead of tongs, to avoid chilling. The specimens were heated at 845°C. for ½ hr. and quenched into constant-temperature salt baths held at various temperatures from 205' to 650°C. The time required to transfer the specimens was found to be about 1½ sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 2I°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1942

By David B. Reger

Wildcat drilling for new supplies of gas and the expansion of previously discovered oil and gas pools were the principal petroleum activities in West Virginia .during 1942. Much of the new gas exploration is still uncompleted and still indecisive but various wildcats made substantial extensions to existing pools. Out of 53 wildcats drilled 27 resulted in commercial gas and 6 in commercial oil. Four of the oil discoveries also had commercial gas. No strictly new pools of oil or gas can safely be described as discovered but several scattered oil and gas wells previously drilled have been confirmed as the openers of definite pools; also, various completions closed wide gaps between apparent gas pools already discovered. The proved oil territory of the state was increased about 4850 acres and the proved gas territory about 51,000 acres. The new proved oil reserves should about balance withdrawals and the new gas may represent a substantial increase. Aside from the drilling in four rather lively pools, oil activity was slight because of unfavorable operating conditions and prices. Gas drilling also declined for reasons beyond the control of the operators. The account of operations, as gathered from trade journals and other reporting services, shows that 797 new wells were drilled, providing 119 new oil wells with 2762 bbl. of daily new production; 536 new gas wells with 1,228,501,000 CU. ft. of daily open flow: and 142 dry holes. Also... 76 old wells were drilled to deeper sands, with 71 bbl. and 26,034,000 cu, ft. of added production. On the new wells the oil average was 23.21 bbl. per well per day; and the gas average was 2,270,406 CU. ft. per well per day. On new wells the ratio of dry holes to completions was 17.82 per cent. On deeper drilling the ratio of failures was 21.05 per cent. Production of oil for the year was estimated by the Oil ad Gas Journal as 3,492,000 bbl., as compared with 3,378,000 bbl. in 1941. Production of natural gas for the year is estimated by the author as 220,000,000,000 cu. ft., as compared with the U. S. Bureau of Mines final figures of 207,000,000,000 cu. ft.* in 1941. General State op Industry Leasing of wildcat acreage increased considerably. The total land of all classes under lease may now exceed 5,000,000 acres. Taking into consideration completions, abandonments and corrected figures or estimates, Table I shows cumulative and late annual statistics. New Pools and Extensions Table 2 shows the principal areas of drilling activity during 1942. Various consolidations of territory, hitherto treated as separate pools, have been made. in addition to these active pools, extensive drilling was done in numerous other areas where pool boundaries can hardly be defined. Summary or Exploration Table 3 gives a summary of important wildcat or exploratory wells drilled during

Jan 1, 1943

By Mario L. Villa

Oil activities and the petroleum industry in general have suffered severely in this country as a result of present war conditions. War has imposed a very heavy and unpleasant burden on the shoulders of those whose duty it is to keep .Argentina supplied with the necessary oil to meet industry's growing demands. Since 1940, imports of manufactured products from Europe and the United States have fallen to a minimum, making it necessary to manufacture as many of them as possible locally. This has brought about the establishment of many new industries and the enlargement of already existing plants, creating new demands for fuel that drain heavily the country's stocks, which already were overtaxed because of the diminished supply imported. To cope with this problem, a plan for an intensification of oil-field activities was drawn up by Yacimientos Petroliferos Fiscales (Argentine Government Oil Fields) which included the drilling of many new

Jan 1, 1943

By J. M. De La Garza Cárdenas

The total production of oil in Mexico in 1942 was 34,715,547 bbl.; that is, 8,179,254 bbl. less than the amount produced in 1941. The daily average for 1942 was 95,111 bbl., while that for 1941 was I17,520 barrels. The reduction of 22,409 bbl. per day in production was due to a decrease in exports because of the scarcity of tankers. This reduction has affected principally the Northern and Southern districts of the Tampico area; in December the Northern district (Panuco) was producing less than zoo0 bbl. per day with 445 wells shut down and the Southern district (GolJen Lane) less than $000 bbl. per day with 140 wells shut down. Drilling.—During the year 14 wells were drilled in Mexico, of which five were productive. Seven dry holes were drilled in Ebano, Tampico Northern district, in search for new producing fractures; plans are being made to explore this area by means of resistivity measurements. Three producing wells were completed in Poza Rica. Drilling in this important field will continue during 1943 to determine its extension to the west. In the Isthmus of Tehuantepec no wells were completed. Two gas wells were completed in northeastern Mexico. Wildcats.-—Two wildcat wells were completed during the year, to test the extension of the Golden Lane to the south; both were unproductive. In the Isthmus a deeper sand was found in the El Plan field* This discovery has made an important increase in the reserves in this field and will allow an increase in the production of the area during 1943. In December, three exploration wells were being drilled, two in the Tampico area and one in the Isthmus. Operating Technology.— Satisfactory progress has been made in Mexico in the application of petroleum engineering to the development and operation of the oil fields. Mud control is now an established practice and has lessened the number of fishing jobs and has allowed more open hole to be carried than formerly was possible. During 1942 the first effective use was made of determinations of bottom-hole pressure, and other modern production practices such as gun-perforating and squeeze-cementing are being introduced. Plans for 1943 The oil production during 1943 is expected to be slightly larger than that of 1942, especially if tankers are available for exporting crude and refined products. The Government proposes to increase exploration and drilling activities to increase the reserves and potential production of the country; about 50 wells will be drilled during the year, including wildcat wells in northeastern Mexico, Tampico and Isthmus areas and exploitation wells in the Ebano-Panuco, Poza Rica, El Plan and Cuichapa fields. Acknowledgment Mr. A. Barnetche, of the Production Department, "Petr6leos Mexicanos," assisted the writer in the preparation of the statistical data.

Jan 1, 1943

By Walter Miller

AFter a year's continued impact of war, the task of the petroleum-refining industry stands out clearly and looms up in larger aspect. This time it is not, as it was so largely in the first World War, simply a matter of increased quantity—more and more of the same petroleum products that had substantially been standard for years. In this era the emphasis is largely on newer and improved materials which had been produced, if at all, in comparatively insignificant quantities, and for which manufacturing equipment was not available on a large scale. At the beginning of 1942 four great product needs (besides a number of lesser ones) confronted the industry: 100-octane aviation gasoline, toluene for T.N.T. production, high-quality lubricating oils for aviation and Army equipment service, and petroleum chemicals for synthetic rubber manufacture. The difficulty in presenting a review of engineering progress in petroleum refining during 1942 is that there is so little one is free to say about so much which has been and is being accomplished. At the opening of 1942 the program was to increase the then existing capacity of 50,000 bbl. a day of aviation gasoline to over 150,000 bbl. daily by building new plants at an estimated installation cost of $150,000,000. Later in the year. after the announcement by President Roosevelt of a large increase in the program for war-plane building, additional contracts were made between the Reconstruction Finance Corporation and rehers to raise the capacity to 250,000 bbl. per day. The greatly increased scope of the war activities in all parts of the world, the obligation of the United States as the arsenal of the United Nations, and the greater importance and use of bomber, transport, and cargo planes will undoubtedly bring about plans and installations for a further increase in production of aviation gasoline over the present announced plan. In this connection, Jesse Jones, Reconstruction Finance Corporation Chairman, announced that as of Oct. 31 the R.F.C. had through its subsidiary Defense Plant Corporation entered into contracts for the construction, expansion, or equipping of 28 plants to increase 100-octane aviation gasoline production, but gave no data on 'capacity involved or completion dates. His list did not, of course, include a number of existing plants, and some installations being made by companies who are themselves financing the construction. Production from existing operating installations was materially increased in a number of instances as a result of pooling knowledge of improvements in operation and also by the exchange of Components going into 100-octane blend to enable greater quantities of aviation gasoline to be produced from the over-

Jan 1, 1943

By R. H. Dourson, B. H. Sage, W. N. Lacey

The compositions of coexisting phases in the methane-propane-n-pentane system were determined at 160° and -2 20°F. throughout the two-phase region, at pressures above 500 lb. per sq. in. The experimental results permitted the calculation of gas-liquid equilibrium constants as well as the establishment of the critical behavior of this ternary system. Although many binary paraffin hydrocarbon systems have been investigated, the experimental work relating to the phase behavior of ternary paraffin hydrocarbon mixtures at elevated pressures is relatively scarce, being limited to a study of the meth-ane-propane-PL-pentane system at 100°F.l,2 However, Guter and co-workers have studied the phase behavior of the methane-ethane-ethylene system at relatively low temperatures. Information concerning the phase behavior of ternary systems is of value in predicting the behavior of the components in multicomponent systems, since the influence of pressure, temperature, and concentration may be individually ascertained. In the light of the importance of such information, the study of this ternary system was extended to higher temperatures in order to increase the field of temperature in which the data could be applied. Since all states encountered in this investigation are above the critical temperature of methane, the details of its phase behavior are not of direct significance. The properties of propane in the heterogeneous region were taken from a correlation3 based upon recently published data. The corresponding information for n-pentane was taken from experimentally measured vapor pressures and volumetric data.4 The rnethane-propane system has been studied throughout the two-phase region at temperatures above 70°F.,5 while the phase behavior of the propane-n-pentane system has been established for temperatures above 160°F.6 The volumetric and phase behavior of the methane-72-pentane system has been studied in detai1.7,8 The experimental measurements serve to establish with adequate accuracy the phase behavior of the components and of the constituent binary systems for this ternary system. It is believed that, with the exception of the measurements for the methane-propane system, the uncertainties in the earlier data relating to the pure substances and the binary mixtures are probably less than those associated with the values reported here. Method The methods and apparatus employed in this investigation have been described.137 In principle, the method involved the withdrawal of samples of the coexisting gas and liquid phases from a vessel containing a heterogeneous mixture of methane, propane and n-pentane. Provision was made so that

Jan 1, 1943

By D. F. Botkin, B. H. Sage, W. N. Lacey

Joule-THomson coefficients for two natural gases were determined at pressures up to 600 lb. per sq. in. throughout the temperature interval between 70" and 310°F. From these primary data and available information relating to the isobaric heat capacities of the components at infinite volume, the heat capacities of these gases were computed throughout the above-mentioned range of pressures and temperatures. The enthalpies of the gases were computed as a function of state and the results compared with values obtained by several methods of prediction currently available. Table i .—Composition of Gas Samples Components Gas A Gas B Carbon dioxide................ 0.0090a 0 .042 0 Methane...................... 0.8255 0.8385 Ethane.......................0.0901 0 .0637 Propane....................... 0.0462 0.0374 Isobutane..................... 0.0074 0.0039 n-butane................ ...... 0. 0126 0 .0095 Isopentane.................... 0.0032 0.0016 n-pentane..................... 0.0022 0.0011 Hexanes and Heavier........... 0.003& 0.0023 Experimentally determined Joule-Thom. son coefficients for natural gases afford a satisfactory means of checking the accuracy of prediction of their thermodynamic properties from the behavior of the components in the pure state and in binary mixtures. Relatively small samples of these natural gases were available, together with their analyses, and the Joule-Thomson coeffi- The Joule-Thomson coefficients were determined by measuring the change in temperature resulting from the passage of the gas through a porous thimble with a known pressure difference and under such conditions that the process was substantially isonthalpic. The details of the apparatus employed for this purpose have been described.' It is believed that the changes in temperature and pressure were ascertained with an uncertainty of not more than 0.3 per cent. However, as a result of deviations from steady flow, it is probable that uncertainties as large as 2 per cent may exist in the measured Joule-Thomson coefficient. The gases utilized in this work were taken from high-pressure separators and were dried prior to use by passage over calcium chloride at pressures in excess of 300 lb. per sq. in. The gases were subjected to the conventional fractionation and Orsat analyses. The results are recorded in Table I. The composition is typical of gases from such sources, with the possible exception of the presence of significant quantities of carbon dioxide in each of the samples. The experimental results obtained for the two natural gases are graphically Portrayed in Figs. I and 2. The experimental

Jan 1, 1943

By F. C. Oliphant, George H. Fancher

Two samples of drilling mud from the Hastings oil field, Texas, were tested, and the solids in each were separated into small fractions of a limited range in particle size. The mineral composition of each fraction by X-ray analysis is reported, and the results are interpreted in relation to other measured quantities, such as the physical properties of the original samples and the density of the various fractions. It was found that only 7 to 8 per cent by weight of the solids was of colloidal dimensions and that neither of the samples contained montmorillonite but did contain illite. Considerable calcite was also found. These data should be useful to the geologist interested in the origin and history of sedimentary strata as well as to the petroleum engineer. Introduction The questions, What is good drilling mud? What constitutes bad drilling mud? are pertinent, because the proper use and control of drilling fluids has been a factor of great importance in the successful drilling and completion of oil wells since the days of Captain Lucas. Adequate control of the characteristics of drilling fluids has assumed greater significance comparatively recently because of the problems introduced by caving formations in deep wells, costly blowouts and impressive mud bills. Much is known about the solution of some of the problems but, despite extensive research directed toward a better understanding of the physical and chemical properties of clay suspensions, it is difficult to define precisely a drilling mud, and much more difficult to say what constitutes a good mud. It is generally believed that the smaller particles of a drilling mud greatly affect its physical properties. In fact, it is customary to blame the colloids in a mud for nearly everything that goes amiss, because colloidal properties have effects out of all usual proportion on viscosity, filtration rate and reaction to electrolytes. It is germane to know whether drilling muds possess colloids and if so, the quantity and kind. Source oF Samples Two drilling muds from the Hastings oil field, Brazoria County, Texas, were selected because it is generally agreed that in this oil field good natural muds made solely from formations penetrated by the drill can be used until the well is nearly ready for completion. Customary drilling procedure in this field is to spud in with water, set a protective string of pipe, drill to 2500 ft. and set the surface casing. Drilling is continued to 5500 ft. with no treatment of the drilling fluid other than addition of water to

Jan 1, 1943

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 A. V. Deforest, C. W. Macgregor, A. R. Anderson

One of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing or the A.S.T.M., 1938. The work of Mann.' Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserves especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by P ALo plotting So = 1/A0 as a function of eo = ALr,o where A0 and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors.7'8 It was shown that the true physical behavior of the material in the tension test could best be represented P by plotting the average true stress, S = 2P as a function of 6 = q' = log —r = log ~9L where P, A, L, S, E, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximin load point to fracture. The construction of such curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain dificulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece diameters to fracture under impact conditions offers considerable experimental difficulty. In order to make it feasible to

Jan 1, 1942

Jan 1, 1943

Jan 1, 1943