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By R. B. Woodworth

Discussion of the paper of R. B. Woodworth, presented at the New York meeting, February, 1916, and printed in Bulletin No. 107, November, 1915, pp. 2247 to 2312. R. B. WOODWORTH, Pittsburgh, Pa.-This is a very long paper. It is a structural engineer's contribution to the art of mining and is written from his standpoint rather than from that of the mining engineer, and is, therefore, a study in the development of drilling structures by one who has made it his business to design structures rather than mechanism and machinery and rather than to utilize those structures in the actual exploitation of oil and gas. Drilling practice varies widely in different oil and gas fields. The , problems of western Pennsylvania are much simpler than the problems of the Mid-Continent and of the Gulf Coastal Plain and these again are simpler than problems of the Pacific Coast. The history of the commercial development of oil and gas is recorded in the annual publications of the U. S. Geological Survey and other bodies whose business it is to make record of statistics. The mechanical and structural features of the art of drilling have not yet received adequate treatment by the historian. Scattered references may be found on the subject in almost any work dealing at large with petroleum and its production. These references, however, are to those particular aspects of the matter that were contemporary with the publications themselves, but so far as I am aware there is no continuous and comprehensive account written of the development of drilling structures from their beginnings down to the present time, and certainly the more modern application of steel in the construction of such structures has not previously had an adequate discussion. With this latter phase of the subject I have been intimately associated, indeed, taking to myself the credit for having, in a way, been responsible more than any one else in the United States for the application of steel in the manufacture of drilling structures, and the purpose of the paper which is now before you is to record particularly the steps in that development while the subject is still fresh and the data available.

Jan 5, 1916

By R. W. Gould, B. G. LeFevre, A. G. Guy

The resistivity anomaly known as the K state was studied in Ni-Mo alloys containing 10.5 and 14.0 at. pct Mo. Both these alloys exhibit a large K effect which depends on the mechanical and thermal treatment. On the basis of X-ray diffuse scattering studies which were correlated with resistivity measurements, it appears that the K state in dilute Ni-Mo alloys can be associated with changes in the degree of short-range order within the a phase. An interesting phenomenon that has received much attention in recent years is the K state. The K state is marked by anomalous changes in some of the physical properties of certain alloys without the occurrence of observable microscopic structural changes. One of the early pieces of work in this area was by Thomas' who studied alloys of Ni-Cr, Ni-Cu, Ni-Cu-Zn, Fe-A1, Fe-Si, and Ni-A1. Upon annealing specimens which had been previously cold-worked or quenched from an elevated temperature he found an anomalous increase in resistivity over a certain temperature range. He also found that specimens which had been appropriately annealed to develop the K state showed a decrease in resistivity upon subsequent cold working. These effects are opposite to those found in normal alloys. Although the resistivity anomaly has been rather arbitrarily taken as the "definition" of the K state, there are several other interesting effects which accompany the resistivity increase. In Ni-Cr alloys,2, 3 for example, it was found that the hardness increases with increasing resistivity. It was also found that specimens which have been treated to develop the K state can be cold-worked for as much as an 80 pct reduction of area without an increase in the hardness. In Fe-A1 and Fe-Si alloys4 the K state is accompanied by an increase in flow stress and by a lattice contraction. In Ni-A1 alloys,5 specimens which have been treated to develop the K state also show an increase in elastic modulus. In Ag-Pd alloys6 the increased resistivity observed on annealing a cold-worked specimen is accompanied by an increase in the thermoelectric power and an increase in the Hall coefficient. The explanations of the K state phenomena are varied and depend upon the particular alloy in question. Several theories have been advanced to explain the increased conductivity with cold work on the basis of changes in the electronic configuration of the alloy as a result of local lattice distortions.7"9 Most investigators, however, believe that some type of local order in the solid solution, either short-range order (SRO) or clustering, is responsible for this effect. Theories concerning the relationship between ordering and the K state have for the most part been speculative, since there is little direct X-ray evidence that can be correlated with the above property changes. Much of the previous work on the K state was done in the Ni-Cr system where the small difference in the X-ray atomic scattering factors of the components nickel and chromium makes it very difficult to use X-ray diffuse-scattering measurements to determine the role of local order. In the Ni-A1 system, however, Starke et al.10 succeeded in detecting a connection between local order and the K state. It was found that a small but measurable K effect correlated with increasing SRO in the nickel-rich a phase. The manner in which local order might increase the resistivity of K state alloys is not completely clear. Since most of the known K state alloys contain at least one transition element, significance has frequently been attached to the presence of an unfilled d shell. It has been suggested that during the formation of the K state the number of conduction electrons decreases as a result of the transfer of s electrons to the d shell where they are more tightly bound.1'11'12 Koster and Rocholl13 have proposed that SRO can cause an increase in resistivity for alloy systems in which the number and mobility of charge carriers are reduced when the percent solute is increased. According to this hypothesis, the local environment of a given solvent atom changes in the same manner with increasing percent solute as it does with an increasing degree of SRO; hence the change in physical properties should tend in the same direction. In this hypothesis, SRO is considered only in a statistical sense, and the increased resistivity of the K state is attributed to a change in the mean distribution of electrons and holes in the s and d states as a result of SRO. From the work of Chen and Nicholson on Ag-Pd alloys,6 it appears that the K state can occur in systems for which the d shell is completely filled. These investigators explained the increased resistivity by picturing the SRO as small domains of some form of long-range order (LRO). According to ~ibson,'~ the number of effective electrons can be reduced by the creation of a new Brillouin zone boundary near the Fermi surface of an alloy as a result of the changing crystallographic symmetry that accompanies the formation of a superlattice. This idea may be expressed in terms of the superzone concept.15 In the present work the role of local order in the formation of the K state in Ni-Mo alloys was investigated. The principal tools used in this study were X-ray diffuse scattering and electrical resistivity measurements; however, these data were supplemented by electron microscopic and field-ion microscopic data. The purpose of the work was to determine whether or not the K state in Ni-Mo alloys can indeed be attributed to the formation of SRO as has been proposed by previous investigators.

Jan 1, 1969

By A. A. Smith, J. S. Smart

THE controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modem copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range 0 to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously.1-2-3 Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,1, 2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of 3/8-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 850°C. from a surface scale. Test wires were drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at o.3125, 0.257, o.204 and o.162 in., and a final cold reduction of 95 per cent t0 0.081 in. Oxygen-bearing slugs made by remelting were hot-rolled to 5/16 in., drawn to 0.162 in., annealed for 30 min. at 600°C. and cold-drawn 95 per cent to 0.081inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 5/16-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700° to 800°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals were of one hour duration followed by a rapid quench in 10 per cent H2SO4. EFFECT OF PHOSPHORUS The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1945

By Eugene H. Dawson

MICA is a mineral that once was a familiar sight as fireproof windows in stove and furnace doors and as lamp chimneys and shades. Since 1878, the beginning of the electrical age, the use of mica for such purposes has gradually declined and its use in electrical equipment and appliances has developed to such an extent that the known sources of supply are scarcely equal to the demand. With the increasing capacity of electric generating units, the size of mica sheets found in nature was inadequate. However, in 1894, a process was developed whereby thin films or splittings cemented with shellac or other binders could be pressed into large sheets. 18 The introduction of radio in the early 1920s created such a heavy demand for the smaller sizes of mica that on March 22, 1938, mica was included among 23 commodities on the list of strategic materials approved by the United States Army and Navy Munitions Board. To be included in this list, the material must be one whereof the domestic supply is not sufficient to meet the demand. COMPOSITION Mica is a complex mineral composed principally of the silicates of potassium, aluminum, and magnesium. Less prevalent species contain, as essential components, lithium, vanadium, and chromium. Iron usually is present either as an essential component or as an impurity. The mica group comprises some nine different species, five of which, muscovite, phlogopite, vermiculite, lepidolite, and biotite, are widely used in industry. Lepidolite and zinnwaldite (lithium micas) and roscoelite (vanadium mica) are sources of lithium and vanadium. Muscovite, "white mica," is potassium mica. Theoretical formulas H2KAl3(SiO4)3. There are two varieties, distinguished as to color, known in industry as ruby and green. In crystals or "books," the colors each range through varying shades of red and green. However, when split into thin films, all micas, except biotite and phlogopite, are colorless and transparent. Muscovite frequently is stained red or black by thin films of iron oxide between the laminae. The staining usually is derived from magnetite, which sometimes is found as unaltered crystals.

Jan 1, 1949

By Colin C. Harris, Nathaniel Arbiter

The flotation operation can be analyzed in terms of three groups of variables. The first, largely independent of control by the operator, embraces the fixed physical and chemical properties of the ore minerals. The second includes all chemical and physical effects imposed on an ore after mining that influence its floatability. These can be either purposefully or accidentally applied. The third embodies the flotation-machine characteristics which realize the potential floatability of selected ore minerals in terms of grade and recovery levels. The machine effectiveness thus depends not only on its own contribution, but on the prior influence of all other variables on floatability. HISTORICAL DEVELOPMENT From the earliest days, flotation mills used many types of machines. Hoover 20 in 1914 mentioned as then important the Potter-Delprat tank for gas generation by acid, the DeBavay cones for skin flotation, the Elmore mixer and separation chamber for vacuum flotation, and his own modification of the Mineral Separation cell for the agitation froth process. Less important at the time were the MacQuisten tube and the Hyde cell. By 19274~ scores of machines had been developed and dozens had found their way into mills. From then on, however, under the scrutiny of competitive tests, many fell into disuse. Taggart in 19454~ classified processes broadly as skin flotation and froth flotation, dividing machines for the latter into the three categories: bubble column, pulp body, and combination.* Under 'bubble column' he listed all pneumatic, cascade, and subaeration cells; and under 'pulp body' those cells in which gas was generated by boiling, chemical action, and pressure reduction, as well as the agitation-froth type. At that writing skin flotation, the cascade machines, and all pulp body and combination machines were said to be extinct, leaving pneumatic and subaeration types dominant (u. S. practice). The process of elimination has continued to the present, with almost all pneumatic cells succumbing to the pressure of competition from subaeration machines. The only new machines to appear in recent years have been double-impeller types f and these have met with only limited acceptance.

Jan 1, 1962

By John Ryan

SIR HUMPHREY DAVY'S epoch-making treatise delivered on Nov. 9, 1815, before the Philosophical Society of London, first announced and demon¬strated a flame safety lamp for detecting methane in mine air. Coal mining was known in England as early as 1180, more than 600 years before the advent of a safe lighting and gas-detecting appliance. Mining, no doubt, took place first in outcrop coal, and danger from gas did not become apparent until the workings became deeper and more extensive. Davy's lamp did much to increase the safety of miners, and a modified Davy lamp is still widely used for detecting the presence and approximate amount of combustible gas in mine air. No factor in coal mining has improved more rapidly during the past 15 years than safety measures. This progress came about not only as a result of the work-men's compensation laws now in force in most of the states of the Union, but because the research work of the U. S. Bureau of Mines has demonstrated some dan¬gers incident to coal mining which were not considered to be serious matters prior to that time. Electric power and explosives are necessary but 1-potential hazards in American coal mines. A general mechanization program is now under way, while the mines are growing deeper and more extensive. Conse-quently ventilation problems are more complex and a demand has been created for positive detecting devices for carbon monoxide as well as methane. Scientists and manufacturers, working hand in hand during the past 10 years, have invented and developed appliances which make systematic and effective examination of mine air possible. The object of this paper is to describe briefly the approved testing devices in use today, with the hope that they may lead to the saving of life. Dangerous coal mine gases may be placed in two groups: (1) those that are dangerous because of their explosive properties, and (2) those that are dangerous because of their toxic properties. Methane (CHI) is the important gas of the first group, and in so-called gaseous mines constantly exudes from the coal and rock; it may accumulate and form an explosive mixture.

Jan 2, 1927

By A. G. McGregor

In the Southwest a number of large steel chimneys discharge the gases from the copper smelting furnaces. Some of these chimneys show no deterioration after twenty years, others show serious deterioration after tour years service. A steel stack 20 ft. 7 1/2 in. (6.3 m.) in diameter by 279 ft. (85 m.) high, Fig. 1, used for roaster gases only at the Calumet & Arizona Mining CO.'s plant at Douglas, Ariz., was lined to the top of the bell, 40 ft. (12 m.) from the base, with common brick placed on end, lime and cement mortar being used. Above the bell, the stack was lined with 4 by 4 by 8 in. (10 by 10 by 20 cm.) building tile, placed on end, making a lining 4 in. thick. The tiles were supported on angle-iron rings, riveted to the inside of the chimney shell about 15 ft. apart. The chimney was put into use in the latter part of 1913. Four years later, considerable of the tile lining had fallen out of place and mixed with the flue dust at the bottom of the chimney. About a year later, several flattened and distorted sheets were noticed about 70 ft. below the top. An investigation showed that the thickness of these distorted sheets, which was originally 1/4in., had been reduced one half. One year later, or six years after the chimney went into use, several holes, a square foot and smaller in area, appeared near the flat spots mentioned. Soon afterwards, when the chimney was shut down for repairs, it was found that most of the tile lining for 125 ft, from the top had fallen out and that the steel shell was badly corroded; but where the lining remained in place the shell was undamaged. Many of the tile which had fallen out of place had become soft or flaky and crumbling, others were as hard as when placed. An analysis of the hard and soft tile is shown on p. 2. These tile were of a fireclay mixture, and were used instead of common brick on account of lower cost. The steel forming the upper 125 ft. (38 m.) was replaced, and a 4 1/4-in. (11-cm.) lining of firebrick was laid from the bell to the top of the chimney. The brick were placed on end, wedges and keys being used. After each 8-in. course was set, keyed, and wedged tight, thin mortar —water, sodium silicate, and finely ground silica—was worked into the joints. The brick are supported on angle-iron rings, every 15 ft., in the same way as the tile.

Jan 1, 1921

By Joe B. Alford

Founding of the Institute The advance of population and civilization in the U. S. moved through the woodlands of the East, and reached the edge of the great central plains about the middle of the nineteenth century. There the advance paused for almost a generation - ahead were vast reaches of prairie country, uncharted, forbidding, and populated by hostile tribes of the native Indians. The turmoil of the Civil War, and the readjustments following it, further delayed the advance. By about 1870, the Nation was becoming stabilized again, the conflict with the Indians was closing, and the pressure of growth was forcing population to resume its westward movement. In addition to geography, the Nation had another frontier: the development of its immense natural resources. Conditions of the time brought into sharp focus the need for coal, iron, steel, gold, silver, and other minerals. The application of engineering and science was necessary for the production of these minerals and their manufacture into products to meet the needs of a growing nation. The requirements of the time were eloquently expressed in a paper by AIME member Edmund C. Pechin in 1872 : We find, the world over, the most intense activity everywhere displayed in enterprises requiring prodigious quantities of iron. Railways of colossal magnitude are projected. . . . The growing scarcity of timber is compelling the use of iron in buildings; bridges of wonderful size and strength; huge ocean steamships; barges and boats for lake and river traffic; churches; cars, and thousands of minor articles of every shape and size. . . . The time has come when scientific research is to assume its true position - the day of "sheer force and blind stupidity," whose only protection is a high tariff, has gone forever . . . the physicist, the geologist and mineralogist; the chemist, the engineer, are as essential to success as the [blast] furnace itself. . . . There is no merely practical man, no matter how varied may have been his experience, or how long his practice, that will not benefit from the results of scientific investigation. That there is a growing sense of the importance of having thoroughly prepared scientific men in every department of business is evidenced by the institutions [of learning] that are springing up in different quarters, provided with

Jan 1, 1971

By W. H. Bassett

ALTHOUGH brasses and bronzes have been made for ages, a systematic study of their physical properties has been carried out only during the years of the present century. Among these properties may be included those which are to be detected by means of microscopic examination; in other words by the science of metallography. The earlier workers in this field, both in this country and abroad, gave their attention to steel. When the senior author explored the situation in 1902, there was little encouragement to be found in undertaking the study of the non-ferrous alloys. A start was made, and the metallography of the brasses and bronzes, as well as of the copper-nickel- zinc alloys developed materially under his direction. Annealing experiments were begun in 1902, and in the succeeding years the effect of temperature, and the influence of previous working, on the grain size of brass were studied. The conclusions so well known and widely published today were largely reached during those earlier years. In 1905 the first complete annealing series were made. By this it is meant that brass and copper sheet, 5 B & S Nos. hard, was machined into tensile test specimens, then annealed under accurate control for 30 min. at temperatures up to the melting point of the material. Various determinations were made, including tensile strength and elongation in 2 in. There rapidly followed similar series on all of the copper-zinc alloys from 100 to 60 per cent. copper, on the bronzes, cupronickels, and on copper-zinc-nickel alloys. At this point there was published by Grard, in October, 1909,1 the very comprehensive and complete work on the tensile properties of cartridge brass, 90-10 copper-zinc, and electrolytic copper. The excellent photomicrographs in that paper illustrated the changes in structure produced by cold rolling as well as by annealing at different temperatures, but where Grard's work was confined to copper and to two alloys, the investigations in this laboratory have been over the entire fields of the commercial copper-zinc alloys, copper-tin alloys, representative copper-nickel and copper-nickel-zinc alloys as well as aluminum bronzes and others of a more special nature.

Jan 1, 1927

By G. F. Loughlin

MORE than 20 years have passed since the publication of Lindgren and Ransome's report on the Cripple Creek District,1 which was made when the district was much more active and prosperous than in recent years. They concluded that the output of the district, which had reached its maximum of about $18,200,000 in 1900, would gradually decline, and their conclusion has been confirmed by records of subsequent production. Between 1905 and 1915 annual declines were partly compensated by encouraging increases, especially in 1908, 1914, and 1915; but a rapid continuous decline followed, due largely to the war and its after effects, until in 1922 the value of output was only slightly more than $4,000,000. It rose to nearly $5,000,000 in 1924, but declined again in 1925 and in 1926, when it was about $4,400,000, and represented ores mainly from deep levels in the Cresson and Portland mines. The profitable operations of these two mines were the principal factors leading to a study of ore at deep levels in the district by the U. S. Geological Survey in coopera-tion with the Colorado Metal Mining Fund. The principal reasons for Lindgren and Ransome's conclusion were three: (1) the greater cost and difficulty of deep exploration; (2) the decrease in the number of veins with increasing depth, and (3) the probability that the telluride ore, believed to have formed at comparatively low temperature, would not persist indefinitely -in depth. Operations since they made these statements have verified the first two, but call for some modification of the third. Rich telluride, ore is being mined at a profit in the Portland mine 3000 ft. below the present surface, or 5000 ft. below the original surface of the Cripple Creek volcano, as interpreted by Lindgren and Ransome. The question arises, therefore, as to the number and extent of such deep deposits, and the answer, so far as it can now be given, must be based mainly on structural data, supplemented by data on the processes of ore deposition. Presentation of these data based on a study of deep mines in the southeast quarter of the district, the only

Jan 1, 1927

By G. F. Loughlin

More than 20 years have passed since the publication of Lindgren and Ransome's report on the Cripple Creek District,1 which was made when the district was much more active and prosperous than in recent years. They concluded that the output of the district, which had reached its maximum of about $18,200,000 in 1900, would gradually decline, and their conclusion has been confirmed by records of subsequent production. Between 1905 and 1915 annual declines were partly compensated by encouraging increases, especially in 1908, 1914, and 1915; but a rapid continuous decline followed, due largely to the war and its after-effect's, until in 1922 the value of output was only slightly more than $4,000,000. It rose to nearly $5,000,000 in 1924, but declined again in 1925 and in 1926, when it was about $4,400,000, and represented ores mainly from deep levels in the Cresson and Portland mines. The profitable operations of these two mines were the principal factors leading to a study of ore at deep levels in the district by the U.S. Geological Survey in cooperation with the Colorado Metal Mining Fund. The principal reasons for Lindgren and Ransome's conclusion were three: (I) the greater cost and difficulty of deep exploration; (2) the decrease in the number of veins with increasing depth, and (3) the probability that the telluride ore, believed to have formed at comparatively low temperature, would not persist indefinitely in depth. Operations since they made these statements have verified the first two, but call for some modification of the third. Rich telluride ore is being mined at a profit in the Portland mine 3000 ft. below the present surface, 07. 5000 ft. below the original surface of the Cripple Creek volcano, as interpreted by Lindgren and Ransome. The question arises, therefore, as to the number and extent of such deep deposits, and the answer, so far as it can now be given, must be based mainly on structural data, supplemented by data on the processes of ore deposition. Presentation of these data based on a study of deep mines in the southeast quarter of the district, the only

Jan 1, 1927

By W. H. Bassett, C. Davis

Although brasses and bronzes have been made for ages, a systematic study of their physical properties has been carried out only during the years of the present century. Among these properties may be included those which are to be detected by means of microscopic examination; in other words by the science of metallography. The earlier workers in this field, both in this country and abroad, gave their attention to steel. When the senior author explored the situation in 1902, there was little encouragement to be found in undertaking the study of the non-ferrous alloys. A start was made, and the metallography of the brasses and bronzes, as well as of the copper-nickel-zinc alloys developed materially under his direction. Annealing experiments were begun in 1902, and in the succeeding years the effect of temperature, and the influence of previous working, on the grain size of brass were studied. The conclusions so well known and widely published today were largely reached during those earlier years. In 1905 the first complete annealing series were made. By this it is meant that brass and copper sheet, 5 B & S Nos. hard, was machined into tensile test specimens, then annealed under accurate control for 30 min. at temperatures up to the melting point of the material. Various determinations were made, including tensile strength and elongation in 2 in. There rapidly followed similar series on all of the copper-zinc alloys from 100 to 60 per cent, copper, on the bronzes, cupronickels, and on copper-zinc-nickel alloys. At this point there was published by Grard, in October, 1909,' the very comprehensive and complete work on the tensile properties of cartridge brass, 90-10 copper-zinc, and electrolytic copper. The excellent photomicrographs in that paper illustrated the changes in structure produced by cold rolling as well as by annealing at different temperatures, but where Grard's work was confined to copper and to two alloys, the investigations in this laboratory have been over the entire fields of the commercial copper-zinc alloys, copper-tin alloys, representative copper-nickel and copper-nickel-zinc alloys as well as aluminum bronzes and others of a more special nature.

By E. F. Bailey, W. J. Harris

THE temperature of the ferrite to austenite re-action is established frequently by continuous heating experiments. However, equilibrium studies of this reaction have demonstrated that austenite may form at temperatures considerably below those at which the reaction is first observed during continuous heating. Because of this discrepancy, tempering is sometimes performed above the true critical temperature and in these cases austenite forms during tempering. The lowest temperature at which austenite forms and the kinetics of the reaction have been studied by Bain,' Bleakney and Gros-venor,2 and Dube and Cunningham. This austenite can affect the properties either as austenite per se, if it is retained at room temperature, or as a decomposition product if it transforms. The effect of austenite formation during tempering on low temperature impact properties of an 8 1/2 pct nickel steel was reported by Brophy and Miller4 in work published after the present investigation was initiated. They concluded that the improvement in low-temperature notch toughness which followed tempering at certain temperatures could be attributed to the austenite formed during tempering. Kramer et al.5 found anomalous hardness increases and embrittlement after tempering of a low-carbon manganese-nickel steel. They concluded that austenite formed during tempering, and that the decomposition products were responsible for the increase in hardness and the embrittlement. Quan-titative correlations of the microconstituents and mechanical properties were not made by these investigators. The present study was undertaken in order to establish the kinetics of formation of austenite at various temperatures, the characteristics of the decomposition of this austenite, and the relationship between mechanical properties and the phases present. Experimental Procedure A low-carbon manganese-nickel steel was selected because of the sluggishness of its austenite decom-position reactions. The composition of this steel in percent was: C, 0.10; Mn, 3.52; Ni, 2.34; Mo, 0.52; Cr, 0.17; Si, 0.19; V, 0.15; P, 0.019; and S, 0.020. Samples were prepared by forging sections from a large ingot to 3/4 in. bars. Formation and decomposition of austenite were investigated by dilatometric techniques which were checked by X-ray measurements. Dilatometer specimens were hollow cylinders 1 in. long, 1/2 in. diam, with a 1/8 in. central hole. All specimens were aus-tenitized for 1 hr at 1650°F and quenched in water prior to insertion in the dilatometer. Oxidation was prevented by using an inert atmosphere of purified nitrogen. Dilation was measured with a dial gauge which could be read by interpolation to 0.00005 in. Temperature was maintained within ± 3°F by a Brown Electronik Controller. Chromel-alumel thermocouple leads were welded to opposite ends of the specimen with the specimen serving as the hot junction. As a check on temperature uniformity comparison was made of the specimen temperature as measured with the chromel-alumel leads and the temperature of the center of the specimen as measured with a calibrated platinum—platinum-rhodium thermocouple embedded in asbestos in the central hole of the specimen. During heating a 5°F temperature difference was noted below 1000°F, but none above, while in cooling, a 5°F difference was observed from 1300" to 735°F, but none below. Heating rates of 35°F per min and cooling rates of 60°F per min were employed for all dilatometric studies. For transformation studies below room temperature, the dilatometer was allowed to cool to 150°F and then was quenched into liquid nitrogen.

Jan 1, 1951

By Arthur H. Redfield

In estimating the unmined petroleum reserves of Central America, it is not feasible to employ the methods that have been worked out in thc oil fields of the United States. No producing wells have been brought in and no drilling sections have been made public. It is accordingly necessary to fall back on a crude "barrels per square mile" estimate. The method chosen is a comparison of the structure of the foreign field of unknown reserves with that of some supposedly analogous North American field of which the reserves have been estimated. This method makes no pretense at scientific accuracy, but furnishes a working basis for an estimate. The areal geology of Central America is illustrated in the inap prepared by Sapper and more recently in the geologic map of North America accompanying U. S. Geological Survey Professional Paper No. 71, "Index to the stratigraphy of North America." Disregarding for the present the narrow Quaternary coastal plains and alluvial deposits of the river valleys, three chief zones may be distinguished. These arc: A zone of late eruptive and effusive rocks; a zone of highly folded prr-Cambrian(?) or early Paleozoic crystalline schists and slates, considerably intruded by pre-Tertiary plutonic rocks; and a zone of more or less folded sediments, chiefly of Cretaceous or Tertiary age. The zone of late eruptive and effusive rocks of Central America begins in southeastern Chiapas, Mexico, and extends, with increasing breadth, across southern Guatemala, across practically the whole of El Salvador, and across southern Honduras to the valley of Rio Goascorhn, where the igneous zone attains a width of about 100 mi. (160 km.) East of the Goascordn Valley late eruptives and effusives play a subordinate part, being confined largely to thc Departments of Valle and Choluteca. Dikes and sills of igneous rocks intrude the sedimentary formations of central and northern Honduras. Late igneous rocks cover about four-fifths of the area of Nicaragua. In Costa Rica, late igneous rocks form the diagonal ranges of the Sierra de Guanacaste and the Cordillma Central, and play a part in the upbnild-

Jan 1, 1923

By Arthur H. Redfield

In estimating the unmined petroleum reserves of Central America, it is not feasible to employ the methods that have been worked out in thc oil fields of the United States. No producing wells have been brought in and no drilling sections have been made public. It is accordingly necessary to fall back on a crude "barrels per square mile" estimate. The method chosen is a comparison of the structure of the foreign field of unknown reserves with that of some supposedly analogous North American field of which the reserves have been estimated. This method makes no pretense at scientific accuracy, but furnishes a working basis for an estimate. The areal geology of Central America is illustrated in the inap prepared by Sapper and more recently in the geologic map of North America accompanying U. S. Geological Survey Professional Paper No. 71, "Index to the stratigraphy of North America." Disregarding for the present the narrow Quaternary coastal plains and alluvial deposits of the river valleys, three chief zones may be distinguished. These arc: A zone of late eruptive and effusive rocks; a zone of highly folded prr-Cambrian(?) or early Paleozoic crystalline schists and slates, considerably intruded by pre-Tertiary plutonic rocks; and a zone of more or less folded sediments, chiefly of Cretaceous or Tertiary age. The zone of late eruptive and effusive rocks of Central America begins in southeastern Chiapas, Mexico, and extends, with increasing breadth, across southern Guatemala, across practically the whole of El Salvador, and across southern Honduras to the valley of Rio Goascorhn, where the igneous zone attains a width of about 100 mi. (160 km.) East of the Goascordn Valley late eruptives and effusives play a subordinate part, being confined largely to thc Departments of Valle and Choluteca. Dikes and sills of igneous rocks intrude the sedimentary formations of central and northern Honduras. Late igneous rocks cover about four-fifths of the area of Nicaragua. In Costa Rica, late igneous rocks form the diagonal ranges of the Sierra de Guanacaste and the Cordillma Central, and play a part in the upbnild-

Jan 1, 1923

By P. Marier, T. R. Ingraham

When anhydrous cupric sulfate is heated in a stream of nonreactive gas, cupric oxysulfate is formed. When this reaction is complete, the cupric oxysulfate then decomposes to cupric oxide, which is the normal end product of reaction. The kinetics of each of these reactions has been studied using pellets prepared from finely divided cupric sulfate and from finely divided cupric oxysulfate. In each case, the reactant-product interface within the pellet is well-defined, and by normalizing the decrease in inter facial area with the weight fraction of the pellet decomposed it has been shown that the interface migrates into the pellet at a uniform rate at constant temperature. The activation energy estirnated for the decomposition of cupric sulfate is 57 ± 7 kcal per mole and that for cupric oxysulfate is 67 ± 8 kcal per mole. The rate of interfacial reaction is flow-sensitive, increasing with increasing flow of a sweep gas in the range from 50 to 2000 cu cm per min. The rate of decomposition is retarded by sulphur trioxide in the sweep gas. The relationship between sulfur trioxide Partial pressure and rate is consistent with the Langmuir Adsorption Isotherm governing the retention of sulfur trioxide in the interfacial layer. MOST of the work reported on the thermal decomposition of cupric sulfate and of cupric oxysulfate is related to the thermodynamics of the individual decompositions.'-4 No information is available on the rates of the individual reactions, on their activation energies, or on the effects of gas flow or of partial pressure of sulfur trioxide on the reaction rates. Some dubious conclusions based on relative reaction rates have been drawn from studies on the oxidation of sulfides. For example, on the basis of the products observed in a quenched system, it has been suggested5" that, when copper sulfide is roasted, the cupric oxide which is formed arises from the decomposition of either cupric sulfate or cupric oxysulfate. This is very difficult to reconcile with the thermodynamics of the C-S-O System,3 which support the probability that both cuprous oxide and cupric oxide precede cupric oxysulfate and cupric sulfate in the sequence of products formed during the oxidation of cuprous sulfide. In this paper the individual sulfate decomposition reactions will be examined and suggestions will be advanced for the mechanism of reaction. This will be based on the effects on reaction rate of changes in interfacial area, flow rate, and back-pressure of sulfur trioxide. EXPERIMENTAL Materials. The copper source material used in all experiments was Fisher Certified Reagent Grade anhydrous cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared by roasting cupric sulfate for 48 hr, with frequent rabbling, in an open tray in a muffle furnace maintained at 725°C. At this temperature, cupric sulfate develops about 0.16 atm pressure of combined sulfur trioxide, sulfur dioxide, and oxygen. Cupric oxysulfate develops only about 0.05 atm pressure, and is stable until

Jan 1, 1965

By M. P. Tixier, F. Segesman

Explanations bused on theory and laboratory tests tire offered for certain unusual features of SP logs which may befog their interpretation, namely the "sawtooth" SP and the reduction or increase of SP with time. The sawtooth SP is frequently seen in SP recordings of thick, very permeable watcr. sands of the Louisiana Gulf Coast. Using SP data from a resistor network analog, this anomaly is explained on the basis of a thin shale streak within the sand. under which the invading filtrate accumulates by gravity segregcitiorr. The electromotive force then appearing across the shale streak gives rise to the anomalous SP. Reduction of the SP on successive logging runs Ira often been observed in very permeable sands when as indicated by the resistivity curves, the invasion depth has been reduced to practically zero. Laboratory results verify that this phenomenon may be due, to the presence of air electromotive force, across the mod rake when the fluids on either side differ in activity. Also, there is, in some cases; an increase of SP deflection on successive logging runs, because the emf initially present across the mud cake disappears as the somewhat saline water just behind the mud cake is progressively flushed out by the invading filtrate.. Field example and laboratory data are presented. I N T R ODUCT1ON Some unusual features are frequently observed on certain SP logs which make interpretation difficult. The purpose of this paper is to offer explanations of several cases of interest. All of these arc related to the conditions of invasion. The cases to be discussed are as follows. 1. The sawtooth SP anomaly which is frequently seen within the thick, highly permeable saltwater sands of the Louisiuana Gulf Coast 1. Reduction of the SP deflection from the usual sand line in very permeable sections when the depth of invasion is practically nil. As will be explained, such a reduction is attributable to a membrane electromotive force across the mud cake. 3. An increase of the SP with time just after the iormation is drilled as a result of progressive flushing of the invaded zone. FUNDAMENTALS OF SP PHENOMENA An explanation of SP phenomena must begin with the following basic ideas. 1. The SP log derives its character from ohmic potential differences in the hole produced by currents flowing through the mud.' These currents are driven by electromotive forces which are primarily electrochemical in origin. Other possible types of SP-producing electromotive forces may be disregarded for the purposes of this paper. 2. The electrochemical emf's associated with permeable formations are now understood to consist of liquid-junction emf's and membrane emf's.',' As schematically shown by thc battery symbols in Fig. 1, the liquid-junction emf, E,,,, exists at the contact between waters of different chemical activities, a,,,, (mud filtrate) and tr,,. (formation water); the shale membrane emf, lS.sn. exists across the adjacent shales whcn they separate waters of different activities. The emf's just cited are additivc in producing SP currents (arrowed circles of Fig. I). Thus, neglecting for the moment any possible membrane emf across thc mud cake, the total electrochemical emf, E,, will be given by their sum, where K,., -! K,q,, = 12 + 59, or 71 at 75 °F. In the log interpretations the SP of a thick sand (i.e.. the static SP) is generally related to the activities of the filtrate and formation water through Eq. 1. by setting the static SP equal to - E,.

By T. O. Anderson, E. J. Stahl

Tests to increase knowledge concerning the process of hydraulic fracturing have been performed on three wells in the Allegheny field in western New York. The fracture orientation and its physical appearance at the well-bore was determined by impression packers run at appropriate times throughout the program. Fract~tre azi171uth and its dimensions thus determined were compared to the rock properties and treatment conditions. Logs to provide data concerning rock properties and to improve identification of vertical fractures were run before each step of the fracture treatment. Pressure osc~illu~iot~s were studied after each phase of tile treatments surface pressures during treatment. These measurements show that subsurface pressures exhibit many of the same characteristics as surface pressures during treatment of a well; however, transient pressures are dampened and deelayed in time at the bottom of the well when COmpared with surface pressures. Data obtained from this study provides a means to help locale and determine orientation of vertical fractures made in the open wellbore. Although these rests were performed in only one area, much of the information gained may be applied to fracturing programs in orher areas. INTRODUCTION In this study, various tests were made to provide data to better understand formation fracturing in situ. The reservoir studied is the Richburg oil sand which is a part of a series of predominantly grey sandstones and shales with occasional brown sandstone layers, known as the Caneadea unit of the Canadaway group of Upper Devonian age. Average physical characteristics of 12 cored wells in this area are 13-ft thick gross sand formation, 12-ft thick net sand. 1.7 md permeability, 11 percent porosity, 44 percent oil saturation (before secondary recovery) and 16 percent water saturation (before secondary recovery). This particular area of the Allegheny oil field was originally drilled prior to 1890. The first waterflood secondary recovery attempt was made in 1929. The present sustained waterflood development began in 1951 and is being carried out on a 4.5 to 5-acre spacing. Objectives of these tests were to (I) study fracture azimuth and dimension in relation to rock properties and treating conditions, (2) improve fracture identification techniques, (3) compare surface and subsurface pressure during all phases of treatment and (4) compare the periods of the fluid column oscillations occurring after each phase of treatment. Although the areas of investigation listed appear divergent in purpose, the program was designed primarily to increase knowledge of down-hole conditions leading to rock failure and extension of the fracture thus created. TEST PROCEDURES Wells upon which tests were conducted are designated as Wells 1 through 3. Well 2 was located 440 ft north of Well 1, and Well 3 was located approximately 880 ft west of Well 1. Wells 1 and 2 were completed with cable tools, while the producing interval of Well 3 was rotary cored using fresh water as the drilling fluid to obtain oriented cores. Tests were divided into separate phases on each well as the fracturing program progressed and consisted of measurements performed prior to treatment, during and after the formation breakdown operation. during fracture treatment and after treatment. To verify location and azimuth of the fracture created, and to obtain an impression of wellbore irregularities, a packer was used (Fig. 1). This packer was lowered on tubing into the wellbore opposite the interval under study and inflated in stages to allow the impression material to conform to the wall of the wellbore. A magnetic compass was attached to the tool for orientation reference. Impressions made prior to treatment showed no existing fractures in the wells under study. Impressions made after both formation breakdown and treatment pro-

By H. M. Strong

Nickel and carbon form a metastable nickel-nickel carbide eutectic system which was ohsen)able by freezing latent-heat arvests at pressures 210 khars. The eutectic freezing temperature Is pressure had a slope of -0.9°Cper kbar. At 50 khars, the nickel-nickel carbide eutectic was at 1297° * 5°C and 0.34 mole fraction Ni3C. The composition of the eutectic increased at an initial rate of 0.004 mol fraction per kbar. The carbon content of the a phase also increased with pressure. Seveval illustrations of nickel carbide microstruc-tures are given and data on the lattice expansion of nickel in terms of carbon content are included. IRON, cobalt, and nickel form a variety of carbides with compositions varying between MeC and MC. Of the three, the carbides of iron are most easily recovered. The nickel carbides are so unstable at temperatures above 900°C that their occurrence in Ni-C alloys is unusual. Under sufficient pressure, however, the temperature range for the stability of the ferrous metal carbides is likely to be increased, or their decomposition suppressed (e.g., see Hilliard' on FesC), providing an opportunity to study the unstable carbides more closely. This was found to be true for nickel carbide which, under pressure, formed a eutectic with nickel. This paper describes the conditions of formation of nickel-nickel carbide eutectic compositions and their subsequent recovery. Despite the comparative instability of the nickel carbides, something is already known about them through various chemical reactions at temperatures not exceeding a few hundred degrees, and from their recovery by the very rapid quenching of molten Ni-C alloys from temperatures of about 1450°C or above. At least four carbides of nickel have been reported: A discussion of the state of knowledge about Ni3C is given by ansen.' The studies of Morrogh and williams7 who obtained Widmanstatten nickel carbide structures and of sidorenko8 who first obtained nickel carbide eutectic structures are also of interest. Sidorenko used short heating times for molten nickel in a graphite crucible followed by very rapid quenching to obtain the eutectic structures. Long heating times produced only the nickel-graphite eutectic probably due to the presence of graphite crystals in the melt which nucleated graphite crystallization. According to the early work summarized by anssen,' nickel carbide may form at temperatures far above the melting point and may be recovered by very rapid quenching. More recently, Giardini and Tydings, working on diamond synthesis, found evidence for "free nickel carbide'' in high-pressure reactions carried to temperatures far in excess of the limit for diamond growth, followed by rapid thermal quench. They stated that nickel carbide was not found in association with diamond growth. In the present work, observations were made on the melting and solidification temperatures of Ni-C alloys as a function of composition, temperature, and pressure. The nickel-nickel carbide eutectic was found at pressures above 10 kbar and its variation with pressure followed up to 60 kbar. Nickel-nickel carbide microstructures were recovered by quenching under pressure from temperatures of about 1400°C and higher. The formation of nickel carbide structures under ordinary diamond-growing conditions was usually observed but the role of carbide formation as an intermediate step in diamond growth needs more study. EXPERIMENTAL METHODS The melting and solidification temperatures of various nickel-graphite compositions were observed by latent-heat arrests in the sample holder illustrated in Fig. 1. The samples were composed of mixtures of carbonyl nickel powder and National Carbon Co.'s SP-1 graphite packed to densities of about 6.4 g per cu cm. They were contained within

Jan 1, 1965

By Nelson W. Taylor

With the extensive deposits of potash minerals which have been discovered in the southwestern states, and their rapid development, a permanent American supply of potassium compounds is now assured. The 325-year history of the potash industry in this country has been told by H. I. Smith1, of the U.S. Geological Survey, and the more recent activities of the Survey and of American potash companies were described last year by the same author2. In fact, it may be stated that so great is the productive capacity that two mines in New Mexico and one in California are able to supply more than half a million tons of crude and refined salts over and above that produced for agricultural purposes. The era of scarcity has given way to an era of superabundance. This situatiori makes it desirable for the potash producer to look for other applications for his product, and it is with this in mind that the writer presents some information pertaining to present and possible future uses for potassium compounds in the ceramic industry. Ceramic Products Ceramic products are essentially solid materials containing one or more oxides such as SiO2, Al2O3, CaO, MgO, FeO, K2O, Na2O, TiO2, which are the oxides of greatest abundance in the earth's crust. The typical ceramic process is that of firing or burning the batch, and the product may be glassy, crystalline or mixed. In the glassy or vitreous group come glass, porcelain enamel and glazes; in the crystalline group, refractory materials such as silica brick, or chromite or magnesia; and in the mixed group, porcelain, chinaware, stoneware, tile, brick, etc., which contain both a vitreous and a crystalline phase, in variable proportions. The ceramic industry of the United States is a billion dollar industry, and is important not only because of its magnitude but also because of the key position occupied by certain ceramic products in the whole manufacturing structure. From the standpoint of use of potash, the field of refractories is of no great interest, since K2O lowers the melting point of a refractory oxide and

Jan 1, 1938