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By J. D. Miller, J. E. Sepulveda

Tar sand deposits in the state of Utah contain more than 25 billion bbl of in-place bitumen. Although 30 times smaller than the well-known Athabasca tar sands, Utah tar sands do represent a significant domestic energy resource comparable to the national crude oil reserves (31.3 billion bbl). Based upon a detailed analysis of the physical and chemical properties of both the bitumen and the sand, a hot-water separation process for Utah tar sands is currently being developed in our laboratories at the University of Utah. This process involves intense agitation of the tar sand in a hot caustic solution and subsequent separation of the bitumen by a modified froth flotation technique. Experimental results with an Asphalt Ridge, Utah, tar sand sample indicated that percent solids and caustic concentration were the two most important variables controlling the performance of the digestion stage. These variables were identified by means of an experimental factorial design, in which coefficients of separation greater than 0.90 were realized. Although preliminary in nature, the experimental evidence' gathered in this investigation seems to indicate that a hot-water separation process for Utah tar sands would allow for the efficient utilization of this important energy resource. The projected increase in the ever-widening gap between the domestic energy demand and the domestic energy supply for the next few years has motivated renewed interest in energy sources other than petroleum, such as tar sands, oil shale and coal. Although a number of research programs on the exploitation of national coal and oil shale resources have already been completed, very few programs have been initiated on the processing of tar sand resources in the United States. In recognition of their significance as a domestic energy resource, investigators at the University of Utah have designed an extensive research program on Utah tar sands. An important phase of this program, and the main subject of this publication, is the development of a hot-water process for the recovery of bitumen from Utah tar sands, as a preliminary step toward the production of synthetic fuels and petrochemicals. The term "tar sand" refers to a consolidated mixture of bitumen (tar) and sand. The sand in tar sand is mostly a-quartz as determined from X-ray diffraction patterns. Alternate names for "tar sands" are "oil sands" and "bituminous sands." The latter is technically correct and in that sense provides an adequate description. Tar sand deposits occur throughout the world, often in the same geographical areas as petroleum deposits. Significantly large tar sand deposits have been identified and mapped in Canada, Venezuela and, the United States. By far, the largest deposit is the Athabasca tar sands in the Province of Alberta, Canada. According to the Alberta Energy Resources Conservation Board (AERCB),2,3 proved reserves of crude in-place bitumen in the Athabasca region amount to almost 900 billion bbl. To date, this is the only tar sand deposit in the world being mined and processed for the recovery of petroleum products. Great Canadian Oil Sands, Ltd. (GCOS) produces 20 million bbl of synthetic crude oil per year. Another plant being constructed by Syncrude Canada, Ltd. is expected to produce in excess of 40 million bbl of synthetic crude oil per year. According to the Utah Geological and Mineral Survey (UGMS), tar sand deposits in the state of Utah contain more than 25 billion bbl of bitumen in place, which represent almost 95% of the total mapped resources in the United States.4 The extent of Utah tar sand reserves seems small compared to the enormous potential of Canadian tar sands. Nevertheless, Utah tar sand reserves do represent a significant energy resource comparable to the United States crude oil proved reserves of 31.3 billion bbl in 1976.5 Tar sands in Utah occur in 51 deposits along the eastern side of the state.4 However, only six out of these 51 deposits are worthy of any practical consideration (Fig. 1). As indicated in Table 1, Tar Sand Triangle is the largest deposit in the state and contains about half of the total mapped resources. Information regarding the grade or bitumen content of Utah deposits is still very limited. The bitumen content varies significantly from deposit to deposit, as well as within a given deposit. In any event, the information available6-8 seems to indicate that Utah deposits are not as rich in bitumen as the vast Canadian deposits which average 12 to 13% by weight.9 Although many occurrences of bitumen saturation up to 17% by weight have been detected in the northeastern part of the state (Asphalt Ridge and P. R. Spring), the average for reserves in Utah may well be less than 10% by weight. Separation Technology As in any other mining problem, there are two basic approaches to the recovery of bitumen from tar sands. In one

Jan 1, 1979

By R. D. Pehlke, J. F. Elliott

The equilibrium pressure of nitrogen gas over pure silicon metal and silicon nitride has been measured in the temperature range 1400° to 1700°C. From the experimental data, the standard free energies and enthalpies of formation of Si3N4(a) have been calculated as functions of temperature over the above temperature range. Utilizing data in the literature and the results of this investigation, the specific heat, molar enthalpy, molar entropy, standard enthalpy of fornation, and standard free energy of fornation are estimated for the temperature range 298° to 1400°C. THE high-temperature thermodynamic properties of many metallic nitrides are not well established at present. This is a serious deficiency because nitrogen and nitride-forming metals are important alloying additions to steels, and knowledge of the interaction between nitrogen and these elements is essential to a better understanding of the behavior of steels. Metallic nitrides also are used as refractory materials. Consequently, the investigation reported here was undertaken to provide more complete information on the standard entropy and free energy of formation of silicon nitride. The experimental technique provided a direct measurement of the equilibrium pressure of nitrogen gas in the range of 1413 to 1700°C for the reaction: 3 Si(1) + 2N2 (g) = Si3N4 (a) [ 1 ] and below 1413oC for the reaction: 3Si(c) + 2N2(g) = Si3N4(a) [2] APPARATUS The experimental system consisted of a crucible assembly, a reaction chamber, and a gas supply and vacuum system. The Crucible Assembly which contained the equilibration specimen and molybdenum radiation shields with a susceptor for induction heating is shown in Fig. 1. Two covered, high-purity alumina crucibles, one nested within the other, contained the susceptor, shields and specimen. Central openings in the upper shield and crucible covers permitted on optical pyrometer to be sighted into the central cavity of the specimen. The specimen itself was a 5/8 OD by 1-in.

Jan 1, 1960

By L. G. Westgate

PART I.-AREAL GEOLOGY§ PIOCHE lies 240 mi. southwest of Salt Lake City, in southeastern Nevada, 19 in. west of the Nevada-Utah line. It is at the end of a branch line (33 m.), which connects at Caliente with the Los Angeles and Salt Lake division of the Union Pacific System. Its commercial relations are with Salt Lake City and Los Angeles, chiefly with the former. The surrounding area is part of the Great Basin, an arid region of alternating mountain range and intermont plain, the latter floored with outwash from the mountains. About Pioche the plain varies between 4700 and 6000 ft. above sea level. The town lies in a valley at the east base of a low northwest-southeast range (the Pioche Hills) 12 miles in length, which rises about 1000 ft. above the adjacent flat. West of the. Pioche Hills is a higher north-south range consisting of two parts: to the south the Highland Range, between Bennett Pass and Stampede Gap; to the north the Bristol Range, from Stampede Gap to Bristol Pass. This double range reaches altitudes of 8000 to 9000 ft., or more, (the highest point, Highland Peak, is 9395 ft.) and rises some 2500 ft. above the surrounding plain. It is continued in lower hills to north and south. Smaller ranges rise from the flat west of the Highland and Bristol ranges. The area studied and shown on the map (Fig. 1) is covered by 3 one inch to the-mile topographic sheets: the Highland Range, the. Bristol Range, and the Panaca, the latter mapped in part only. The sedimentary rocks of the district include Paleozoic limestones, sandstones and shales, Pliocene tuffs, and modern wash. Igneous rocks are represented by intrusive dikes and stocks and by extensive lava flows of mid-Tertiary time.

Jan 1, 1927

By E. A. Holbrook

RESEARCH, primarily, is finding out the truth. Research applied to engineering opens the door to new principles and processes, the application of. which benefits mankind in a material way. The engineer believes that investigation instituted with the primary view of making the results directly applicable to the industries is the highest type of research. Coal is essentially the basis of modern industrial civilization; therefore, any, considerable research pertaining to coal must link itself to the industry by, practical application of the results of the research. In other words, all investigational work connected in any way with coal leads to conclusions that permit a better understanding of the origin, nature of occurrence, composition, better and safer mining, more careful preparation, or greater efficiency in utilization of coal. Modern engineering research has been fostered essentially by universities and in the laboratories of institutions of learning. Coal problems that lend themselves to solution in the laboratories have been first attacked and are perhaps the farthest toward solution. For example, a great amount of research work has been carried out with the various phases of chemistry connected with coal. On the other hand, the equally important problems connected with methods of mining have received but little attention, primarily because their solution involves the continued use of a great and expensive laboratory, which is none other than the mine itself. As many of the problems already solved have had chemistry as their background, so many of the problems unsolved have physics as their background; there are also unsolved problems that deal in- coal economics. Even psychology must be called upon in future coal-mining research as a basis for solving those great problems that deal with human relationships. In general, considerable advance has been made in coal research dealing with chemistry, not so much progress has been made with problems having physics and engineering as a background, while there is a tremendous range of untouched problems that deal essentially with business and psychology.

Jan 9, 1919

By H. C. George

THE Wisconsin. Zinc District, or the Upper Mississippi Lead and Zinc District as it is often called, lies in the southwestern corner of Wisconsin, in, Grant, Iowa and Lafayette Counties, and it includes adjoining parts of Illinois and Iowa. The district is about 70 miles long, north and south, and about 40 miles wide, east and west. It lies wholly within what is geologically known as the non-glaciated area of the Upper Mississippi Valley. HISTORY OF THE DISTRICT The district was first opened up as a lead producer in 1822. From this time until 1860, about 205,000 tons of cog lead (galena) and washed lead (galena) was produced from shallow crevices and openings. From 1860 to 1900, about 74,500 tons was produced, and since that time, from 5000 to 7000 tons has been produced annually. Since-1900, most of the lead concentrate produced has been as a byproduct of the zinc mines. The first zinc ores were mined about 1862. These were the carbonate ores, locally known as " drybone." Very little zinc blende was mined in the district, previous to 1875. The zinc blende ores mined from 1875 to 1900 were mostly of the high-grade, hand-cobbed, sheet-ore class, which usually contained from 45 to 60 per cent. metallic zinc. Such nines as the "Sallie Waters," ? Quinlin," "Lead Mine," "Benton Blende" and "Ida Blende," located near Benton, Wis., were mines which produced ores of this type, during this period. The mines located at Highland, the "Coker Mine" located at Livingston, Wis., and the "Opencut Mine" located at Shullsburg, Wis., were mines that were heavy zinc carbonate producers, previous to 1900.

Jan 12, 1917

By Chester Purington

THE AUTHOR hopes that this paper will meet with criticism and debate by fellow members of the Institute rather than with that attitude of passiv-ity and indifference which one is inclined to adopt when considering a field completely foreign to one's own experi-ence. After several years of study of voluminous literature, maps, and statistics, and many personal journeys and field inspections of various parts of Siberia, the conclusion is reached .that the area adjacent to the Stanovoi, Zhugd-Zhur, and Yablonoi ranges as below defined is that which .is most accessible to the western world and will soonest give results from exploration. HISTORY The first incursion of the Russians into Siberia east of the Yenesei River appears to have been in 1632 when the fort of Yakutsk was founded on the middle Lena. The early expeditions were in quest of furs. As the Siberians say, "the sable beckoned" and the post of Anadyr was founded in 1639, two thousand miles further northeast. Thus nineteen years after the Pilgrims landed in Massachusetts, the Russians had established a trading post within 700 miles of what is now the town of Nome, Alaska. Parties of Cossaks penetrated to the shores of the Okotsk1 Sea early in the seventeenth century, but it was not until 1688 that the town of Okotsk was founded. In 1712 a grand project was elaborated at St. Petersburg for building a port at Okotsk, but it came to nothing. Vitus Bering, the Alaska explorer, built ships at Okotsk, and made this his point of depar-ture. It is stated that the iron work used in these ships was brought overland partly from Yakutsk, and partly even from St. Petersburg, 5500 miles away. Accord-ing to report a copper deposit was worked on the river Urak, not far from the coast, and copper was smelted for sheathing the bottoms. Grassgrown mounds con-taining slag and shots of copper were inspected by the writer last summer, at the site of the ancient shipyard.

Jan 11, 1923

By J. T. Price

The study was undertaken to investigate the effect in the charge to a blast furnace of zinc and alkali contents, which tend to form accretions and scaffolds in the upper sections of the furnace. Commercial iron oxide pellets were reduced in a CO:N2, 40:60 gas mixture in a 5-cm by 5-m counter-current reactor (Rist-type apparatus) designed to simulate blast-furnace conditions. Pellets from a commercial magnetite concentrate were prepared in the laboratory with zinc (1% ZnO) and alkali (1% KOH) additions to the concentrate. Reducibility, crushing strength and swelling tests were carried out and the results compared with test data from pellets prepared without additions. The results indicated normal behaviour for those pellets containing zinc, whereas those containing alkali swelled catastrophically under the same reducing conditions.

Jan 1, 1977

By N. H. Fisher

GEOGRAPHICAL DISTRIBUTION THE most important known deposits in Australia of what are commonly referred to as the beach-sand minerals are along the most easterly part of the Australian coast, between Southport, 17 miles north of the Queensland-New South Wales border, and Ballina, 50 miles south of the border, and most of the production has come from this area (Fig 1). Smaller deposits are known to occur farther to the south at intervals for several hundred miles, and beaches have been worked at Yamba, 96 miles south and Woolgoolga, 150 miles south of the border and at Swansea, 60 miles north of Sydney. Important deposits have been shown to exist on north Stradbroke Island and others have been located farther to the north, as far as Tin Can Bay at the south end of Frazer Island. (Fig 2). Table I gives the list of operators with the location of their deposits and workings, their approximate maximum monthly capacity expressed in tons of heavy mineral produced by their concentrating plants before separation into individual mineral concentrates, their methods of mining and concentrating the minerals, and the products obtained. This table applies as of June 1948, but all the operators are remodeling or improving their plants and plant practices will be modified accordingly. In addition, active boring campaigns have been carried out by Alluvial Gold, Ltd., of Sydney, in the Cudgen-Cudgera area, and by Zinc Corporation. Ltd., of Melbourne, on Stradbroke Island, and in other places. PHYSIOGRAPHY Submergence of the order of 100 to 200 ft at the close of the Pleistocene period left the pre-existing hills as promontories and the valleys as deep inlets. Wave action has built bay-bars and sandspits in a northerly direction from the headlands, and lakes and marshes have formed between these bars and the initial post-submergence coast line. These lakes and swamps have been or are being filled in by river-borne sediments or wind-blown sand. Beasley1 has presented evidence that suggests a recent emergence of the coast line of about 10 ft. The evidence for this belief is the presence of a black sand seam 1/3 mile inland and 17 ft above sea level (Fig 3), and although it is not entirely certain that this seam is of beach formation and owes nothing to windblown concentration, other evidence supports the suggestion of recent emergence. Such emergence would undoubtedly aid the formation of bars and sandspits and the easterly progress of the beach front, leaving a series of parallel dunes (Fig 4). This belt of north-south coastal dunes ranges up to 1/2 mile in width and as many as 15 lines of dune have been counted (Fig 3). The foredune is generally the highest, up to 25 ft high, and there is in many places a flat platform in front of the dune known as the berm. The dunes behind the foredune are lower and less well defined

Jan 1, 1947

By C. D. Henry, M. L. W. Jackson

Environmental geologic maps of the Wilcox and Jackson-Yegua lignite belts of the Texas Coastal Plain delineate land areas on the basis of their natural characteristics. Criteria used to define map units include substrate, soil, topography, geologic process, vegetation, and land use. The maps are useful in planning and reclamation of lignite mines and in meeting the requirements of state and federal surface mining laws. Specific applications include identification of land capability, recharge areas and geometry of aquifers, flood-prone areas, areas that may qualify for prime farmland status, and other areas sensitive to lignite mining.

Jan 1, 1984

By Donivan L. Gordon, Fred H. Dorheim

Often, as viewed by the public and many in the mining industry, abandoned limestone and gypsum quarries offer a simple, economic solution to the twofold problem of solid-waste disposal and land reclamation. In a state where about 75% of the existing quarries are in hydrologic connection with carbonate aquifiers the rationale for considering the storage of solid waste in them must be critically examined. Consistent with the requirements of water resources protection, criteria are suggested to evaluate the potentiality of using abandoned limestone and gypsum quarries as sanitary landfill sites.

Jan 1, 1975

By H. B. Pulsifer

The unprecedented high price of zinc ore prevailing through the early months of 1915 caused great activity in the Joplin district of Missouri. The Media mill is conspicuous as one of the first of the new "big mills" of the district. The mill was built over a mine previously worked but abandoned in 1912 because of the leanness of the ore and the large quantity of water encountered. The ore prices prevailing—$100 a ton in June, 1915, as against $50 in 1912-—favored the new undertaking. The mill was designed for good recovery so that it might operate in times of depression. In design and equipment, the mill is exclusively local in conception and construction. Former Exploitation The tract of land is a part of the large Guinn holdings; 70 acres are comprised in this particular lot, which is situated just a mile north of the center of Webb City on the Alba line of the Southwest Missouri Electric Railway. The ore lies 242 ft. below the surface at the top of the knoll which is surrounded by the well known properties: Black Cat, Ground Floor, Florence, Hurry-Up, Electrical, and Mercantile. Since the abandonment, in 1913, of the Yellow Dog a bit farther to the north, the Black Cat, Ground Floor, and Florence workings had been flooded. However, as there was no cut through from this side into the area it was proposed to exploit, it was thought that moderate pumping facilities would take care of the water. Three shafts had already been sunk to the ore horizon during the previous operations; the ground was connected by wide drifts and possibly 10 acres mined out, principally about the two southerly shafts which at surface are 8 and 13 ft. lower, respectively, than the collar of the shaft at which the new mill was built. The former mill on the lease was known as the Bohemian Girl. This mill, built in 1910, was removed after some 3 years' work. A head frame and hopper still existed at the middle shaft, sometimes known as the lower Hold Out shaft, but at the most northerly

Jan 1, 1918

By James A. Barr

[CONTENTS PAGE Foreword. By JAMES A. BARRI A New Core Barrel for Prospecting for Phosphate in Florida. By I. M. LEBARON 2 Prospecting for Phosphate in Tennessee. By W. F. GUENTHER 6 Machine Prospecting in Tennessee Brown Phosphate. By H. O. PICKARD, JR8 Diamond Drilling through Flint Horizons in Tennessee. By HENDON R. JOHNSTON9] Foreword PROSPECTING methods used in Tennessee have gradually improved with the years, as required by depletion of the easily accessible and shallow deposits and the universal trend toward mechanization, and as necessitated by exploring deeper beds, often occurring under limestone and flinty overburden. In the early days it was a very simple matter to dig pits by hand, using a plentiful supply of local farm labor to expose relatively shallow deposits of "brown rock" under shallow clayey overburden that would stand up without timbering. Visual inspection of the exposed phosphate and expert judgment of the"grade" analysis, aided by a "biting" test to reveal presence of unwanted silica, furnished most of the information required. All this might be helped by a few samples sent to the local chemist[t] who supplemented his income by judicious trading or tanning a few bear skins. The extra curricula activities did not affect the accuracy of the analysis which hold up even under present day standards. Some shot and core drilling was done in Hickman County, mostly for the limestone-like blue Phosphate deposits. The next step was the use of a 4-in. posthole auger, hand operated as described by Guenther, followed by- a completely mechanized rig, as described by Pickard. Both these methods are practically adapted to the prospecting of the relatively soft brown rock deposits at moderate depths of clay overburden. For prospecting in areas of deeper overburden, such as are often found in Hickman County, up to 150 or even 200-ft depths, a modified core-drilling method is described by Guenther. Johnston describes a special diamond-drilling technique, developed by TVA, to penetrate flint horizons, which was adopted by the International Minerals and Chemical Corporation to prospect in Hickman County where deposits had previously been prospected at considerable expense and with difficulty, by Small, temporary, hand-dug shafts.

Jan 1, 1947

By J. M. W. Mackenzie

A microelectrophoresis technique has been used to measure the zeta potential of quartz over a range of pH and ferric iron concentration. The results have been discussed in terms of the adsorption of ferric cations and ferric hydroxide to the quartz surface. Possible relationships between the experimental results and the flotation of quartz have been examined. The adsorption of multivalent cations at the surface of quartz has been studied by many investigators who have used a variety of experimental techniques ranging from streaming potential 1 to radiometric2 measurements. Two possible mechanisms of cation activation of quartz have emerged from the results of these investigations viz: the adsorption of the cation to the negatively charged quartz surface, followed by adsorption of the collector anion to the adsorbed cation site, or: formation of a cation-collector complex which is then adsorbed to the quartz surface. In many natural and industrial systems one of the most prevalent activating species for quartz is ferric iron, this is especially so in the acid-circuit, anionic flotation of iron ore. The adsorption of ferric iron to the quartz surface is complicated by the ability of ferric iron to form complexes with anions, a phenomena which is of minor importance in one of the most widely studied quartz activation processes, ca ++ activation.* *The pK value for [ca(oH)+]/ [ca2+] [oh-] is 1.46 indicating that the influence of Ca (OH)+ ions will be minor in all but strongly alkaline solutions. In order to obtain a better understanding of quartz activation by ferric iron the zeta potential of quartz in the presence of ferric iron has been measured over a range of pH and ferric iron concentration. EXPERIMENTAL METHODS Materials: Selected samples of "rock clystal" quartz from New England, N.S.W., were ground in a pebble mill, washed for three hours in boiling concentrated hydrochloric acid, washed in hot chromic acid and then washed repeatedly with distilled water until the washing water gave no trace of chloride ion.

Jan 1, 1967

By Roderick K. Davey

Introduction in any business, it is essential that we select those alternatives which are not only technically feasible, but will be the most profitable to the business m terms of corporate objectives Some of the studies and activities requiring support of financial analysis to select the alternatives which most closely satisfy the management objectives and technical considerations are as follows 1 ) Cutoff grade determination. 2) Ore reserve estimation. 3) Production forecasts (long- and short-term) for an operating mine, development of a new mine, or expansion of an existing mine. 4) Evaluation of haulage alternatives. 5) Evaluation of equipment.

Jan 1, 1979

By W. D. Robertson, R. E. Reed-Hill

Slip on (11221 planes, which do not contain a close-packed direction, has been identified on crystals strained at —190°C. Evidence is also presented to show that (1071) pyramidal slip is a mode of deformation at 25ºC in a limited orientation range. PYRAMIDAL slip (l011) <1120> in magnesium at elevated temperatures has been established for some time.1-2 More recently, Burke and Hibbard reported this mode of deformation at 25ºC, but their results were questioned by Craig.&apos; Also, as far as the present authors know, slip in magnesium on pyramidal planes of the second order, Type II (1122)) has not previously been reported, although Gilman"," identified (1122) slip in another hexagonal metal

Jan 1, 1959

By W. H. Schacht

The operations of the Copper Range Co. are located in the Michigan copper district at the southern end of the Keweenaw Peninsula, 8 miles southwest of Hough ton (the center of the district). All the producing mines are situated in a long narrow zone paralleling the peninsula and occupying the central portion. This zone is about 25 miles long and 3 to 4 miles wide. The important mines, in their order from northeast to southwest, are, Mohawk, Ahmeek, Allouez, North Kearsarge, Wolverine, South Kearsarge, Centennial, Calumet & Hecla, Osceola, Franklin, Quincy, Isle Royale, Baltic, Trimountain, and Champion; the last three are operated by the Copper Range Co. The existence of copper deposits in this district became known soon after the discovery of America. Many references by early explorers show that copper was found in the possession of many of the American Indians that inhabited the Great Lakes region. There is abundant evidence that exploration of these copper deposits extended into prehistoric times; and some indication that the American Indians carried on operations shortly before the advent of white men. An account of the finding of primitive mining appears in the Government publications of 1850-51 by Foster and Whitney. Although earlier expeditions by white men had been made to the Keweenaw peninsula, an attempt to commercialize the district was not made until after 1765, when Alex. Henry, a British subject, searched the shores of Lake Superior for mineral treasure. His first expedition took him to the Ontonagon River, where he found the famous mass of copper now on exhibition at Washington. In 1771, he started operations along this river with a crew financed by English capital; but after much difficulty and only meager success he found only detached masses while in search for a major deposit. There is no record of any cxploration from 1774 to 1820. In 1838, Dr. Douglas Houghton was appointed state geologist. Prior to that time he had made several visits to this region; and was the first white man to find

Jan 1, 1925

By John F. Burst

Nanafalia aged bauxitic kaolins which straddle the Chattahoochee River in a NE-SW trending line anchored by Eufaula, Ala., and Andersonville, Ga., apparently derive from the same Piedmont source. A genetic interpretation is offered which describes the Nanafalia as a shoreline deposit in which the blanket elastics of the Andersonville area represent an ancient freshwater swamp and the lenticular Eufaula bauxites represent meander fills in an ancient tidal flat or barrier island. Mining operations in both areas are described and economic forecasts are presented.

Jan 1, 1975

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962

By E. Marburg

Most ingots complete solidification vertically rather than transversely. This conclusion is based on complete solidification patterns of big-end-up and big-end-down ingots developed from dumped and split ingots. New mechanisms for segregation in ingots are proposed. Internal soundness in ingots is found to depend upon adequate width of vertical core. A LTHOUGH it has long been recognized that the A internal soundness of ingots is principally been recognizedthatthedependent on the process of solidification, knowledge of this process is still only fragmentary. The mechanisms causing the several types of segregation in ingots, which mechanisms are necessarily related to the solidification process, are not well understood. In absence of a better conception of the solidification process, it seems hardly surprising that mold design varies widely. Guiding principles for mold design are needed. At stake in the improvement of ingot quality are not only improved properties of steel but also appreciably higher yields of sound steel, which would considerably decrease manufacturing costs. In the present study, following a general description of the several types of segregation in ingots, Fig. 1, complete solidification patterns of a big-endup and a big-end-down ingot, including the zones of accelerated solidification, have been reconstructed. In both ingots, a core of vertical solidification extends from the base cone to the hot-top junction. Based on the finding that ingots complete solidification vertically rather than transversely, as has been previously assumed, new mechanisms for segregation in ingots are proposed. Internal soundness in ingots is found to depend upon the width of the vertical core, which in turn depends principally upon the width to height (w/h) ratio of the ingot. Solidification patterns of ingots are of three general types: 1—those in which vertical solidification does not reach the top, 2—those in which vertical solidification just reaches the top of the ingot, and 3—those in which vertical solidification reaches the top some time before transverse solidification would reach the middle of the ingot, so that a vertical core of definite width at the top of the ingot is developed. Axial defects vary characteristically with the solidification pattern. Examples of ingots of each type are presented. Dumped ingot data reported by Nelson&apos; have been used in developing families of curves of transverse and vertical solidification, and in deriving the effect of the w/h ratio upon the solidification pattern. Photographs of many ingots split at Homestead and at Duquesne Works, United States Steel CO., as well as those published by the British Iron and Steel Institute,&apos; have been studied and analyzed. In the interest of brevity, only typical ingots of each type or classification from the above sources have been reproduced. Segregation in Ingots Segregation in ingots falls into three principal classifications: 1—lamellar segregation, as revealed in sulphur prints (Figs. 2 and 3); 2—zone segregation, or broad variations in composition; and 3— interdendritic, or microsegregation. The last class, of minor importance, is not considered here. When liquid metal cools, according to the theory of differential or selective solidification,2 metal of relatively high purity selectively solidifies first. Liquid segregates (principally carbon, phosphorus,

Jan 1, 1954

By E. P. Klier

The work of Klier and Lyman1 on the bainite reaction has led to the full description of this reaction for medium-carbon low-alloy steels. Certain experimental data reported by Klier and Lyman appear, however, to be improbable of obtaining in very high-carbon steels. The study herein reported consists of an analysis of the transformation characteristics of a 3 per cent chromium, I per cent carbon steel by means of X-ray and metallographic methods. From the results obtained it is concluded that the bainite reaction in this steel is more complicated than that reported by Klier and Lyman for the low-carbon low-alloy steels. Henever, the mechanism of bainite formation in this steel appears to be essentially the same as proposed for the low-carbon low-alloy steels with the modification that the first volumes to transform are carbon-rich rather than carbon-poor. Experimental Procedure The analysis of the steel studied was: Cr, 2.89; C, 1.02; Mn, 0.33; Si, o.35; S, 0.012; P, 0.020. The stock was received from the Carpenter Steel Co. in rolled bars. Specimen Preparation Specimens were austenitized at 1200°C. (2192°F.) for 25 min. in purified nitrogen. The resultant A.S.T.M. austenite grain size was 0-1. Isothermal transformation was allowed by quenching the specimens into liquid metal baths controlled to 5°C. at 540°C. (1004°F.) and above, and to 2°C. at 490°C. (914°f.) and below. Following the desired degree of transformation all specimens were water quenched. Metallographic Examination Specimens 1/4 in. round by 1/4 in. were used for nietallographic examination. Etch-ants used were Vilella&apos;s reagent (I gram picric acid, 10 ml. hydrochloric acid to make 100 ml. ethyl alcohol solution) and alkalinc sodium picratc (electrolytic). Vilella&apos;s reagent was effective in revealing all microconstitucnts, while the alkaline sodium picrate developed the carbon-rich structures or carbides only. X-ray Examination Two X-ray techniques were used—the Debye-Scherrer method and a back-reflection method. &apos;The small specimens necessary for the Debye-Scherrer method were austenitized and then allowed to transform, or were cut from the larger metallographic specimens. The metallographic specimens were used for the back-reflection X-ray analysis. When it was desirable to determine the structure of the carbide present, sliver specimens were electrolytically etched to develop a carbide coating, then were exposed in the cameras. This technique was frequently necessary to allow positive identification of the carbide.

Jan 1, 1945