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By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria 'Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By John Chipman, Helen Towers

DEVELOPMENT of a simple radioactive tracer technique for measurement of the diffusion coefficient of calcium ion in liquid slag has already been reported. The investigation was of a preliminary nature designed to explore the possibilities of using radioactive isotopes and to establish a method, and no great accuracy was claimed for the results. It was shown, however, that Ca15 could be used successfully, and the values obtained for the diffusion coefficient appeared to be of the right order of magnitude. However, it was considered that a better technique could be devised for carrying out the diffusion. The experiments were, therefore, continued to find a more accurate method, to check the calcium results, and to extend the investigation to include measurements of the diffusion coefficient of silicon in the same slag. There were two flaws in the original technique. Convection was the cause of too many failures, and the interface between the two slags in the diffusion cell was curved rather than plane, probably due to a surface tension effect caused by the addition of the tracer Ca45 in the form of chloride. Two methods of overcoming these defects were tried. Since it was planned to study diffusion of the short-lived isotope Si"' also, the development of methods was restricted to those which gave promise of being reasonably rapid. Method 1—The principle was identical to that previously used with respect to the diffusion conditions, but there were three differences in technique. Temperature control was more rigid, the tracer was added to the slag as Ca45O rather than the chloride and, finally, an effort was made to translate to high temperatures the elegant method developed by Cohen and BruinV or bringing together the two liquid layers and beginning the diffusion. A master slag was melted in graphite, ground to a fine powder, and analyzed (38.5 pct Ca0-20.9 pct Al2O3-40.5 pct SiO2). The tracer was received as Ca45C12 in an aqueous solution of CaC12 + HC1. From this, calcium oxalate was precipitated, ignited to calcium oxide, and added as such to the slag to give an activity of approximately 5 µc per g. The mixture was then melted into the form of a cylinder 3/16 in. diam and about 1 in. long. A solution identical to the tracer solution without Ca45 was given exactly the same treatment. The resulting Ca40O was mixed with that slag which was to form the tracer-free half of the diffusion cell, and this was likewise melted into a cylinder of the same size. Slag cylinders, two with and two without Ca15, were set in graphite blocks as shown in Fig. 1, and the crucible was lowered into position in the fur-

Jan 1, 1958

By H. Hooykaas

A few years ago Marsal published a method of predicting oil recovery as a function of time for an edge-water-drive reservoir with several rows of wells.' The method is based solely on oil- and water-production data obtained during a short period for the first row of wells and the gross productions (past and future) of all wells. This paper presents a streamlined version of the original publication and experimental evidence showing the reliability of this version. For this purpose scaled experirnents were performed in a large model (750 X 500 X 23 cm, 24.4 ft X 16.2 ft X 8.9 in.) in which edge-water-drive reservoirs with three rows of production wells were simulated. From the results of the experiments it is concluded that the method gives a fairly accurate prediction of the future production behavior of the reservoir and enables us to select the most profitable production plan. Results obtained with the method were always slightly conservative. INTRODUCTION The calculation method developed by Marsal aims at forecasting future reservoir behavior.' It can be applied to floods in which a number of down-dip wells are rapidly going to water. Essentially it is a method for predicting the future behavior of the up-structure wells on the basis of the observed behavior of the down-structure wells. As such, the method is especially useful for predicting behavior of edge-water drives toward several rows of wells. The requirement to be met for justifying the approach is identity of production mechanism in all regions of the reservoir. The attraction of the method then lies in the fact that it applies even when we have no complete description of the prevailing production mechanism. The original publication was in the German language and for this reason, perhaps, did not attract widespread attention. In our opinion it deserves to do so because it does offer in a simple way results which are in fair agreement with observed data. The aim of the present paper is to bring the method to the attention of a wider audience. The method in its most simplified form is reviewed and experimental data in support of it are presented. PRINCIPLES To show Marsal's principle. we will first write the continuity equation for very simple conditions, linear flow (in the positive x-direction) in an incompressible porous body [cross-section A(x), porosity +(x)], saturated with incompressible fluids (oil saturation S). When the oil in this formation is displaced by water, injected at x = 0 (inlet face), we get where q(t) is the total gross displacement rate and f the fractional oil flow. The equation can be solved if we make the assumptions: (1 ) that the fractional oil flow (f) is a univalent function of saturation (S); and (2) that the function is the same throughout the porous medium. Then: f = f(S) Solving this equation with the method of characteristics, we obtain

Jan 1, 1966

By John W. Bell

In the introduction to an excellent pamphlet, John Gross' makes the following statements: Although marked progress has been made along mechanical lines, the theory and conception of underlying principles have not advanced so rapidly. This lack of advance in theory may be attributed to the unfortunate situation resulting from the controversy as to whether the Rittinger or Kick law is applicable to crushing. Many pages of the technical literature are burdened with theoretical discussions in favor of one or the other of these laws, which have tended to cloud rather than to clear the atmosphere. Realizing the situation, the Milling Committee of the American Institute of Mining and Metallurgical Engineers, through its secretary, E. A. Hersam, studied the milling industry and, because of the apparently hopeless lack of agreement in the Kick versus Rittinger dispute (5, 13, 14, 0, i8, 19, 21, 22, 23. 24, 30. 34), concluded that a foundation for the theory of crushing was of primary importance. The numbers in the paragraph quoted refer to papers listed by Mr. Gross in his Bibliography on Crushing and Grinding.1 One is obliged to infer that these papers show "hopeless lack of agreement in the Kick versus Rittinger dispute." No. 22 is a paper by Arthur O. Gates2 and No. 23 is one by the writer.3 Employing the subject matter contained in papers Nos. 22 and 23 2,3 the writer will show that their authors formulated identical conclusions, based solely on experimental evidence. Exactly the same defect in the Stadler hypothesis was described in each of the two papers, although entirely different experimental methods were employed in uncovering it. Both of the authors, independently, formulated the conclusion that Rittinger's was a true hypothesis and Stadler's false. The evidence in a third paper4 will be employed to prove that Stadler's hypothesis, when examined experimentally, is worthless. STADLER'S HYPOTHESIS WORTHLESS It is the writer's opinion that the evidence available in 1915 and the corroborating evidence in 1916 was amply sufficient to eliminate the need for any further consideration of Stadler's hypothesis. Certainly the evidence produced in 1918 dealt this hypothesis its coup de grace. It follows, therefore, that in the year 1918 there was only one credible hypothesis left-the Rittinger hypothesis. Gates' Opinion What information is available in Mr. Gates' paper?2 His conclusions are not consecutively summarized, none the less they are perfectly clear. On page 876, Gates says, and it is a very significant utterance: But my results show, among other things, that many more of Stadler's energy units are obtained per foot-pound-applied in coarse than in fine crushing. This suggests a doubt as to the correctness of his unit, since one would expect a foot-pound-applied to produce the same number of "energy units," whether the feed and resulting product were coarse or fine. When Rittinger's theory is applied, the number of mesh-tons (my unit of surface produced) is

Jan 1, 1942

By John W. Bell

In the introduction to an excellent pamphlet, John Gross' makes the following statements: Although marked progress has been made along mechanical lines, the theory and conception of underlying principles have not advanced so rapidly. This lack of advance in theory may be attributed to the unfortunate situation resulting from the controversy as to whether the Rittinger or Kick law is applicable to crushing. Many pages of the technical literature are burdened with theoretical discussions in favor of one or the other of these laws, which have tended to cloud rather than to clear the atmosphere. Realizing the situation, the Milling Committee of the American Institute of Mining and Metallurgical Engineers, through its secretary, E. A. Hersam, studied the milling industry and, because of the apparently hopeless lack of agreement in the Kick versus Rittinger dispute (5, 13, 14, 16, 18. 19. 21, 22, 23, 24, 30, 34). concluded that a foundation lor the theory of crushing was of primary importance. The numbers in the paragraph quoted refer to papers listed by Mr. Gross in his Bibliography on Crushing and Grinding.I One is obliged to infer that these papers show "hopeless lack of agreement in the Kick versus Rittinger dispute." No. 22 is a paper by Arthur 0. Gates2 and No. 23 is one by the writer.3 Employing the subject matter contained in papers Nos. 22 and 232,3 the writer will show that their authors formulated identical conclusions, based solely on experimental evidence. Exactly the same defect in the Stadler hypothesis was described in each of the two papers, although entirely different experimental methods were employed in uncovering it. Both of the authors, independently, formulated the conclusion that Rittinger's was a true hypothesis and Stadler's false. The evidence in a third paper4 will be employed to prove that Stadler's hypothesis, when examined experimentally, is worthless. Stadler's Hypothesis Worthless It is the writer's opinion that the evidence available in 1915 and the corroborating evidence in 1916 was amply sufficient to eliminate the need for any further consideration of Stadler's hypothesis. Certainly the evidence produced in 1918 dealt this hypothesis its coup de grace. It follows, therefore, that in the year 1918 there was only one credible hypothesis left—the Rittinger hypothesis. Gates' Opinion What information is available in Mr. Gates' paper?2 His conclusions are not consecutively summarized, none the less they are perfectly clear. On page 876, Gates says, and it is a very significant utterance: But my results show, among other things. that many more of Stadler's energy units are obtained per foot-pound-applied in coarse than in finc crushing. This suggests a doubt as to the correctness of his unit, since one would expect a foot-pound-applied to produce the same number of "energy units," whether the feed and resulting product were coarse or fine. When Rittinger's theory is applied, the number of mesh-tons (my unit of surface produced) is

Jan 1, 1943

By John W. Bell

In the introduction to an excellent pamphlet, John Gross' makes the following statements: Although marked progress has been made along mechanical lines, the theory and conception of underlying principles have not advanced so rapidly. This lack of advance in theory may be attributed to the unfortunate situation resulting from the controversy as to whether the Rittinger or Kick law is applicable to crushing. Many pages of the technical literature are burdened with theoretical discussions in favor of one or the other of these laws, which have tended to cloud rather than to clear the atmosphere. Realizing the situation, the Milling Committee of the American Institute of Mining and Metallurgical Engineers, through its secretary, E. A. Hersam, studied the milling industry and, because of the apparently hopeless lack of agreement in the Kick versus Rittinger dispute (5, 13, 14, 16, 18. 19. 21, 22, 23, 24, 30, 34). concluded that a foundation lor the theory of crushing was of primary importance. The numbers in the paragraph quoted refer to papers listed by Mr. Gross in his Bibliography on Crushing and Grinding.I One is obliged to infer that these papers show "hopeless lack of agreement in the Kick versus Rittinger dispute." No. 22 is a paper by Arthur 0. Gates2 and No. 23 is one by the writer.3 Employing the subject matter contained in papers Nos. 22 and 232,3 the writer will show that their authors formulated identical conclusions, based solely on experimental evidence. Exactly the same defect in the Stadler hypothesis was described in each of the two papers, although entirely different experimental methods were employed in uncovering it. Both of the authors, independently, formulated the conclusion that Rittinger's was a true hypothesis and Stadler's false. The evidence in a third paper4 will be employed to prove that Stadler's hypothesis, when examined experimentally, is worthless. Stadler's Hypothesis Worthless It is the writer's opinion that the evidence available in 1915 and the corroborating evidence in 1916 was amply sufficient to eliminate the need for any further consideration of Stadler's hypothesis. Certainly the evidence produced in 1918 dealt this hypothesis its coup de grace. It follows, therefore, that in the year 1918 there was only one credible hypothesis left—the Rittinger hypothesis. Gates' Opinion What information is available in Mr. Gates' paper?2 His conclusions are not consecutively summarized, none the less they are perfectly clear. On page 876, Gates says, and it is a very significant utterance: But my results show, among other things. that many more of Stadler's energy units are obtained per foot-pound-applied in coarse than in finc crushing. This suggests a doubt as to the correctness of his unit, since one would expect a foot-pound-applied to produce the same number of "energy units," whether the feed and resulting product were coarse or fine. When Rittinger's theory is applied, the number of mesh-tons (my unit of surface produced) is

Jan 1, 1943

By Cyril Stanley Smith

ON the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1958, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Cavallo3,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold-working restored it. He encountered some samples of brass that could not be rendered magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condition, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitters in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant,9 Honda and Shimizu, 10,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1941

By John L. Lamont, Walter Crafts

SECONDARY hardening in tempering has long been recognized as a typical characteristic of steels containing large amounts of carbide-forming alloys. These steels, when quenched and tempered, tend to soften somewhat after tempering at low temperatures, and to reharden at intermediate tempering temperatures before finally softening to low hardness. This behavior in tempering has been studied by many investigators, chiefly with respect to the secondary hardening of high-speed steels. The initial softening has usually been ascribed to decomposition of martensite and growth of iron carbide particles. The secondary hardening has been explained by formation of fresh martensite from residual austenite, formation of very fine alloy carbide particles and by precipitation hardening of metallic compounds in the ferritic matrix. However, factors derived for the calculation of tempered hardness in low-alloy steels1 indicated only a tendency toward retarded softening rather than a discontinuous rehardening. A study was, therefore, made to determine whether fresh martensite from residual austenite and precipitation hardening are essential to rehardening and the degree to which tempered martensite could be rehardened by precipitation of alloy carbides. The mechanism of carbide rehardening was also investigated to determine the nature of the process. The causes of secondary hardening in high-speed steel have received serious consideration for about thirty years. Among the earlier workers Bain and Jeffries2 in 1923 recognized residual austenite as a significant factor, but in addition, emphasized the effect of the formation of alloy carbide particles of "critical" size. They conceived that freshly quenched martensite forms low-alloy iron carbide at low tempering temperatures; with further tempering the iron carbide is then modified by alloying elements that can diffuse most readily at intermediate temperatures (850°F); and that the iron carbides grow in size by coalescence so that the steel tends to lose hardness. At higher tempering temperatures carbide stability rather than alloy availability becomes the controlling influence and in high-speed steel "iron-tungsten carbide is the most stable one and forms to the elimination of the earlier formed carbides. . . . The iron-tungsten carbide particles reach approximately the size for critical dispersion after a short reheat at 1100°F." This concept, the formation of alloy carbide nuclei, redissolving of the iron carbide, and diffusion of carbon to the alloy carbide, was restated for vanadium steel in 1932 by Houdremont, Bennek, and Schrader.3 Subsequent studies have confirmed that iron carbide changes to alloy carbide at 1000 to 1100°F, but the mechanism of the process has received little consideration .

Jan 1, 1948

By Ivor Jenkins

PROCESSES employing controlled atmospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been associated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and difficult problems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases Controlled atmospheres such as dissociated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties: especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,1 but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1947

[¦Abad, Leopoldo F., College of Min., Univ. of California Berkeley, Cal. '23 ¦Abarquez, Ramon F., Met., Bureau of Science Manila, P. 1. '24 ¦Abbey, Robert Graham, Student, Case School of Applied Science Cleveland, Ohio. '21 Abbott, A. N., Mines Supt., Mazapil Copper Co., Ltd ...Concepcion del Oro, Zacatecas, Mexico. '23 Abbott, Clarence B., Gen'l Supt., Iron Mines Div., Tenn. Coal, Iron & R. R. Co., 1405 Minnesota Ave., Bessemer, Ala.' '04] [ ]

Jan 1, 1925

By B. S. Butler

The principal ore deposits of Arizona are in the southern, cen-tral, and western portions of the state, which physiographically are part of the Basin and Range province, southwest of the Colo-rado Plateau (Pl. I). The Basin and Range province is characterized by numerous subparallel mountain ranges separated by plains or valleys. Most of these ranges trend northwest to north, parallel to the margin of the Colorado Plateau; but in southeastern Arizona, southern New Mexico, and northeastern Sonora, they trend northward, transverse too the edge of the Plateau. The mountains rise abruptly from plains or valleys, the margins of which in many places are pediments cut on hard rock. Some of the plains form closed basins (bolsons, playas), but most of them are drained. The Basin and Range province in Arizona is divisible into the Mountain Region and the Desert Region4 (Pls. I and II). The Mountain Region forms a belt 60 to 100 miles wide that contains most of the large ore deposits. Its longest range measures about 55 miles, the widest 20 miles, and the highest peak more than 10,000 feet above sea level or 7,000 feet above adjacent valleys or plains. Broad plain-forming valleys are exceptional, but several with maximum widths of 20 to more than 30 miles appear in the southeastern portion. In the Desert Region the mountains are relatively low, narrow, serrated, and steep, with sharply angular profiles. There are a few exceptionally large ranges of which the longest measures nearly 100 miles and the widest 18 miles. The highest peak is some 7,000 feet above sea level, and the maximum local relief amounts to about 5,400 feet. Broad and comparatively low desert plains form 50 to 75 per cent of the area.

Jan 1, 1939

By Howard N. Eavenson

FROM the Pittsburgh coal bed in the four states of Pennsylvania, Ohio, Maryland and West Virginia has been produced an output that, at mine prices, represents a greater value than any other single mineral deposit in the world has yielded.12 While this distinction may in a few years pass to the gold reef of the Witwatersrand, it is possible that eventually, owing to the tremendous reserves still remaining, the ultimate yield of the Pittsburgh bed will be greater than that of any other known single deposit. Considering its importance, not a great deal has been written of its early history and development as a whole; most of the accounts have been of limited localities, or, at the most, of the area within a single state. In "Coal through the Ages" the writer mentioned some references to its early history, but this study will deal not only with its history but with the character of the bed, where and why it was first developed, and its effect upon the states in which it is found. It has not been the intention to write a detailed history of the development of the seam in each locality, as neither time nor inclination were available for doing such work, but only to show the influences that tended to hasten or retard such development. In general the historical matter ends about 1830, when geological surveys began to be made. Some of the maps show data available only since that time, and the sections about coal preparation and coking have been extended to the present time to show the changing conditions. It is believed that the early history includes all published records, and many more sources than those shown in the bibliography were consulted. It is quite likely that some references to coal in this area may be found in the unpublished papers of some of our early soldiers and colonizers, which exist in several libraries, and it is hoped that some future

Jan 1, 1938

By Rollin E. Hook, Attwell M. Adair

The yield and fracture behavior of recrystallized chromiztm have been studied in order to gain an understanding of the recrystallization embrittlement-rheotropic recovery phenomenon. The duc tile-brittle tensile transition temperature of recrystallized chromium was found to vary from 225 ° to -80°C as the ratio of specimen diameter/mean planar grain size decreased. The applicability of this observation to other bcc metals is briefly discussed. Brittle fracture in recrystallized chromium was found to be initiated predominately from intercrystalline rupture nuclei. Single crystals exhibit a high degree of ductility at 23 "C. The experimental data indicate that grain boundaries play a significant part in the yield and fracture behavim. Pres training significantly reduces the transition temperature, and high temperature aging does not result in re-embrittle-ment until complete recovery or re crystallization occurs. SEVERAL theories have been used to explain the recrystallization embrittlement-rheotropic recovery phenomenon in chromium. Wain, Henderson, and ohnstone' propose a Cottrell dislocation locking mechanism due to nitrogen, and Weaver and Gross and weaver 3 propose a strain-induced precipitation mechanism involving a chromium nitride precipitate. The researches of many investigators seem to leave little doubt that brittleness in chromium is promoted by interstitial impurities. Smith and seybolt4 have shown that the ductile-brittle transition temperature is lowered as the interstitial content is reduced. weaver3 provides evidence for a 150°C reduction in the tensile transition temperature as the nitrogen content is reduced from 20 to 5 ppm. Maykuth and affee' have suggested that the amount and orientation of grain boundary impurities may be responsible for the brittle nature of recrystallized chromium. This suggestion was based on their findings that wrought iodide chromium possessing a fiberous grain structure is ductile in tension at room temperature while a recrystallized grain structure is completely brittle. Previous investigations have not studied this phenomenon sufficiently to determine its cause. Perhaps this has been largely due to previous experimental findings that brittle fracture observed in chromium has been almost entirely transgranular.' In addition McNeil and imb,' who investigated coarse-grained as-cast chromium, describe the point of initiation of fracture as cleavage, close to the (100) plane, near or at grain bound-daries, or at included particles or voids. However, Hook, Adair, and ipsitt found that fracture in coarse-grained recrystallized chromium is initiated by intergranular rupture and then propagates nearly entirely by cleavage. This result, together with their finding that room temperature ductility in bending is observed for single crystals and coarse-grained polycrystalline specimens for which the number of grains through the specimen diameter is small, suggests that grain boundaries may play an important role in the brittle behavior of chromium. The recrystallization embrittlement problem can be resolved into two questions. These are, whether the controlling mechanism is predominately one of crack initiation or crack propagation, and whether brittle fracture is initiated predominately by slip or twin induced intergranular rupture or by cleavage. The following research was designed to study the role of grain boundaries on the brittle fracture of chromium in an effort to resolve these questions. EXPERIMENTAL PROCEDURES, RESULTS, AND DISCUSSION General Procedure. All tensile specimens (except 0.04 in. diam wires) were prepared from 1/4 in. diam swaged rod fabricated from one ingot. Details of fabrication are given elewhere. The results of impurity analysis for the swaged rod and for the

Jan 1, 1963

By E. S. Machlin, Morris Cohen

GRENINGER and Troiano' were the first to establish the fact that the habit planes of mar-tensitic products are usually planes of high indices. In steels containing 0.55 to 1.4 pct C, the habit plane indices are {225}A.* In steels with more than 1.5 pct C and in Fe-Ni alloys, the indices are {259In. The presence of both habits in certain alloy steels has been reported recently." Several investigators"-" have subsequently attempted to provide an understanding of these complex habit relations. Bowles'6 work is the most recent and the most successful. Like Greninger and Troiano, Bowles concluded that the transformation occurs in two steps, the first, a strain (or displacement) that is homogeneous throughout the volume of the martensitic plate, while the second is a strain that is homogeneous only within relatively small portions of the martensitic plate. The first strain yields the measured tilt of the specimen surface, but does not produce the final martensitic structure. This and the correct lattice orientations are achieved by the second strain. Bowles also reasoned that each strain could be described by the motion of a plane of no rotation and no distortion (hereinafter called the invariant plane) in a direction not necessarily contained in the plane.** In applying these considerations to steels with {225}a habits, Bowles found that the habit plane coincided with the invariant plane of the first strain, a result which signified that the atoms move along certain paths during the transformation. Whether this correlation results from the existence of some sort of a plate nucleus6 lying along the invariant plane of the first strain, or whether the invariant plane primarily defines the preferred directions of propagation of the first strain, will be discussed in a later section. There are two obstacles to the general acceptance of Bowles' treatment: 1—it has not been shown that elements of his double-strain analysis are unique, and 2—it is not known whether his treatment applies to transformations yielding the {2591A habit. Unless these two questions are resolved, the correlation between the habit and invariant planes in the {225}A systems might be regarded as coincidental. Experimental Procedure Using a 70 pct Fe-30 pct Ni alloy as an example of a {2591A habit system, preliminary attempts were made to obtain a double-strain solution based on a Nishiyamax** set of orientation relations and on a Greninger-Troianot set, adopting the stereographic technique described by Bowles" who used the Kurd-jumow-Sachstt set in connection with the {225}A habit. These attempts were unsuccessful because the method is essentially one of trial and error and requires either exceedingly good luck or a prior knowledge of the results being sought. Consequently it was decided to measure independently the strain associated with the formation of a martensitic plate as well as the habit-plane indices of the particular plate. By means of matrix algebra, the measured strain was applied to the austenite lattice, whose orientation with respect to the strain was determined, in order to ascertain whether the resultant structure would have the lattice of martensite. This was not found to be the case, and hence it was assumed that the measured strain was the first of two Bowles-type strains, characterized by the motion of an invariant plane. A solution of this displacement was obtained in terms of the invariant-plane indices and the direction of motion of the atoms. Then the second strain

Jan 1, 1952

By B. K. Larkin, H. R. Bailey

One of the most complicated and potentially one of the most promising secondary recovery methods is that of underground combustion. A number of field tests1,2,3 have been performed recently, apparently indicating that the underground combustion process is technically feasible. Relatively little has been published concerning laboratory or theoretical investigations of the underground combustion process. A few results of laboratory tube runs have been published4,5 and these data are valuable in understanding the process. The tube run data also emphasize the complexity of the thermal recovery process. Under various conditions, problems in heat transfer, multiphase fluid flow and combustion rates arise. For example, at low temperatures the combustion process proceeds so slowly that the front cannot be propagated. It is a problem in heat transfer to predict what injection rate of air is necessary to sustain combustion in a particular reservoir. Certain fluid flow aspects of underground combustion have been studied by Wilson, et a13. In the development of some of the flow equations, assumptions of adiabatic combustion were made. Vogel and Krueger1 have devised an analog model of the heat conduction process for a constant temperature cylindrical source moving radially outward in a homogeneous conducting medium. Jenkins and Ramey7, in a discussion of the Vogel and Krueger paper, present an analytical solution of a heat conduction problem related to problems considered by Vogel and Krueger. In the present paper an idealized model of the heat conduction problem is considered, which is more general than the model of Vogel and Krueger or Jenkins and Ramey. In particular, initial well heating, vertical heat losses and arbitrary frontal velocities are included. Equations for the temperature are obtained in terms of integrals. These integrals have been evaluated numerically for the case of frontal movement corresponding to a constant air injection rate and the case of constant frontal velocity. These results are presented graphically. From these graphs one may estimate conditions under which nearly adiabatic temperatures are obtained. The application of these results requires some knowledge of reservoir thermal properties, combustion rates and residual fuel content. Assuming no vertical losses it is possible to obtain explicit evaluations of these integrals in the linear con- stant velocity case and in the radial case corresponding to a constant air injection rate. PRESENTATION OF RESULTS The geometry of the radial system is illustrated in Fig. 1 where the reservoir is represented as a slab of thickness h. By making an energy balance for an infinitesimal volume, one obtains the following equation. T= x T+F(z.r).........(1) where F (z,r) =HWv1/pc (r-r1), if z h/2 = 0, if z >h/2 . In Eq. 1, V- represents the Laplacian operator and 8 is the Dirac delta function. Eq. 1 is the well-known diff-sion equation with a source term and may be applied to a linear system. For example, if the source is moving in the direction of the x axis, then the argument of the delta function is x - 1,. In deriving Eq. 1 the following approximations were made concerning the actual combustion process: (1) all heat transfer is by conduction in a homogeneous medium, (2) the formations bounding the reservoir have the same thermal properties as the reservoir, (3) the combustion fuel is consumed instantaneously as the front arrives, (4) there is a constant fuel concentration

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and "{2,3,10)" or "(127)". (It is now thought1' that the "{0,1,13)" habit reported for the Fe-Ni-C alloys'' is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove.' The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and tj2 = vi (i = 1, 2, 3), the Kz qd 771 elements are given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics cij Iand cij reduce to the unit tensors 6ij and 6ij so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and 77~ are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By M. Bevis, A. G. Crocker

A. G. Crocker and M. Bevis (Battersea College of Technology)— Richman and Richman and conard17 have recently published the very interesting results of their studies on the plastic deformation of Fe-Ni-C martensites and of an Fe-5 wt pct Be alloy. Other work on the range of Fe-Be alloys containing between 16 and 27 at. pct Be has also been reported by Richman." One of the fascinating features of this work is that the materials investigated deform primarily by means of twinning and that several twinning modes are operative in addition to the well-established (112 ) mode of bcc materials The composition planes of these unusual twins were determined using a single-surface analysis and reported as (0131, "{045)" or "{089)", and It is now thought1' that the "{0,1,13)" habit reported for the Fe-Ni-C alloys'' is more likely to be near "{127)". Although the full twinning elements of these unusual twinning modes could not be determined directly from the experimental results, the authors attempt to deduce the elements by considering twin intersectionslQ and by using the projection technique of Jaswon and Dove. The basic assumption of their approach is that the (013) habits are truly rational planes but that the other habits are irrational and merely approximated to by the indices quoted above. They thus deduce that the twinning mode describing the (013) habit is either Type I or compound and that the modes describing the other habits are Type 11. This deduction must however be false as all twinning modes in cubic structures obeying the classical orientation relationships of deformation twinning must be compound. Type-I and Type-I1 modes can occur in all of the other crystal systems (indeed in the triclinic system compound modes are not allowed), but in the cubic system only compound modes can arise. This fact, which does not appear to be well-known, fol- lows immediately from the relations between the four twinning elements defining a twinning mode. Thus for a Type-I mode which is uniquely defined by the rational twinning elements K1 = hi and given by: where the summation convention of the tensor calculus has been adopted. For cubic materials the metrics and reduce to the unit tensors and j so that we have It is clear from these equations that both ki and ui must take on integral values; i.e., Kz, and ql must be rational, if hi and vi are integers, i.e., if K1 and are rational. Thus for cubic materials a Type-I mode must degenerate into a compound mode and the same result also arises for Type-II modes. The apparently irrational habits observed by the authors can thus not be explained in terms of Type-I1 twinning if the classical laws of deformation twinning are to be obeyed. An alternative explanation of the irrational habits is that they may arise from twinning modes with four irrational twinning elements. These modes, which do not obey the classical orientation relationships associated with deformation twinning, have been shown to arise as the result of double twinning processes in magnesium,22 but may also describe a simple shear on an irrational plane in an irrational direction. Indeed double twinning processes in bcc

Jan 1, 1963

By M. F. Goudge, R. V. Tomkins

Sodium sulfate is an important chemical raw material that is being used in ever increasing quantities in modem industry. It comes on the market mainly in three forms: (1) Salt cake (Na2SO4), a relatively crude form of the anhydrous salt containing up to 3 pct impurities, and comprising about three-quarters of the North American production; (2) anhydrous sodium sulfate (Na2SO4), a refined form containing less than 0.3 pct impurities; (3) Glauber's salt, the decahydrate (Na2SO4.10H2O) containing 55.9 pct water of crystallization. Competing with salt cake from natural sources is byproduct salt cake from a number of industrial operations. For instance there is Mannheim cake resulting from the manufacture of hydrochloric acid by the reaction of salt (NaCl) and sulfuric acid in Mannheim furnaces; rayon cake, a high-quality product, resulting from the process of making rayon by the viscose process; chrome cake from the processing of sodium chromate to dichromate; phenol cake from the manufacture of phenol; also byproduct sodium sulfate resulting from the conversion of lithium sulfate to lithium carbonate; from the processing of sodium tetraborate to boric acid; from converting sodium formate to formic acid; and in the manufacture of cellophane. Sodium sulfate is also obtained as a byproduct in the manufacture of isosebasic acid. In addition strong competition has resulted from imports of byproduct salt cake from the chemical industries of a number of highly industrialized European countries. However in recent years due to technological changes the output of byproduct salt cake is rapidly diminishing and the natural deposits are becoming the most important source of sodium sulfate used in North America. For instance, the production of hydrochloric acid in Mannheim plants has become obsolete and thus the greatest single source of byproduct salt cake will disappear. Also viscose rayon is meeting strong competition from nylon and other synthetic fibers and production of byproduct salt cake from this source may do little more than remain at the present level. These factors together with increasing demand for sodium sulfate point to increased production from natural sources. In 1958, 36 pct of the total United States production was derived from natural sources and in addition 97,000 short tons was imported so that over 40 pct of the total consumption was supplied by natural sources whereas in 1953 the proportion was only 24 pct. The rapid growth in production is shown in Table 1. Principal Sodium Sulfate Minerals There are many minerals in which sodium sulfate is a constituent but those of commercial importance at the present time, and consisting wholly of sodium sulfate in either the hydrous or anhydrous states, are mirabilite and thenardite. Minerals of potential importance but consisting in part of compounds other than sodium sulfate are glauberite in which sodium sulfate is combined with calcium sulfate, and blödite in which sodium sulfate is combined with magnesium sulfate. Mirabilite (Na2SO4.10H2O) the decahydrate, consists of 24.8 pct SO3, 19.3 pct Na2O, and 55.9 pct H20. It is a colorless to opaque, soft, water-soluble mineral with a slightly bitter taste. It has a hardness of less than 2 and a specific gravity of 1.48. It forms long needle-

Jan 1, 1960

?AARONSON, ALFRED E , Vice-Pres , Mid-Co Petroleum Co, Mid-Co Bldg, Tulsa, Okla '18 ABADIE, EMILE R, Min Engr Address wanted '76 || ABADILLA, QUIRICO A, Geol Dept, Cia Mexicana de Petroleo "El Aguila," S A, Edifico "El Aguila," Esq, Calles Aurora y Comercio, Tampico, Tamaulipas, Mexico '20 ABBOTT, CLARENCE E, Gen'l Supt, Iron Mines Div, Tenn Coal, Iron & R R Co, 1405 Minnesota Ave, Bessemer, Ala '04 ABBOTT, LOUIS BENJAMIN, Chief Engr, Consolidation Coal Co, Elkhorn Div, Jenkins, Ky '15 ABBOTT, ROBERT R Met Engr, Peerless Motor Car Co, Cleveland, Ohio '12 ABE, ASAKA Fujita Min Co, Dojima, Osaka, Japan '14 ABEEL, GEORGE H, JR, Cons Min Engr, 635 St Paul Ave, Los Angeles, Cal '18 ABEL, ALBERT E, Asst to Pres, Valley Mould & Iron Corpn, Sharpsville, Pea '19 ABEL, W D, Min Engr Forum Bldg, Sacramento, Cal '19 ABELL, O J, Pres & Treas, Abell-Howe Co, 332 South Michigan Ave, Chicago, Ill '19 ABERNATHY G E Willow Springs, Mo '20

Jan 1, 1923

By L. W. Blau

THE entrance of geophysics and geochemistry into petroleum engineering may be viewed with apprehension by some engineers. They may not remember the time when "practical oil men" opposed the invasion of engineers into the field of petroleum production. By their excellent contributions they established themselves. In the popular mind, engis veers are practical men whereas physicists and chemists are suspected of being theoretical. It will be best to annihilate this misconception right now at the beginning of a closer relationship between petroleum engineers. geophysicists, and geochemists.

Jan 1, 1943