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By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale forma¬tion) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. EXPERIMENTAL PROCEDURE Silver.-The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By W. R. Phibbs

THE blast furnace of the Columbia Steel Corpn., at Ironton; Utah, was put in blast April 30, 1924, and its operation has presented some interesting problems. The coke for the furnace is furnished by 33 Koppers Becker type ovens of 15 tons capacity each. The coal is shipped from the company's mine at Columbia, Utah, which is approximately 123 miles from Ironton, and is probably the highest volatile coal that is being coked for blast furnace use in this country. The analysis of the coal is: PER CENT. Moisture 3.90 Volatile 39.00 Fixed carbon 51.10 Ash.... 6.00 Sulfur : 1.07 The analysis of the coke is: PER CENT. Volatile 0.55 Fixed carbon :...:.::: :..:.:: 89.70 Ash 9.75 Sulfur 1.05

Jan 1, 1928

By M. E. Lombardi

ThE Coalinga oil field is located on the west side of the San Joaquin Valley, California. The structure is in general a monocline, the edges of the oil horizon resting on the foot hills and dipping gently toward the east. One prominent anticline occurs plunging southeast. The earlier drilling was done in the foot hills comparatively near the outcrop and the wells were shallow. The sands were followed eastward and, in the case of the anticline, along the plunge, the wells becoming deeper and deeper until the depth of 4,000 ft. was reached and passed. There is nothing to show that the oil will not be found in quantity at still greater depth. In fact, some of the best producers have tapped the sand at close to 4,000 ft. The recovery of oil still farther to the east, and therefore at greater depth, seems to be mainly a question of drilling. In this territory the formations drilled through are chiefly sands and shales; they will not "stand up" in an open drilling hole; the casing has to be carried close to the bit, and it is always difficult to keep the casing free for any considerable distance. Ability to carry casing of comparatively large diameter without conductor pipes for distances of 2,000 or 3,000 ft. or over is desirable in such territory chiefly for two reasons. It makes it possible to enter the oil sand with a pipe of ample diameter; it eliminates one or more expensive strings of casing which act only as conductors for the water string, and furthermore, in territory where waters are encountered which corrode steel rapidly, it makes possible the construction of a rust- and alkali-resisting water string. It is always desirable to shut off top waters, which may lie within 100 ft. or less of the oil sand, with 10-in. pipe. Where the depth is so great that a practical weight of 10-in. pipe will not withstand the probable collapsing pressures, 81/4 in. at least is desirable. About the limit of rotary drilling to date in California seems to be the setting of the 10-in. string at 3,200 ft., although the rapid advance in rotary work during the past year seems to indicate that this depth may soon be increased. It is my purpose now, however, to treat only of cable-tool drilling. The problem is to reach a depth of 4,000 ft. or more with a string of

Jan 1, 1915

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during the period July 10 to Aug. 10, 1915: William H. Rettie, Yonkers, N. Y. Paul S. King, Wilmington, Del. A. J. Eveland, Pachuca, Mexico. E. E. R. Tratman, Chicago, 111. Chang Fu Wang, Shanghai, China. Courtenay Dekalb, Tucson, Ariz. F. H. Fovargue, Terlingua, Tex. Emil Gathmann, Baltimore, Md. W. W. Elmer, Tuttletown, Cal. Henry S. Drinker, E. M., LL. D., has just completed 10 years' service as President of Lehigh University. A notable gathering of alumni, with their wives and daughters, numbering more than 1,000 persons, met in South Bethlehem on June 5. In accordance with the request of Dr. Drinker, no formal celebration was held, but, nevertheless, a spontaneous and enthusiastic expression- of appreciation and affection was voiced by alumni, students and faculty, testifying to the regard felt for Dr. Drinker and extolling the progress made by the University under his guidance.

Jan 9, 1915

By H. A. Bright, H. C. Vacher, J. G. Thompson

The methods employed for the determination of oxides and oxygen in ferrous materials may be roughly classed in two groups, "wet" methods and "hot" methods, the first group including the iodine, electrolytic, mercuric chloride, hydrochloric acid, nitric acid, and chlorine methods; the second group including the vacuum-fusion and hydrogen-reduction methods. The wet methods depend upon preferential solubility in a selected medium to separate the metallic portion of the sample from the oxygen-containing constituents. Subsequent analysis of the insoluble residue permits the isolation and separate determination of individual oxides and compounds. The hot methods depend upon the reduction of the oxide constituents of the sample by means of carbon or hydrogen at elevated temperatures. With the exception of the recently developed fractional vacuum-fusion method, the hot methods do not identify individual oxides and compounds but yield only a single value representing the sum of the oxygen contents of several or all of the oxide constituents present. With such diversity in the principles and aims of the different groups, it is not surprising that concordance of results by different methods has usually been difficult to obtain. The present cooperative attempt to define more rigorously than has been possible heretofore the accuracy and limits of usefulness of the various methods, originated in correspondence between Dr. John Johnston, Director of Research of the United States Steel Corporation, and other interested metallurgists. The plan was, briefly, to submit identical samples to a number of laboratories for analysis by different methods and to collate the results of these analyses. The project was endorsed by the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers at the annual meeting in February, 1933, and has been conducted under the joint sponsorship of the Iron and Steel Division and the National Bureau of Standards. The latter organization undertook

Jan 1, 1937

By G. F. Comstock

A serious disagreement as to the effect of titanium on the hardenability of steel exists in published references to this subject. Kramer, Hafner and Toleman reported1 that acid-soluble titanium decreased the hardenability, with multiplying factors less than unity according to Grossmann's system for calculating hardenability from the composition. Crafts and Lamont, on the other hand, showed2 how titanium increased the hardenability, with multiplying fdctors up to nearly I.; for about 0.1 per cent titanium, though reducing the hardenability with higher titanium. Their data, however, were obtained almost exclusively from steels containing more than 1.4 per cent manganese, and thus should be considered as applying mainly to manganese steels. Likewise, the results of Kramer, Hafner and Toleman regarding titanium are subject to the limitation that although they eliminated the effect of the insoluble titanium compounds from their calculations, they did not make a similar correc- tion for the carbon that was combined with titanium and therefore occurred in a similarly ineffective form. It is suggested by the literature referred to that titanium may have different effects on hardenability, depending on the mode of its occurrence in the steel. The different effects on strength, ductility, etc., have already been discussed by the author.3 In the present discussion some comparisons, on the basis of hardenability as revealed by the Jominy end-quench test, are given between three titanium and two non-titanium steels heat-treated in the same ways, and between other titanium steels heat-treated in several different ways. Comparison of Plain-carbon, Vanadium and Titanium Steels The five steels used for these experiments were cominercially melted and rolled products received in the form of 1.5-in. rounds from three different mills. Their analyses are given in Table I. Steels 2, 3, and 4 are from the same basic electric heat1 containing 0.009 per cent of phosphorus and the same amount of sulphur. They were made by adding aluminum and low-carbon ferrotitanium to different ingots. No. I is a plain carbon

Jan 1, 1947

By G. F. Comstock

A serious disagreement as to the effect of titanium on the hardenability of steel exists in published references to this subject. Kramer, Hafner and Toleman reported1 that acid-soluble titanium decreased the hardenability, with multiplying factors less than unity according to Grossmann's system for calculating hardenability from the composition. Crafts and Lamont, on the other hand, showed2 how titanium increased the hardenability, with multiplying fdctors up to nearly I.; for about 0.1 per cent titanium, though reducing the hardenability with higher titanium. Their data, however, were obtained almost exclusively from steels containing more than 1.4 per cent manganese, and thus should be considered as applying mainly to manganese steels. Likewise, the results of Kramer, Hafner and Toleman regarding titanium are subject to the limitation that although they eliminated the effect of the insoluble titanium compounds from their calculations, they did not make a similar correc- tion for the carbon that was combined with titanium and therefore occurred in a similarly ineffective form. It is suggested by the literature referred to that titanium may have different effects on hardenability, depending on the mode of its occurrence in the steel. The different effects on strength, ductility, etc., have already been discussed by the author.3 In the present discussion some comparisons, on the basis of hardenability as revealed by the Jominy end-quench test, are given between three titanium and two non-titanium steels heat-treated in the same ways, and between other titanium steels heat-treated in several different ways. Comparison of Plain-carbon, Vanadium and Titanium Steels The five steels used for these experiments were cominercially melted and rolled products received in the form of 1.5-in. rounds from three different mills. Their analyses are given in Table I. Steels 2, 3, and 4 are from the same basic electric heat1 containing 0.009 per cent of phosphorus and the same amount of sulphur. They were made by adding aluminum and low-carbon ferrotitanium to different ingots. No. I is a plain carbon

Jan 1, 1947

By Eugene McAuliffe

AS this is written, the probability A is that the bituminous coal out- put for 1936 will approximate 420,000,000 tons (of 2000 lb.) with an average working time for all mines of 205 days. The results for 1935 approximated 369,224,000 tons, with the mines working about 185 days. The increase in production of 14 per cent is heartening. In anthracite, it is probable that the preliminary figures covering output for 1935, 51,- 003,000 tons, will be exceeded this year although the percentage of in- crease will almost certainly be small. The substantial tonnage of anthracite illegally mined, estimated to be 3,600,- 000 tons in 1935, with a similar large Lonnage in 1936, is in addition to the figure given above; it represents an open and flagrant disregard of law and property rights. It is hard to understand why the officials of the State of Pennsylvania do not enforce the laws against theft and brigandage, more so when the legitimate employees of the established producing proper-

Jan 1, 1937

By Ulick R. Evans, Maurice Cook

The structural changes in metals brought about by annealing follow-ing a deformation at a low temperature has been the subject of many investigations. No less than eleven metals and alloys have been studied in some detail; namely, aluminum, tungsten,2 iron,3 copperI4 gold, zinc,6 cadmium, tin: lead: brass,1° and cupronickel. As a result, it is possible to frame a qualitative statement of the effect of the degree of deformation and the temperature of annealing on the structure finally attained.

Jan 1, 1925

By Charles T. Malcomson

In the United States, improvements in methods of combustion have made possible the use of the smaller sizes of anthracite. This coal is now being reclaimed from the culm banks accumulated by the miners in the more prodigal years. To-day the freshly mined "slush" is segrega,ted and stored against the time when, through briquetting or some other means, it may be utilized as a commercial fuel. For many years Europe has achieved enviable results in the conservation of her small coal by briquetting. This profitable industry, first placed on a commercial basis in France in 1842, has grown to such magnitude that the production during 1913 exceeded 36,000,000 short tons. Briquets produced in Great Britain are used principally for steam purposes and the greater part of the output is either exported or taken by the Admiralty. On the Continent the briquets are sold in all branches of the coal trade. The French railways consume from 16 to 40 per cent. of their fuel in briquet form, and in Germany the lignite briquets (of which 20,000,000 tons were produced in 1913) are as familiar and interesting to the American traveler as the huge porcelain stoves in which they are burned. It is not strange, therefore, that aggressive and far-sighted promoters heralded this means of converting our ubiquitous coal waste into revenue. To the superficial student the briquetting process seemed so simple as to make success easy. It is for this reason principally that the path of the industry in America has been strewn with failures. The rash enthusiast had either not worked out the mechanical problems involved or had failed to grasp the local conditions under which the briquets must be made and sold. It may be confidently stated, however, that in spite of the many vicissitudes through which it has passed, coal briquetting is now an accomplished economic success in this country, and as a profitable adjunct to the coal industry it has come to stay. Several valuable contributions relating to coal briquetting are found in the Transactions. Charles Dorrance, Jr., has sketched briefly the history of the anthracite briquetting plants from the time of Loiseau's pioneer plant down to that of the Lehigh Coal & Navigation Co. at Lans-ford. Since then this phase of the industry has remained practically at

Jan 1, 1915

By John D. Ridge

For mining geologists, the most important trends during 1962 have been the increased concentration of the exploratory activities of American mining companies in the United States and Canada and the greater use of the combined techniques of geology, geophysics and geochemistry in searches over larger areas for wider varieties of metals and minerals. The principal reasons for these changes in approach have been the deterioration of the political-economic climate in many areas of the globe of equal or greater geologic promise and the realization that modern exploration is most efficiently and economically conducted through the use of all available means of detecting ores in areas sufficiently large to raise to a maximum the chances of success. The attitude of certain major U.S. metal-producing companies can be shown by the officially ex- pressed positions of their principal officers. Early in 1962, Clyde E. Weed, Chairman of the Board of Anaconda, remarked that "because of unsettled conditions and disruptive influences in many of the copper-producing areas of the world, it is imperative that domestic copper-producing capacity be improved and made as efficient as possible in order to meet consumer demands at reasonably stable prices." In November, Robert G. Page, President of Phelps Dodge, pointed out that his company is not only concentrating most of its exploratory effort on this continent but is also increasing the number of metals for which it is searching. Frank R. Milliken, President of Kennecott, recently said that "most of our exploration money is going into the northern part of the Western Hemisphere."

Jan 2, 1963

By John B. Hastings

THE occurrence of such a large amount of gold in the Hartsel granite, even though the surmised existence of similar areas is not new, brings freshly to mind the pegmatite type of magmatic differentiation lately brought again to attention by occurrences at Silver Peak, Nev., described by Spurr; and in Alaska, described by both Spurr and Brooks. In both localities graunitic rocks or dikes are thought to pass into metalliferous quartz-veins. An interesting association in this connection is the occurrence of diamonds in residual pegmatitic clay of San Juao de Chapado, Brazil, described by Derby :1 (P. 142) "Bodies of pegmatite are quite common in the older rocks of Brazil, both in the. diamond regions and elsewhere, occurring not only in the gneiss and granite, but in the schistose series as well. Those that have been examined are dike-like in their mode of occurrence and granitic in composition." (P. 143) "The question of the eruptive or secretionary origin of pegmatites has long been a subject of discussion among geologists. . . . The recent studies . . . seem to have clearly established that most if not all of them are essentially eruptive masses, though possibly modified in some way by aqueous agencies. Even before becoming acquainted with the literature of the subject this view had seemed to me to be the only acceptable one as regards the typical pegmatites of Brazil." What is pegmatite ? J. F. Kemp says ". . . veins or dikes-it is an open question which is the more correct term-are met formed of very coarsely crystalline aggregates of the same minerals that constitute granite. These are called pegmatite and in them is the home of graphic granite, the curious intergrowth of quartz and feldspar, such that a cross fracture of the blades of quartz suggests cuneiform characters. . . . In regard to the larger veins or dikes it seems improbable that true igneous fusion could have afforded such coarsely crystalline aggregates, and so we are forced to assume such abundance of steam and other vapors, i.e, mineralizers, as to almost, if not quite, imply solution."

Jan 5, 1908

By Geoffrey Gilbert

The material that forms the basis of this paper was collected in the spring of 1922, during a ten-day visit to Ducktown by the writer in the company of Prof. L. C. Graton. The time available for the work was far too short to allow anything like a thorough study of the deposits, and structural and stratigraphic questions, though they have an important bearing on the origin of the primary ores, were necessarily left untouched. Attention was focussed on the zone of oxidation and enrichment; and by devoting most of our time to the upper levels, open pits, and old workings, and examining the deeper levels only thoroughly enough to obtain a fair idea of the nature of the primary sulfide ore, we were able to make a reasonably complete survey of the various orebodies. With this field work for a background, the writer later made a study, in the Harvard laboratories, of the specimens obtained during the visit. As some of the facts brought to light by this study appear to be new, it seems worth while to set forth the outstanding features and a proposed explanation of them. Much of the Ducktown material that is obviously of greatest significance, as regards oxidation and enrichment, is soft and crumbly. Notwithstanding the desirability of gaining from such material all possible information as to its mineral composition and textural relationships, but little has heretofore been learned regarding it; but, by suitable preparation of this material in connection with the present study, it has been possible to examine it under the microscope without any disturbance of its texture and about as satisfactorily as if it were hard, fresh ore. The information thus gained has contributed measurably to the results set forth in this paper.

Jan 1, 1924

By Frank Woolley, John F. Elliott

The high-temperatzrre solulion calorimeter has been modified and an extension dynamic analysis of i/s transient behavior has provided an improved basis for interpretation of the experimental data. The partial molar heats of mixing, Him, of aluminum, copper, and silicon in the corresponding binary liquid-iron alloys haz,e been measured directly at 1600°C. The resulls in kcal per g-alom are: THE high-temperature1,2 solution calorimeter was planned and designed to obtain directly the partial molar heat of solution of solute elements in a variety of liquid metals that might serve as solvents. Results obtained in the temperature range of 1000° to 1200°C were described in the two earlier publications. However, a long-term goal in the program has been to obtain measurements at 1600°C of the heats of solution of elements in liquid iron. Hence, subsequent to the work last reported,2 and based on the experience of the first two studies, the calorimeter system has been modified and operated at 1600°C to obtain measurements on the Fe-Si, Fe-A1, and Fe-Cu systems. This paper reports the results of the work. THE MODIFIED SYSTEM It was clear from the earlier results that the most precise measurements can be obtained with the high-temperature solution calorimeter when the solution time is less than approximately 30 sec. This can be achieved only when the bath temperature, Tb, is above the melting (liquidus) temperature of the solute material being dropped. A second point of importance is that the refractories used earlier liberated considerable water so that, although the oxygen potential of the atmosphere in the system was satisfactory for work with nickel and copper, it was too high for work with iron, silicon, and so forth. Third, for work at 1550" to 1650°C, an improved temperature-sensing unit is needed. The modified calorimeter in its latest form is shown schematically in Fig. 1. The refractory brick and the Kanthal-Super heating elements which formed the furnace for heating the solute addition have been replaced by a smaller resistance-heated tube furnace which is insulated with bubble-grain alumina. A more elaborate gas purification system was installed to maintain a satisfactorily low oxygen potential in the atmosphere of the calorinieter chamber and of the solute addition furnace. As was the case in the earlier work, at the beginning of a run the calorimeter chamber is evacuated and then filled with purified argon so that a total pressure slightly in excess of 1 atm is maintained during the run. When either of the furnaces within the enclosure attains a red heat, 6 pct H2 is added to the atmosphere. Throughout the run, gas from the calorimeter is circulated through a de-oxidation system at the rate of approximately 5 standard liters per min; the changeover time for the gas within the calorimeter enclosure is approximately 1 hr. The essential stages of the deoxidation system are: a copper furnace at 600°C, a drying tube of anhydrite, and a titanium furnace at 800°C. The oxygen potential of the gas stream in the purification system can be monitored at several points by a stabilized zirconia oxygen cell. This cell is invaluable in detecting the development of leaks in the container vessel and the gas circulating system. The installation of the solute-addition furnace allowed either of two types of temperature-sensing units to be mounted on a water-cooled probe. The first was a small optical device using a silicon diode that was

Jan 1, 1968

By I. Javandel, P. A. Witherspoon

The finite element method was originally developed in the aircraft industry to handle problems of stress distribution in complex airframe configurations. This paper describes how the method can be extended to problems of transient flow in porous media. In this approach, the continuum is replaced by a system of finite elements. By employing the variational principle, one can obtain time dependent solutions for the potential at every point in the system by minimizing a potential energy functional. The theory of the method is reviewed. To demonstrate its validity, nonsteady-state results obtained by the finite clement method are compared with those of typical boundary value problems for which rigorous analytical solutions are available. To demonstrate the power of this approach, solutions for the more complex problem of transient flow in layered systems with crossflow are also presented. The generality of this approach with respect to arbitrary boundary conditions and changes in rock properties provides a new method of handling problems of fluid flow in complex systems. INTRODUCTION Problems of transient flow in porous media often can be handled by the methods of analytical mathematics as long as the geometry or properties of the flow system do not become too complex. When the analytical approach becomes intractable, it is customary to resort to numerical methods, and a great variety of problems have been handled in this manner. One such method relies on the finite difference approach wherein the system is divided into a network of elements, and a finite difference equation for the flow into and out of each element is developed. The solution of the resulting set of equations usually requires a high speed computer. When heterogeneous systems of arbitrary geometry must be considered, however, this approach is sometimes difficult to apply and may require large amounts of computer time. The finite element method is a new approach that avoids these difficulties. It was developed originally in the aircraft industry to provide a refined solution for stress distributions in extremely complex airframe configurations. 27 Clough has recently reviewed the application of the finite element method in the field of structural mechanics.6 The technique has been applied successfully in the stress analysis of many complex structures.l, 27, 28 Recognition that this procedure can be interpreted in terms of variational procedures involving minimizing a potential energy functional7 leads naturally to its extension to other boundary value problems. In the field of heat flow, there recently have been introduced several approximate methods of solution that are based on variational principles.2-4, 17 By employing the variational principle in conjunction with the finite element idealization, a powerful solution technique is now available for determining the potential distribution within complex bodies of arbitrary geometry. In the finite element approximation of solids, the continuum is replaced by a system of elements. An approximate solution for the potential field within each element is assumed, and flux equilibrium equations are developed at a discrete number of points within the network of finite elements. For the case of steady-state heat flow, the technique is completely described by Zienkiewicz and Cheung.33 Since the flow of fluids in porous media is analogous to the flow of heat, Zienkiewicz et al. have employed the finite element method in obtaining steady-state solutions to heterogeneous and anisotropic seepage problems. 34 Taylor and Brown have used this method to investigate steady-state flow problems involving a free surface.25 The work of Gurtin has been instrumental in laying the groundwork for the application of finite element methods to linear initial-value problems.12 As a result, Wilson and Nickell have recently

Jan 1, 1969

By Roy Lindgren

SINCE the year 1643, when the first blast furnace in America for treating iron ore was built at Saugus, Mass., out of mica schist quarried in the neighboring district, the procurement of a suitable refractory for furnace lining has been a problem of concern to the operators of furnaces. The stacks built of mica schist continued to smelt iron ore until about 1836, when, according to F. H. Norton, the first firebrick were produced1, at Queens Run, Pa. Other writers speak of brick having been molded and burned in Massachusetts about the year 1834. In 1841, Andrew Russell began to produce medium refractory plastic clay brick near East Liverpool, Ohio, that were used for lining blast furnaces1. The well-known Kentucky clay-producing district was not opened up until the year 1871, but since then it has produced a large percentage of the linings for iron blast furnaces. While some strides have been made by the refractories industry during the 100 years that have passed since the first firebrick were produced, it has been only during the last two decades that any real progress has been made towards bettering the product, even though the method of production had improved. Perhaps the fault lies with the user of the brick rather than with the producer, for not sooner demanding a supe-rior product. During the past 15 years the tonnage produced per lining has increased from 500,000 gross tons to 1,000,000 gross tons, and now some furnaces are producing 1,600,000 gross tons and better on a single lining. It is true that enlarged capacity of furnaces and improved practice have accounted for some of this increase in tonnage, nevertheless better quality in firebrick must be given credit for its share. However, we are not yet ready to say that we have reached a maximum life of furnace lining. We believe that a better product can be produced and that the refractories industries of America will, through their extensive research depart-

Jan 1, 1937

By Arthur Winslow

Introductory.—The following paper is based upon a report on the lead- and zinc- deposits of Missouri, prepared for the State Geological Survey, which is now being printed. This report is the outcome of work prosecuted by the writer, assisted by Mr. J. D. Robertson, during the past five years. The studies in the State were supplemented by examinations of the similar ore deposits in Wisconsin and Arkan- sas. The report will contain in all about 800 pages, and the aim has been to make it complete and exhaustive, especially in descriptive matter. Naturally, only a brief outline can be presented here, and the reader is referred to the report itself for further details. Contents. I.—History and Statistics, . . 636 II.—Topography of the Region, . 639 III.—General Geology, . . .639 The Archean, . . .639 The Algonkian, . . 640 The Silurian, . . .640 The Devonian, . . 640 The Lower Carboniferous, 641 Tie Coal Measures, . 641 The Tertiary, . . .641 Structural Geology,. . 642 IV.—The Ore-Deposits, . . .643 Geologic Distribution, . 643 The Forms of the Ore-Bodies, . . .641 The Composition if the Ore-Bodies, . . .645 Gangues, . . . 645 Minerals, . . .618 Paragenesis of Minerals, . . . 651 The Structure of the Ore-Bodies, .... 651 V.—Descriptions of Types, . . 652 The Eagle Mines, . . 652 Shaft No. 23, . . 652 The Western Zinc Company or Oswego Lands, 651 The Gobar and Tomlinson Shaft, . 655 The Alba Company's Mine, 656 The Victor Mine, . . 658 The Bonne Terre Mines, . 660 General Geology, . 660 The Ore-Bodies, . 661 The Vallé Mines, . . 664 The Garatee Mines, . 664 The Corn-Stalk Diggings, . . .665 The Virginia Mine, . 666 The Conlogue Mine, . 667 VI.—The Mode of Formation of the Ore-Bodies, . . 670 The Formation of the Cavities. . . . 670 The Filling of the Cavities, . . . .675 The Formation of the Breccia Deposits, . . 673 The Formation of Circle Deposits, . . .674 The Impregnated Deposits of the Southeast, . 676 VII.—The Origin of the Metalliferous and Other Minerals, 676 1. Originally Deposited in Concentrated Condition, 676 2. Derived from Great Depths, . . .677 3. Original Diffusion, Supplemented by Lateral Secretion, . . . 678 4. Concentrated Through Surface Decomposition, 681

Jan 1, 1895

By R. R. Jones, R. W. Kraft

Zn-Mg2Znn eutectic alloys nzay freeze willr either rodlike or lanzellar rnorphology. Alloys with slighlly more than /he eutectic arrzount of rnagnesillrn usually contain three-cnned dendrjles of MgzZnll in a eutec-lic ttlulris. All three morphologies haue the same cryslallographic orientution relationship: (0UOl) zn - 11 (111) Mg2Znll and (2310)Zn 11(101) Mg2Znll, but u3ith different prej-erred groulth direclions. The lurnellae lo rods transifion in con/rolled ingols qf euleclic cotnposition occurs because lhe large kinelic undercooling due to MgzZnll minirrzizes /he ejj-ecl of the solid-solid inlerface energy. The eutectic morphology is influenced by the presence of lhree-nned dendrites 0-f MgzZn11 which may conlrol /he rricroslrccture by acting as nuclealion sites. In recent years there has been much interest in eutectic solidification and several theories have been proposed. One of the confusing factors is the existence of various morphologies in which the solidified phases may form. The lamellar microstructure seems to be most common in metal eutectics, and it has been claimed' that all regular eutectics should be lamellar if sufficiently pure. However, there still remain eutectic alloys which are not lamellar or which change their morphology as a function of growth conditions. The eutectic between zinc and the intermetallic phase Mg2Znll was chosen for this investigation because it has been found to solidify in more than one morphology. The diagram in anssen' locates the eutectic point at 3.0 wt pct Mg and 367°C. lliott gives 364°C as the eutectic temperature, leaving the phase compositions unaltered. Since the growth conditions determine the micro-structure of the solidified alloy, the factors controlling the transition from one morphology to another could be studied. The lamellae to rods transition is of particular interest. PROCEDURE Alloys were prepared from carefully weighed portions of 99.999 pct Zn and 99.97 pct Mg by melting in Pyrex containers under argon and casting into graphite boats. The resulting ingots were remelted under argon and solidified unidirectionally in a horizontal tube furnace at growth rates ranging from 2.0 to more than 50 cm per hr under a temperature gradient, measured over a 5-cm length, of 9" to 14°C per cm. The solid-liquid interface appeared to be planar at all growth rates although no attempt was made to confirm this by decantation or quenching. A few ingots were allowed to freeze uncontrolled. Most alloys were of the nominal eutectic composition, 3.0 wt pct Mg according to Hansen2 and lliott, but some contained as much as 3.35 wt pct Mg. Chemical analyses were not run since metallographic examination confirmed that the desired composition was achieved. Specimens were cut from the middle portion of the ingot normal to the growth axis, polished mechanically, and etched with 2 pct Nital. Suitable areas were selected for the determination of crystallographic orientation relationships by a tiontechniqueof described previously by one of the authors.4 The (2310) planes of zinc and the (8701, {944}? (1032) planes of Mg2Znll were found suitable for orientation determination; experimental error was on the order of 2 or 3 deg. RESULTS Three different morphologies were found in the unidirectionally solidified alloys: lamellar eutectic, rod-like eutectic, and a structure whose most predominant characteristic was the presence of three-vaned (cellular) dendrites of Mg2Znll. These dendrites were only found in alloys with more than the eutectic amount of magnesium. In some ingots fine hexagonal needles of Mg2Znll surrounding a core of MgZn2 were observed. They were probably due to incomplete alloying and seemed to have no effect on the eutectic morphology. In addition hexagonal spirals like those discussed by Fullman and wood5 and Hunt and acksonh ere observed in some ingots frozen without directional control. Both MgZZn,, and MgZnz were detected by X-ray diffraction in these alloys. Since the morphology could not be grown unidirectionally and no characteristic orientation relationship between the phases was found, further study was limited to the lamellar: rodlike, and three-vaned dendrite morphologies. Alloys of Eutectic Composition, No Dendrites. The mcrostructures of allovs with no three-vaned dendrites were either lamellar or rodlike depending on the growth rate. At rates below 10 cm per hr the morphology was lamellar, consisting of two sets of parallel plates intersecting at about 54 deg like the Mg-MgzSn eutectic described by raft.7 At growth rates faster than 14 cm per hr the microstructure showed rods of zinc in a matrix of MgnZnll, while intermediate rates yielded mixtures of rods and lamellae in small groups. The lamellar "grains" were often several millimeters in cross section, but contained small irregular areas which divided each grain into perfect islands 100 or 200 p in diam. Lamellae were parallel to each other throughout the grain in spite of these defects in the structure, Fig. 1. Rods, on the other hand, could only be produced in small groups arranged like fish scales and separated by irregular areas of appreciable thickness, Fig. 2. Alloys Not of Eutectic Composition, With Dendrites. In alloys with 3.1 to 3.35 wt pct ME,-. three-vaned dendrites bf MgzZnll were usually found surrounded by eutectic. At growth rates slower than about 10 cm per hr the dendrites were separated from each other by small areas of both lamellar and rod eutectic, Fig. 3.

Jan 1, 1969

By J. W. Clark, C. T. Sims

Wrought chromium-base alloys containing yttrium, cubic monocarbides of the Ti(Zr)C type, and similay alloys containing manganese and rhenium have been melted and fabricated. Strength has been studied by hot hardness and elevated-temperature tensile and rupture measurements, low-temperature ductility by tensile testing, and surface stability by oxidation testing. In additiod, studies have been conducted of the carbide stability, and of aging behavior. The carbide dispersion generates effective elevated-temperature strength, which is further enhanced hv strain-induced precipitation. The dispersion exhibits classical dissolution and aging response. The ductile-to-brittle transition temperature of these alloys is above room temperature. The alloys reported show fairly good oxidation resistance, but nitrogen contamination can cause fortnation of a hard Cr2N layer under the oxide scale. Manganese does not appear to be a promising alloying element in chromium. In the years 1945 to 1950, the metal chromium was considered as a possible base for alloy systems due to its considerably higher melting point than superalloys, its low density, its high thermal conductivity, and its apparent capacity for strengthening. However, this interest in chromium was short-lived. It was found difficult to melt and cast, to be exceptionally sensitive to the effect of minor imperfections, to have a lack of ductility at both room and elevated temperatures, and to be subject to a deleterious effect of alloying elements upon the ductile-to-brittle transition temperature.' Since then, chromium, as a practical alloy base, has remained virtually unstudied. Further, purposeful ignoring of chromium has been promoted by statements that its bcc structure would not allow it to be strengthened to useful values, when compared to the "austenitic" alloys.2 Recently, a new look has been taken at chromium-base alloy systems. Study of the literature will show that chromium, providing some of its disadvantages could be eliminated or minimized, actually has a rather attractive potential as an alloy-system base. Analysis of rather scattered data suggests that chromium is quite capable of being strengthened to high levels. Also, significant strengthening of its two sister elements in Group VI-A, molybdenum and tungsten, has been demonstrated in a number of commercial and exploratory alloys. Chromium should be similar. Since chromium does not readily form a volatile oxide like tungsten or molybdenum, it offers a much higher probability of giving birth to alloy systems with useful oxidation resistance. Concerns about possible high elemental vapor pressure have been mitigated by recent data.3 In addition, the physical properties exhibited by chromium are attractive for application as a high-temperature structural material. For instance, its thermal conductivity varies from 49 to 36 Btu-ft/hr-sq ft-°F over its range of usefulness (which is two to four times higher than most superalloys), its density is about 7.2 g per cc (20 pct less than most nickel-base alloys), its coefficient of thermal expansion varies from 4 to 8 x 10-6 per OF, and it has a relatively high modulus of elasticity, approximately 42 x 10' psi.4 Alloying studies on a chromium base in the past have usually encompassed rather sweeping solid-solution alloy additions for strengthening. This is not consistent with contemporary alloying practice in Group VI-A. For instance, molybdenum, also in Group VI-A, is primarily alloyed for strength improvement by use of heat-treatable carbide dispersions.5 Chromium and molybdenum are similar in their chemical activity and other properties. Thus, strengthening of chromium by carbide dispersions was studied. Chromium-base alloys are plagued with room-temperature brittleness, although high-purity unal-loyed chromium can be made ductile.4,8 Use of yttrium as a scavenger has done much to improve ductility and resistance to nitrogen embrittlement in chromium systems,7 so it was utilized in this program. It has also recently been found8 that small rhenium additions (1 to 5 pct) create improvement in the ductility of Type 218 tungsten wire. This is apparently related to the remarkable effect of rhenium additions near its terminal solid solubility in all Group VI-A metals.9'10 Investigation to establish if dilute concentrations of rhenium would also be effective in chromium appeared to be logical for this program. Since rhenium is too expensive to be practical in alloys for application as structural components, ductility improvements through solid-solution alloying were also sought by substitution of manganese for rhenium; manganese, like rhenium, exists in Group VII of the periodic system. The optimum amount of carbide dispersion for chromium-base alloys was obtained by analogy with molybdenum. Strengthening in molybdenum is achieved by use of Ti-Zr carbide dispersions. A

Jan 1, 1964

By P. B. Elkin, K. C. Ten Brink, Allen D. Garrison

It is the purpose of this article to present the results of an investigation of certain clay and shale suspensions having viscosities that are materially influenced by fluid motion, and to discuss the bearing of these results upon the choice of policy in the control of drilling fluids. A previous article described the design and the characteristics of an instrument adapted to measure the viscosity of plastic suspensions during continuous uniform motion and at a variety of speeds.' It has long been recognized that the viscosity of a clay suspension depends on the past history of the fluid motion. Since an abundance of literature is available on this phenomenon,2 it is not necessary to describe it in more than general terms. It is usually observed that rapid motion reduces the viscosity of a clay suspension, and that some time is required for the viscosity to fall to its equilibrium value after the steady motion is started. On reducing the speed of motion to some lower value, the viscosity again rises, but it also requires some time to attain a steady viscosity value at the slower rate of motion. Thus clay suspensions are usually observed to be increasing in viscosity as time passes when the measurement has been immediately preceded by fluid motion that was more rapid than that employed in the measurement. And it is usually observed that the viscosity falls as time passes when the measurement has been preceded by more quiescent conditions. Reed,3 and Broughton and Hand4 have reported a condition of observation of clay suspensions in which the viscosity was observed to fall during the first few moments of steady motion, and rise thereafter. The characteristics of the new instrument are particularly well adapted to studies of this kind. With it we have been able to observe all of the phenomena described above, and it is important to understand their nature because they all occur at some time during normal drill-

Jan 1, 1940