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By A. U. Seybol

Eight binary iron alloys were examined after ion nitriding experiments to determine the behavior of the following elements: Al, Mo, Mn, Si, Ti, V,Cr, and C. Only Al, Cr, Ti, and V additions caused hardening in binary iron alloys. A few steels were examined to see the effect of Cr, Cr + Al, Cr + Ti, and Cr + V. It is suggested that a useful new class of ni-triding grade steels might be those containing about I pct V. The nitriding of steel, first described by Fry1 about 45 years ago, rapidly attained commercial application with very little knowledge of the fundamentals involved. While Fry,' in describing the status of nitriding in 1932, apparently correctly postulated hardening by precipitated nitrides, the details of the nitriding process were not understood, nor has the situation changed much since that time. It is also interesting to note that the compositions of some typical nitriding steels given by Fry at that time have changed little in the intervening years. Currently used nitriding steels owe their surface hardening to either chromium (as in 4340 steel) or aluminum plus chromium as in the Nitralloy grades, where both CrN and AlN appear to contribute to harden ing. Titanium additions have been studied experimentally, but thus far titanium steels have not won wide commercial acceptance. This subject will be expanded later. The orthodox ammonia nitriding process has been reviewed very adequately many times as in Jenkins3 and Case and VanHorn,4 and their is no need to outline the process here. Ion nitriding is not as well-known, although there have been several descriptions5-9 of the process given, sometimes with comparisons with the ammonia process. Most of these papers are primarily concerned with a description of the equipment, or of the physics or electrical engineering aspects of ion nitriding, but Noren and Kindbom9 gave the results of a metallurgical investigation using both processes. In brief, ion nitriding is carried out in a vacuum chamber from which the air is exhausted and replaced by a N2-H2 mixture, typically containing 10 to 20 pct N2, at about 5 to 10 torr pressure. While ammonia gas has also been used in ion nitriding, there is no evidence that ammonia makes any improvement in the ion nitriding process. A few hundred volts dc is applied between the grounded container wall (positive) and an insulated center post supporting the work (negative) to be nitrided. A glow discharge is created in the ionized gas, accelerating positive nitrogen ions to the work. These ions contain enough energy to form the normally unstable Fe4N "white layer", thus establish- ing surface nitrogen solubility characteristic of the a Fe/Fe4N equilibrium. This creates a substantial concentration gradient, driving dissolved nitrogen into the steel. The temperature employed is in the same range (around 500" to 550°C) as in ammonia nitriding, but because of factors which are not understood at present the nitriding time is ordinarily considerably reduced in ion nitriding. Other advantages have been cited,9 but it is not the purpose of the present work to contrast the two processes. The present objective was to examine the behavior of binary iron alloys during ion nitriding with respect to the microstructure, hardness level, and depth, and to examine some of these factors in steels as well. In this way it was hoped to be able to find out something about the individual role of these elements in steels. While all the work was done by ion nitriding, there seems to be no reason why any conclusions reached would not equally apply to ammonia nitriding, excepting only the kinetic aspects of the process. Another objective was an exploration of the critical-ity of the ion nitriding variables: gas composition, pressure, temperature, and time. EQUIPMENT AND MATERIALS The equipment used was substantially as described by Jones and Martin.8 The vacuum tank was about 12 in. in diam by about 18 in. high, and consisted of water-cooled stainless steel, with a single small window at the top for viewing inside. This sat on a heavy mild steel base equipped with the main pumping port, pressure control port, and vacuum gaging. A series of variable resistances was interposed between the glow discharge and a large-capacity -40 amp variable primary transformer feeding a 1000-v transformer, but 600 v were about the maximum ordinarily used. With the small l-in.-round, 4-in.-thick discs used for nitriding, the electrical load was usually about 500 v at 0.8 amp. The specimen temperature was controlled by a stainless-steel sheathed chromel-alumel couple, whose junction was in the steel stool upon which the flat discs were placed. These were ground through 400 Sic paper. Cycling of the temperature controller caused -0.2 amp variation in ion current, providing an ample control band. The binary iron alloys were made from vacuum-melted hydrogen-deoxidized electrolytic iron and alloys of 99.9 pct purity. Cast ll-lb-square tapered ingots were forged and hot-rolled to about 11/4-in.-diam rounds. Discs of 1/4 in. thickness by about 1 in. diam were machined from the rods for nitriding specimens. The following alloys were prepared: 1 pct each of Mn, Mo, Cr, Ti, Al, V, Si, and an Fe-0.8 pct C alloy. EXPERIMENTAL VARIABLES Of the variables total gas pressure, nitrogen partial pressure, temperature, and time, only nitrogen partial pressure was found to be critical to the operation. A critical nitrogen partial pressure was found corre-

Jan 1, 1970

By W. O. Philbrook, H. W. Hosking, N. B. Melcher

Rates and patterns of gas flow in an experimental blast furnace were investigated by measurements, at three levels, of gas compo-sitions and temperatures and by direct determination of gas transit time by a new method employing mercury vapor as a tracer. Infer-ences were drawn about localized reaction zones and the mechanism of the onset of' channeling. LACK of precise knowledge of the nature of gas movement in the blast furnace has always been an impediment to better understanding of the blastfurnace process as a whole. The effects upon operation of various types of charge distribution are very largely brought about by the modifications to gas flow which they occasion. Intelligent evaluation of these effects demands a better understanding of the factors influencing gas flow and the ways in which the flow pattern is altered by conditions existing in the stock column. The same knowledge is required before a fundamental approach can be made to the problem of establishing optimum lines for new furnaces. An experimental furnace is operated at the Bureau of Mines Central Experiment Station, Pittsburgh, Pa. Advantage was taken of experimental operation to conduct an investigation to develop and evaluate methods of study which could be applied later to industrial furnaces. The gas composition and temperature determinations were made as a preliminary study so far as gas flow was concerned but yielded significant information relating to other processes occurring within the furnace. The direct measurement of gas transit times by the mercury-vapor method constituted the major object of the investigation. Development of the mercury-vapor method was carried out while the data on gas composition and temperature were being collected. A complete description of the principle and development of the mercury-vapor method is beyond the scope of this paper but is available elsewhere. The results obtained and some consideration of the method's effectiveness and its potential value in the study of industrial problems will be treated here. DESCRIPTION OF FURNACE The general lines of the experimental blast furnace are shown in Fig. 1. The hearth diameter was 3 ft at the beginning of the investigation, and this was later enlarged to 3 ft 9 in. and finally to 4 ft to increase capacity. Tuyere to stockline height is 21 ft 4 in. The bosh depth is 3 ft 4 in. over which it opens to a width of 5 ft, and this diameter is carried up for 2 ft in a cylindrical section. The inwall batter of 1/2 in. per ft. is considerably less than in larger installations This may have influenced the movement of gaseous and solid materials. The furnace is inside a laboratory building and is charged from outside by a skip and hoist. Feeding into the first of three bell chambers, the stock is distributed by rotating the upper bell, the other two being used to obtain an effective gas seal. Three water-cooled tuyeres, with a nozzle dia-

Jan 1, 1960

By F. M. Stewart

A paper by Hurst and van Ever-dingen in 1949 led to the practical solution of many nonsteady-state flow problems.' Subsequently, applications of this material have been discussed by several authors. The purpose of this note is to outline a simplified direct procedure for water-influx pressure predictions for pressures above the bubble point. The prcposed procedure is unique in that after the "time-conversion factor" and the "influx constant" are obtained, predictions are made without trial and error. The elimination of trial and error is made possible by expressing certain PVT characteristics as explicit functions of pressure. The procedure is applicable to fields producing at pressures above the bubble point and under radial water drive from an infinite aquifer. In the usual applications it is required to predict (1) withdrawals given future pressure history or (2) reservoir pressure, given future withdrawals or production. The theory, assumptions and conditions under which the nonsteady-state solutions hold are covered in the references and are not repeated. The simplified direct procedure outlined here has been developed from published solutions for the so-called "pressure case". A similar direct procedure for the same special conditions has been developed for the "rate case"; however, in this instance the procedure is lengthy and offers no advantage over the trial-and-error solution. Consequently, this paper covers only the procedure based on the pressure case. DISCUSSION Under the pressure case prediction of withdrawals from a water-drive field, given the future pressure history, involves the use of a nonsteady-state water-influx term together with the material balance equation. The solution of a particular problem requires the following steps: (1) division of past pressure and production data into equal time intervals; (2) computation of cumulative water influx vs pressure drop for each time interval of past history using the material balance equation; (3) determination of the best values for the "time-conversion factor" and the "influx constant" by equating the nonsteady-state influx term with the influx computed in Step 2 (this requires a trial-and-error procedure); (4) prediction of influx for a given pressure drop using the influx term and the computed factors from Step 3; and (5) calculation of fluids produced using the predicted influx in the material balance equation. A forecast of the water-oil ratio or water production rate is required to complete the calculation. It is assumed that a reliable estimate of original oil in place is available, as well as the production and pressure history, and data on reservoir fluid characteristics. If the original oil in place is unknown, it may be computed simultaneously with the tinie-conversion influx factors2,3. However, the oil in place so computed may be considerably in error3; consequently, it is usually preferable to use oil in place estimated from pore-volume data unless there is considerable doubt as to its accuracy. The Material Balance Equation Above the Bubble Point Above the bubble point the simpli-

By E. H. Burdick

THE difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated minerals-pyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying I per cent is considered good grade; 0.7 to 0.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of 1.0 per cent W03 is exceptional. Inasmuch as buying specifications demand a 60 per cent W03 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 60 to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent WO3, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1942

By E. V. Potter, H. C. Lukens

In general, during all electrowinning processes, large volumes of gas are liberated at the cathodes of the electrolytic cells. Most of this gas escapes from the electrolyte, but much of it may be absorbed or entrapped in the metal being plated. In many cases, this is not objectionable, but since it is liberated when the metal is heated, it is a potential source of trouble where the metal has to be heated or melted. Since this gas is principally hydrogen, in escaping from a melt it may cause minor explosions and scattering of the molten metal, while in other cases it has been reported to make the metal rise in the molds when cast. Therefore such metals would be more generally useful if all or most of the gas were removed before they were used. In an earlier investigation1 the gas content of electrolytic manganese was determined and methods found for removing most of it without detrimentally affecting the properties of the metal. In this paper results of a similar investigation on electrolytic chromium are presented. Apparatus The apparatus used in these investigations is essentially the same as that used in the manganese work1 and is shown in Fig I. It consists of sample chamber A, vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The pressure in the system is measured by the mercury manometer B. Changes in gas volume are measured by volume gauge C which is essentially another mercury manometer in which the volume of the mercury column is large and can be varied by raising or lowering the well H. In this apparatus the tube had a volume of 100 cc for a 60 cm length. Larger changes in gas volume can be accommodated by auxiliary containers attached to the system at F. The sample is heated by furnace G, the temperature of which is regulated within 5°C by an automatic controller. The only change in the apparatus was the sample container which was made smaller because of the chromium metal's containing more gas than the manganese metal and a smaller sample was used. Method The measurements were made as follows: The complete system when cold was evacuated and refilled with H2 until all the air was removed. It was then refilled with H2 to the desired pressure, as indicated on manometer B. The temperature was then raised to the desired value and as gas was either liberated from or absorbed by the sample, the height of well H was changed to alter the volume of the system so as to keep the pressure constant. In determining rates of liberation of gas, volume readings were taken at convenient tirne intervals depending on the rapidity with which the gas was liberated. In determining total volumes, the specimen was held at constant temperature and pressure until

Jan 1, 1949

By W. E. C. Eustis

1st. THE fine iron ore is mixed with a sufficient proportion of fine coking coal, and is coked in any of the ordinary methods for making coke. The effect of this is to convert the iron oxide into sponge in such a shape that the usual trouble of oxidation is avoided. 2d. The resulting mixture of coke and sponge is melted down in an ordinary cupola, the coke furnishing more than sufficient fuel for that purpose. I may briefly point out here that in the first place the iron is sponged, and this sponge, as is well known, contain-, no phosphorus or silicon when the reduction takes place at a low temperature; and in the second place this sponge is melted down in a cupola in which there is no zone of reduction for phosphorus or silicon, and that con¬sequently the resulting iron should be free from both of these impu¬rities. 3d. The liquid sponge, now carburized, is run into an open-hearth furnace, where the requisite degree of hardness or softness is obtained by adding some of the fine ore, and the usual dose of ferronmanganose. I have merely given above the rough outlines of the process, but it is my intention, as early as possible, to bring the process more fully before the Institute.

Jan 1, 1881

By W. E. C. Eustis

1st. The fine iron ore is mixed with a sufficient proportion of fine coking coal, and is coked in any of the ordinary methods for making coke. The effect of this is to convert the iron oxide into sponge in such a shape that the usual trouble of oxidation is avoided. 2d. The resulting mixture of coke and sponge is melted down ill an ordinary cupola, the coke furnishing more than sufficient fuel for that purpose. I may briefly point out here that in the first place the iron is sponged, and this sponge, as is well known, contains no phosphoras or silicon when the reduction takes place at a low temperature; and in the second place this sponge is melted down in a cupola in which there is no zone of reduction for phosphorus or silicon, and that con . sequently the resulting iron should be free from both of these impurities. 3d. The liquid sponge, now carburized, is run into an open-hearth furnace, where the requisite degree of hardness or softness is obtained by adding some of the fine ore, and the usual dose of ferromanganese, I have merely given above the rough outlines of the prows, bat it is my intention, as early as possible, to bring the process more fully before the Institute.

Jan 1, 1881

By Hsun Hu, B. B. Ruth

The rates of migration of high-angle boundaries in zone-refined aluminum crystals rolled 20 to 70 pct in the (110)[i12/ orientation were studied. Following a recovery anneal at an appropriate temperature to stabilize the polygonized structure, boundary migration rates of artificially nucleated grains were measwed isothermally at several temperatures. Results indicate that the rate of boundary migration depends strongly on the amount of deformation and on the cell size of the polygonized matrix, and is related to the driving free energy by a power function. The degree of anisotropy in growth 0.f the re crystallized grains nn&apos;th preferred mientation is independent of deformation; the migration rates of the fast-moving and the slow-moping boundary segments of a gowing grain differ by as much as one order of magnitude. The actir\ation energy fm a grain boundary migration, although nearly the same for both the fast-moving and the slow-moving boundaries for a given deformalion, decreases from 45 to 30 kcal per mole with an increase in deformation from 20 to 70 pct reduction. Re crstallization by the growth of the artificially nucleated grains results in preferred orientation. The Percentuge of&apos; grains favorably oriented for growth increases with increasing deformation. None of these grains corresponds to the ideal Kronberg-Wilson orientation relationship. The observed growth aniso-tropy is discussed in terms of boundary structure. The boundary velocity as a function of the cell inter -facial area, or the driving free energy, is discussed in the light of current theories of boundary migration. It is well established that recrystallization with re-orientation occurs by the migration of high-angle boundaries of strain-free grains. The driving force for this process is provided by the free energy stored in the metal during deformation. A quantitative study of the effect of varying driving force on grain boundary migration in deformed metals has not been possible heretofore, primarily because of: 1) concurrent recovery steadily decreasing the available driving free energy for boundary migration, &apos;-3 and 2) in-homogeneity of strain in the deformed metal.4 Aust and Rutter3 studied grain boundary migration in striated single crystals of zone-refined lead. Although the driving free energy in such crystals remains unaltered during annealing, this method does not provide a range of driving free energies over which measurements of grain boundary migration can be made. In the present investigation, the rates of migration of high-angle boundaries in deformed aluminum zone- refined single crystals were studied at various temperatures, after deformation ranging from 20 to 70 pct reduction by rolling at -78°C in the (ll0)[i12] orientation. The boundary migration rates along different crystallographic directions were determined under steady-state conditions, i.e., in the absence of competing recovery processes or impingement of recrystallized grains growing into the deformed single crystal matrix. Simultaneous recovery was eliminated by suitable anneals prior to the boundary migration measurements. The recrystallized grains, which grew a ni so tropically into the homogeneously polygonized matrix, developed flat boundary segments during early stages of growth. These boundary segments subsequently migrated along a direction approximately normal to the boundary plane into the matrix rystal. Increasing deformation over the range employed was estimated to increase the driving free energy for boundary migration by about five times. The kinetics of the boundary migration process, examined under these conditions, indicate that the boundary velocity is greatly affected by a small change of the driving free energy in the matrix crystals. These results were examined in the light of the current theories of grain boundary migration. EXPERIMENTAL PROCEDURES Single crystal strips (9 by 1 by 0.125 in.) of zone-refined aluminum, were seed-grown by the Bridgman method in a high-purity graphite mold (<lo ppm ash) at 1 in. per hr. Precautions were taken to minimize contamination of the metal during crystal preparation and subsequent handling. Spectrographic analysis of the metallic impurities in the grown crystals is Qven in Table I. The crystals were rolled in the (110)[112] orientation at -78°C to various reductions in thickness, ranging from 20 to 70 pct, in 10 pct increments. The desired reduction was achieved by many rolling passes, each being no more than 0.002 in. To minimize surface friction, the crystal was rolled between two thin layers of teflon. For those crystals rolled more than 40 pct, it was necessary to remove the disturbed surface layers by electropolishing at -5" to -10°C at an intermediate stage of rolling. The edges of deformed crystals were removed by a jeweler&apos;s saw while submerged in alcohol at -78° C to obtain samples of about ? by i in. The distorted metal at the cut edges and the surface layers were then removed by electropolishing, with removal of a minimum of 0.004 in. from each surface. The thickness of the crystals prior to rolling was chosen so that the final thickness was 0.025 in. for all samples. These deformed single crystals were each prean-nealed for 1 hr at an appropriate temperature in the range of 130" to 280°C, depending upon the amount of deformation. The purpose of this preannealing was to

Jan 1, 1970

By Parke A. Dickey, R. Fettke

Drilling activity during 1944 increased considerably in the oil fields and slightly in the shallow gas fields of western Pennsylvania. The number of deep tests (middle Devonian or deeper) completed during 1944 was the same as in 1943 and did not result in discoveries of additional reserves of natural gas or oil. Thus far no commercial oil production has been obtained from sands below the Upper Devonian in Pennsylvania. As a result of the lack of new discoveries, oil production in nearly all of the producing areas in the entire Pennsylvania grade region declined 10 to 11 per cent. Stocks of Pennsylvania Oil The Peilnsylvania grade crude-oil stocks in storage on January 1943 were 2,479,000 bbl. In January 1944 crude stocks totaled 1,846,000 bbl., and during 1944 the stocks of Pennsylvania grade crude declined to a year-ending balance of 1,617,000 bbl. Nearly all of this oil is "unavailable for use," representing pipe-line fill, tank bottoms and limited working inventories at the refineries. The storage of Pennsylvania oil has declined to a point where little or no available crude oil is currently in storage. Prices The posted price of Pennsylvania oil remained constant during 1944; however, on Rug. I, 1944, the wartime Government subsidy was instituted at a rate of 75¢ per barrel. The average price in the Bradford area, including the subsidy, was $3.31 per barrel. New Technical Developments The Pennsylvania Grade Crude Oil Association started a rather ambitious program of research in production fundamentals and technology during 1944. Several well-qualified engineers have been employed and a laboratory is to be equipped at Bradford. The group will investigate, in cooperation with the American Petroleum Institute, the possibilities of bacteria as agents in oil recovery, and undertake other studies of both a fundamental and an applied nature. In cooperation with the Pennsylvania State College, the Research Group worked out a method of measuring water-intake rates in different strata. The method involves injecting salt water down a string of tubing and fresh water down the annulus, determining the location of the interface electrically, and measuring the input rates above and below the interface. The United States Bureau of Mines, in cooperation with oil companies of the Venango district, developed a simple gas-lift tubing string, which is operating successfully in some 20 wells. This device uses the air-gas mixture produced with the oil to lift it by the usual gas-lift principles. The Northern Ordnance Co. is experimenting with a chamber lift device that expels the oil in an unbroken column. These devices hold considerable promise

Jan 1, 1945

By W. C. Hagel

Previous inuestigators have repovted unusually low H* and Do values for self-dzf@szon in certazn bcc metals, e.g., chromium nnd y -uvanium. It has been postulated that this is nn experimental crl -tetion for the existpnce of a four -atom ring meclzanzsm, mid there could be. zmpovtant theoretrcal Implicatlons. By utilizing a precise sectioning technique with Cr51 as the tracer, self-dzffi-lsion measurements in large grains of 99.99-pct Cr were extended from 1200° fo 1600"C. A least- squares analysis of the data yields that D 0.280 exp (-73,20U/RT) cm2 sec-&apos;. These AH* and Do unlues are not anomalous; there is little reason to believe that n vacancy mechanism is not opevatiue. Apparent differences at lower temperatures may result from preferential diffusion along short-circuititing paths and/or sample contamination. WITH continued technological effort, chromium and chromium-base alloys should ultimately become useful high-temperature structural materials. Accurate measurements of self-diffusion coefficients in the pure metal are necessary for a quantitative understanding of sintering, grain growth, creep, and other related rate processes. However, two conflicting determinations have been reported.* Using an Since careful diffusion studies normally yield Do values ranging from 0.1 to 10 cm2 sec-l, the Paxton-Gondolf results require independent experimental corroboration before an undue amount of speculation arises to explain the apparent anomaly. As discussed by Nowick6 and clearly shown by Hoffman and Turn-bull7 for self-diffusion in silver, a low AH* and Do can arise from preferential diffusion along grain boundaries or other short-circuiting paths. The most reliable data come from high-temperature measurements where volume effects predominate. Following a precise sectioning technique developed for determining silver diffusion in the intermetallic compound AgMg8 and cation diffusion in the corundum oxide Cr2O3,9 the purpose of this study was to measure true volume diffusion in high-purity, large-grain samples at higher temperatures than considered previously. Another point of interest is the frequent proposal10-12 that chromium undergoes an allotropic transformation between 1375" and 1800°C where the diffusion data might then show a discontinuity. I EXPERIMENTAL 1) Sample Preparation. The highest purity (99.997 pet) Cr currently available is produced by reduction of chromium tri-iodide. Three pounds of the resulting crystal bar were shipped in a sealed container with a complete chemical analysis from the vendor.* In conformity with the procedure used for

Jan 1, 1962

By W. A. Koehler, M. E. Hinkle

THE oxidation of pyrites and marcasite in coal-mine strata to produce discolored acid mine drainage has long been explained by chemical reactions occurring in three stages: 1. The iron sulphide minerals are oxidized by air in the presence of water to produce a nearly colorless solution of ferrous (iron) sulphate and some sulphuric acid. 2, The ferrous sulphate and part of the sulphuric acid combine with additional oxygen to form ferric (iron) sulphate. 3. The ferric sulphate hydrolyzes to form a reddish-brown precipitate and additional sulphuric acid. Nevertheless, chemical data alone are not sufficient to explain all observed facts. The first stage seems to proceed more slowly in the chemical laboratory than in nature. The second and third stages normally occur to a marked extent within a few days with raw mine water. However, the visible discoloration that characterizes these latter stages will not develop for months if the mine water is sterilized. By means of bacteriological techniques, two organisms have been isolated from acid coal-mine drainage. These are believed to have a part in promoting the chemical reactions summarized above. One organism is considered to be Thio-6aciZZus thiooxidans, which is known to be able to convert elementary sulphur or sodium thiosulphate to sulphuric acid. Its relation to the formation of acid mine drainage has not Yet been established. Apparently it does not Promote the oxidation of ferrous iron compounds in mine drainage to the ferric state. The second organism has not been identified by name but is described as " Gram negative, non-spore-forming rods approximately 0.4 micron wide by 0.8 to 1.0 micron long." A pure culture of this when added to sterile mine water will cause the latter to become amber and develop the typical rusty precipitate. However, it has not been found to convert sulphur compounds to sulphuric acid. Further research is planned to determine whether or not these microorganisms play a significant part in the first stage of oxidation whereby pyrites and marcasite minerals go into solution. Some of the conditions found in abandoned sections of coal mines, such as a reduced Percentage of Oxygen and increased percentage of carboll &apos;dioxide in the air, as well as the existing temperature and acidity ranges, will be tolerated by and may even be favorable to these organisms. Acid Coal Mine Drainage Acid coal mine drainage has been the concern of coal mine operators, industrialists, sportsmen and public officials for many years. The amount of acid flowing into our streams in the coal-producing areas varies considerably from mine to mine and from

Jan 1, 1949

By Y. L. Yao

It is suggested that the binary alloy systems of transition metals may be classified into groups according to "excess energy"E. For systems with positive ?E, the Laves phase, the TiNi3-, the TiCu3- and the Cudu-type rich in the smaller atom and the TizNi-type rich in the larger atom may exist. For systems with negative ?E and composed of two components of different crystal structures, the X, the Cr3O and the phase may exist on the side of the phase digrattz rich in the component with the higher "solubility factor" value am! the Cudu-type and the disordered hcp phase on the other side; if the crystal structure of two components is the same, the Cudu-type may exist on both sides. For systems with weakly positive ?E and cotnposed of different crystal structures, the u phase and the MgCd3-type may replace the Laves phase and the other types; the X, the Cr3O and the a phase may also exist. Finally, the equirnolar compounds of the CuAu- and the CsC1-type may exist irrespective of the sign of ?E. THERE are many factors which play a major role in the formation of binary intermediate phases in alloys, such as the crystal structure, the electronic structure, the atomic size and the electrochemical factor. To find the simultaneous effects of all these factors on the formation of intermediate phases of every metal would be a difficult task, especially because only a small fraction of experimental facts necessary for the complete formulation is known at present. Thus the past surveys of intermediate phases have been usually confined to few metals, several types of intermediate phases and some but not all controlling factors. In a previous paper1 the idea of "solubility factor" of metals was introduced. Although the suggested values are tentative and empirical, the formation of a continuous series of solid solutions in metals could be correlated with the interplay among the atomic size factor, the solubility factor and the crystal structure factor. The purpose of this paper is to demonstrate qualitatively the interplay of these factors in the formation of binary intermediate phases among transition metals. FACTORS CONSIDERED The Crystal Structure Factor. With rare earths excluded, the transition metals are classified into three common crystal structures listed in Table I. There is arbitrariness in the present classification of several allotropic elements. However, out of seventy-odd continuous solid solutions formed among transition metals, only six of them, namely, those

Jan 1, 1962

By G. W. Cullen

Niobium-tin has been prepared on insulating suhstrates hby simultaneous hydrogen reduction of gaseous niobium and tin halides. Stoichiometric material is greater than 98.8pct theoretical density, appears to he single-phase, and has a total impirity level less than 0.3 at. pct. Transition temperatures and lattice constants may he related to composition. Typical current densities in various fields and orientations are given. IT is known that Nb3Sn carries large current densities in high fields, 1 and exhibits an unusually high transition temperature2 and critical field.3 For these reasons high-field solenoids have been constructed of this material.4 Because of the emphasis on solenoid fabrication, much of the materials research has been directed toward development of wire geometries wherein the brittle Nb3Sn is supported by a more malleable metal or alloy. There are, however, basic studies and applications that can be carried out only on Nb3Sn supported by an insulator. Insulating substrates are desirable for a number of reasons: the substrate does not interact with applied or induced currents and fields; diffusion of metallic species into the de- posit is avoided, both during the preparation and during subsequent heat treatment; irradiated samples are not more active than the deposit itself. Unsupported Nb3Sn geometries may also be prepared by preferential chemical dissolution of the insulating substrate. This report describes the preparation and properties of Nb3Sn deposits on ceramic substrates. Experiments currently utilizing material prepared in the manner described in this report include the following: dependence of current-carrying properties on field strength and orientation 5,6 radiation damage,7,8 tunneling,9 thermal conductivity (substrate removed),1° microwave surface impedance," tube magnetization,6,12 resistivity as a function of temperature,13 and current density and transition temperature as a function of annealing.14 Possible practical applications include magnetic shielding, superconductor generators, and frictionless bearings. PREPARATION Methods for the deposition of elemental niobium and tin by hydrogen reduction of the gaseous metal halides have been known for some time,15,18 but only recently a procedure was developed in this laboratory17 for the codeposition of these two metals on a hotwire as the intermetallic compound, Nb3Sn. This method of simultaneous hydrogen reduction of the gaseous niobium and tin chlorides is used for the preparation of Nb3Sn On ceramic substrates. The procedure differs from that employed on a hot wire in that insulating substrates cannot conveniently be heated to temperatures greater than their surround-

Jan 1, 1964

By Thomas F. Bates

ANALYSIS of the chemical and structural differences in minerals often results in a better understanding of the differences in the geological conditions under which they were formed. The minerals in the kaolinite group differ in the amount of interlayer water and in the nature and amount of ordered and/or random shifting of each 1:1 layer with respect to those above and below it. This paper is a progress report resulting from research on the morphology, structure, and origin of fine-grained minerals, supported by Contract N6onr26914 with the Geophysics Branch of the Office of Naval Research. The purpose of the paper is to present data obtained in the laboratories at The Pennsylvania State College and elsewhere, which reveal some of the details of structure of the minerals in the kaolinite group, and to suggest a number of interpretations that bear upon the conditions of origin of these minerals. Be¬cause most of the work in this investigation thus far has been concerned with the relationships of kaolinite, halloysite (4H2O; endellite), and halloysite (2H2O), must of the discussion deals with these members of the group. The first step in the analysis of the differences in two sets of geological conditions is an evaluation of the differences in the minerals that result. Thus the chemical differences between the montmorillonite and the kaolinite clays corroborate other evidence in support of the view that the montmorillonites are commonly formed when solutions are alkaline and leaching poor, while kaolinite usually is associated with acid solutions and good drainage condi¬tions. It is obvious that the greater the differences in the minerals, the more divergent may be the conditions that give rise to them and the more readily one condition can be distinguished from the other. In the kaolinite group, differences between individual members are small, therefore the differences in condition of origin are presumably subtle and difficult to define. At the same time, the very fact that the minerals differ only slightly makes them more sensitive indicators of the exact conditions under which they and the minerals associated with them were formed. Since clay minerals are being used more and more to evaluate the nature, value, and mode of formation of economic mineral deposits, an attempt to define these subtle differences would appear worth while. For purposes of the present discussion, the minerals nacrite, dickite, kaolinite, the so-called "fireclay mineral," halloysite (4H2O), halloysite

Jan 1, 1952

By C. P. Mangelsdorf

Introduction The use of frequency of vibration measurements to determine tension has long been accepted by industries that use electrical or stranded cables of wire ropes in their operations. In contemplating how to determine the tension in chords of a roof truss, it seems almost inevitable that a similar approach should be investigated even though there are some important dissimilarities in physical behavior between a chord of a rod-type Birmingham truss and a stretched wire rope. While the dominant feature of both types of behavior is the existence of tension, the bending resistance of the vibrating truss chord cannot be ignored. And it is common to have attached to the chord, pieces of hardware (turnbuckles, extension sleeves, wedge boxes) that represent concentrations of mass not usually found in a vibrating wire rope. Analytical solutions to the problem of vibrating wires or beams can be found in the literature on vibrations (Timoshensko, 1955; Den Hartog, 1956). But in every case, at least one of the ingredients of the vibrating truss chord is missing. The presence of axial tension, or bending resistance, of concentrated masses and of end conditions peculiar to truss chords is a combination that appears not to have been dealt with before, although the techniques for dealing with it are commonly known. The purpose of this note is to report the results of a project to measure and calibrate such frequencies. The work was conducted by the University of Pittsburgh under the sponsorship of the US Bureau of Mines. Field observations Tests were conducted on 24 different truss installations. The first 18 trusses were installed in shale roofs above Kentucky No. 9 seam and Illinois No. 6 seam. The remaining six were placed against the competent sandstone over the Pocahontas No. 3 seam in West Virginia. Chord tension was determined by two electrical resistance strain gages, in series, applied diametrically opposite to one another on the rod before tensioning. Due to the combined effects of inexact gage placement, rod bending and residual torsion in the chord due to tightening, errors in tension as high as 1780 N (400 lb) were reasonably possible. Due to faulty soldering or damage, three of the first 18 trusses and one of the final six were rendered completely unreliable. In addition to strain, the first natural frequency of vibration was observed to the nearest 0.1 Hz. Dimensions recorded included the span between contact points at the bearing blocks (Fig. 1) and the locations and amount of excess rod and rod gap at the wedge box and turnbuckle, respectively.

Jan 1, 1986

By William A. Mitchell

AN X-ray diffraction pattern for "calcined cold precipitated ferric oxide" is reproduced dia-grammatically along with data for other iron oxides by R. C. Mackenzie.1&apos; This pattern, which shows spacings higher than those for any other form of iron oxide, was obtained from material prepared and photographed at several different times over a period of weeks, but later attempts to reproduce the results were unsuccessful, the pattern of hematite being obtained every time.2 In an attempt to solve this problem, the original photographs showing the strange diffraction pattern were examined and a marked similarity to the hematite pattern was noticed, suggesting that the pattern was in fact due to hematite but corresponded to a shorter wavelength of X-rays than the Cu Ka which was assumed to have .been used. The eight strongest lines were provisionally identified with the strongest hematite lines and, by means of the corresponding hematite spacings, the X-ray wavelength was calculated for each line. This gave an almost constant value, with the exception of the innermost line which was somewhat diffuse, and confirmed the presence of hematite. The value obtained, 0.703 ± 0.015Å, corresponds to the molybdenum Ka wavelength. The X-ray tube used was a four-filament demountable tube with a copper target. Other photographs, mostly of soil clays, taken during the same period gave normal patterns of Cu Ka radiation with one exception. This was a calcined soil clay with a high iron content and also showed Mo Ka lines of the hematite structure. The explanation is almost certainly that the copper target was contaminated with molybdenum, but it is not known how this occurred. Specimens of alumino-silicates gave their normal Cu Ka pattern, but as the K absorption edge of iron is a little longer than the Cu Ka wavelength, specimens with a high iron content greatly reduced the intensity of the Cu Ka diffraction lines relative to that of the lines due to the shorter Mo Ka wavelength. The formation of hematite on calcining cold precipitated hydrated ferric oxide3 is thus confirmed. References R. C. Mackenzie: Investigations on Cold-precipi-tated Hydrated Ferric Oxide and its Origin in Clays. Problems of Clay and Laterite Genesis, p. 69, Fig. 4, F. AIME Symposium, St. Louis, Mo. Feb. 19-22, 1951. Published 1952. &apos;R. C. Mackenzie: Ref. 1. Note added on proof. V. C. Hansen and L. T. Brownmiller: Equilibrium Studies on Alumina and Ferric Oxide and on Combinations of These with Magnesia and Calcium Oxide. American Journal of Science (1928) 5, No. 15, pp. 225-242.

Jan 1, 1954

By F. J. Mehringer, C. W. MacGregor

VARIOUS investigations have been carried out to determine the effects of cold-rolling on the common physical properties as represented by the yield strength, tensile strength, percentage of elongation and ordinary reduction of area. Very little information is available in the literature with reference to the effects of cold-rolling on the true stress-strain properties. Since the ordinary physical properties base both the stresses and the strains on the original dimensions of the test piece, which are greatly changed during the test, they are essentially empirical values and do not represent physically either true stresses or true strains. Consequently, they do not give an accurate picture of the effects of different conditions, both mechanical and metallurgical, on the strength and ductility of the material. It is not, however, the purpose of this paper to review the various advantages accruing from the use of true stress and true strain values, since these have been shown elsewhere,1-12 but to utilize them in representing the various effects considered. The true stress S and true strain (e = q&apos;) values mentioned above for the tension test are defined by1 [ ] where P, A, Ao are the axial load, the instantaneous area and the original area of cross section, respectively. From simultaneous readings of the axial load and the dimension or dimensions determining the instantaneous area of cross section, the true stress-strain curve is constructed by using the relations given in Eq. I. It is then the object of this paper to discuss the general effects of cold-rolling on the true stress and strain values for a low-carbon steel together with the effects of age-hardening and directionality on these properties. PRELIMINARY INVESTIGATIONS The material considered throughout the paper is a low-carbon steel of the following chemical analysis: C, 019 per cent; S, 0. 118; P, 0.092; Mn, 0.85; Si, 0.01. The stock was received in bars, 7 by 3/4 in., and was first annealed for one hour at 1650°F. followed by a furnace cool. Photomicrographs of this material showed considerable directionality even in the annealed condition. In view of the possible effects of the nonhomogeneity and directionality in this material, it was considered important to investigate their influence on the true stress-strain diagrams. In addition, the effect of strain-aging in this steel was also made the subject of a preliminary study. Elect of Aging on True Stress-strain Properties Since a certain time element would elapse between the cold-rolling operation and the final tension tests, it was determined to investigate the aging character-

Jan 1, 1945

By M. M. Mebta, G. W. Dean, W. H. Somerton

With the advent of underground heating operations, interest has developed in the alteration of rock properties by high-temperature treatment. In the present work a number of sandstones were heated to temperatures in the range of 400°C to 800°C under both atmospheric and simulated reservoir pressures. Pertneabilities increased by at least 50 per cent and sonic velocities and breaking strerlgths decreased by an equivalent amount. Differential thermal expansion and other reactions of constituent min-era1 grains are the causes of these alterations. INTRODUCTION In the underground combustion of petroleum reservoirs, temperatures of the order of 600C are reported to have been reached in the combustion zone.&apos; At this temperature rocks are subject to extensive thermal alteration. Temperatures of this magnitude and higher may also occur in subsurface formations when subjected to bottom-hole heating, thermal drilling operations, and underground nuclear explosions. Temperatures of this magnitude might also be generated by conventional rock drilling methods at points of bit-tooth contact. In earlier work, the permanent deformation of rocks resulting from heating was reported. Major structural damage of rocks occurs due to differential thermal expansion of mineral constituents. A number of mineral alterations including crystal inversions, loss of water of crystallization and dissociation, may also contribute to changes in physical structure and properties of rock. In the present work, samples of three typical sandstones were heated to several temperatures up to a maximum of 800C and then allowed to cool to room temperature. Heating was done under both atmospheric pressure and simulated reservoir pressure conditions. Physical properties of the samples were measured before and after heating and comparisons made. Measured properties included permeability, sonic velocity, breaking strength and fracture index. Changes in physical properties were compared to changes in mineralogical characteristics as determined by thin-section. X-ray diffraction and chemical tests. EQUIPMENT AND PROCEDURE Two outcrop sandstones (Bandera and Berea) and one sub-surface sandstone (St. Peter) were selected for the tests. These samples have a wide ranee in composition and physical properties as shown in Table 1. The first series of tests was made on 2-in. diameter by 5-in. long test specimens. Test specimens used in all later work were 3/4-in. diameter by 1 1/8-in. long, this being the specimen size required for heating at simulated reservoir pressures. After careful washing, the cores were oven dried at 100 ± 5C for a minimum of 24 hours before the tests were run. Test specimens were heated in an electric furnace at a constant rate of temperature increase of 3C per minute. When maximum temperature of the run was reached, the sample was allowed to soak for one hour. The furnace was then cooled to room temperature at the same rate of 3C per minute. The entire heating operation was designed for reproducibility without subjecting the test specimens to excessive thermal shock. For samples heated under simulated reservoir pressures, a pressure cell designed by Dean was used (Fig. 1).3 The core sample was inserted into a thin-walled (0.006 to 0.01-in.) copper cup which was then mounted in a high-pressure cell. Provisions were made for the application of internal pore pressure as well as confining pressure. Tests showed that the thin-walled copper cup closed tightly around the core and satisfactorily transmitted confining pressure to the core. The core was heated by placing the entire cell into the electric furnace. The heating program was the same as that used in the atmospheric pressure runs: tempera-ture rise of 3C per minute to maximum temperature of the test, soaking at maximum temperature for one hour, and cooling at a rate of approximately 3C per minute. The cell was designed to withstand 5,000 psi at 1,000C. However, since it was considered likely that repeated heating and cooling would in time weaken the steel, 2,000 psi at 850C was set as a working limit. In the present series of tests, the pore pressure was held constant at 750 psi and the confining pressure at 1.500 psi. The pressure source was a high-pressure nitrogen tank. The two pressures were controlled manually but are accurate well within ± 50 psi.

Jan 1, 1966

By G. L. F. Powell, L. M. Hogan

Large degrees of undercooling have been produced in bulk samples, 400 g, of copper and Cu-O alloys by melting in a slag of commercial soda-lime glass. The maximum degrees of undercooling obtained for copper, hypoeutectic and hypereutectic Cu-O alloy samples were 208°, 218°, and 97°C, respectively. No grain refinement as a function of undercooling was observed for the pure copper samples although in Cu-O alloys there was a marked decrease in grain size at degrees of undercooling greater than 150°C. The grain size change is the result of recrystallization during or immediately following the freezing process. THE first report of a large degree of undercooling in a bulk sample of metal was that by Bardenheuer and Bleckmann1 who produced 258°C undercooling in a 150-g sample of iron by melting in a glass slag. Garbeck2 extended this technique to nickel, cobalt, and copper and reported maximum undercoolings of 220°, 230°, and 60°C, respectively, while Fehling and schei13 undercooled a large number of metals as 2 to 20-g samples slagged in glass. Subsequently, one of the authors4 applied the glass slag technique to bulk samples, -500 g, of silver and obtained a maximum undercooling of 250°C. It was concluded that impurities which normally catalyze nucleation at small degrees of undercooling could be removed by oxidation and solution in a glass slag. Large undercooling of bulk samples of iron, nickel, cobalt, and their alloys has also been reported by other authors.8&apos;10&apos;11 Of the five metals mentioned above, copper was the only one which had not been undercooled by at least 200°C in the form of a large bulk sample. Since copper exhibits high liquid solubility for oxygen, as do iron, nickel, cobalt, and silver, it was considered that a much larger degree of undercooling than that observed by Garbeck for copper should be possible. This was obtained by modification of the technique applied previously to silver and the results of undercooling experiments with 400-g samples of copper form part of this paper. The undercooling behavior of Cu-O alloys was also studied, and the influence of a small oxygen content on the grain structure of undercooled copper was observed metallographically. 1) EXPERIMENTAL The copper was obtained as oxygen-free high-conductivity copper, the major impurities of which were Fe 0.01 pct, Zn 0.015 pct, and Si 0.02 pct. Melting was carried out in an open-ended vertical cylindrical fur- nace wound with Kanthal wire. A schematic diagram of the experimental setup is shown in Fig. 1. The undercooling technique previously used for silver4 involved preoxidation of the samples by melting the silver in contact with the atmosphere. The oxygen content was subsequently reduced by freezing the samples under a glass slag, whereby the oxygen was evolved as gas and the continuous glass cover over the surface prevented re-solution of oxygen when the sample was remelted. Since oxygen is not released as gas when a Cu-O alloy is frozen. the technique had to be modified for use with copper. Also, copper is oxidized during fire refining so that an in situ preoxidation treatment of the samples was not considered to be a prerequisite to large undercooling. Experimentation proved that this supposition was correct. Instead, it was found that care was necessary during melting of the copper under glass to minimize oxygen pickup. Samples of copper weighing 400 g were prepared by adding 50-g pieces of copper to a vitreous silica crucible partly filled with soda lime glass at a temperature of approximately 1000°C. Each piece was quickly immersed in the glass slag and held at this temperature until the oxide coating on the surface decomposed. This change was easily observed and coincided with the formation of gas bubbles in the glass

Jan 1, 1969

By H. L. Lovell, L. H. E. Weyher

Cyclones have been used successfully in the mineral industries to solve solid-liquid as well as solid-solid separation problems in the processing of fine particles. Substantial information is available about the operation of cyclones as thickeners, classifiers, and concentrators using a dense medium. However, very little is known about the operation of the cyclone as a fine coal concentrator not using dense medium. This application of the cyclone, namely to wash fine coal in water, requires that classification phenomena be minimized in order to arrive at an effective separation of the high density ash and sulfur-bearing mineral particles from the low density coal particles over a wide particle size range. The authors have investigated the role of feed pressure, orifice diameters, and vortex-finder length in the cyclone washing of fine coal (--1/4 in.) in water. The results of this investigation show that cyclone washing of fine coal in water is an effective unit operation particularly capable of reducing the inorganic pyritic sulfur content. The combination of hydrocyclones with complimentary equipment such as Sieve bends, shaking tables, and flotation units appears to be especially promising and may ultimately yield fine coal processing systems that could approximate the high recovery efficiencies of today&apos;s coarse coal cleaning circuits. In the future, fine coal beneficiation can be expected to receive even greater research emphasis as a result of increasing sulfur restrictions on all major coal markets. In a previous paper, work, conducted at the Pennsylvania State University, on the hydrocyclone washing of fine coal was discussed.&apos; The initial evaluation based on that wo-rk demonstrated the feasibility of hydrocyclones as fine-coal cleaning devices, and in that previous paper selected test data were presented that showed in principle how product yield and assay respond to variations of the major cyclone operating variables. The present paper reports in greater detail on the findings and presents a comprehensive evaluation of the data as follows: (1) Hydrocyclone throughput rates were related to feed pressure and other variables by regression equations. These equations are compared with other capacity-vs.-pressure drop expressions taken from the literature on classification cyclones. (2) The flow ratio was found to be the most important variable for the separation of the solids. Control of this ratio through various cyclone operating parameters is discussed. (3) The data on the product yield as well as the ash and sulfur assays from the tests were evaluated by means of correlation and multiple regression analyses. Because size-classification phenomena cannot be suppressed completely in hydrocyclone washers, product yield and assay data are regressed against cyclone operating variables separately for different size classes. These equations then reveal how the interactions of the cyclone operating variables vary in terms of the separation for different size classes. (4) Density partitions from additional tests were analyzed by supplementing product-size analyses with sink-float analyses of the separated product size classes. The evaluation of these data show how classification phenomena affect separation by density. The results demonstrate in particular the feasibility of the hydrocyclone washer for removing pyritic sulfur from fine coal. In addition to these specific findings, the investigation points up the value, in general, of using hydrocyclone washers in combination with unit operations such as screening, table concentration, and flotation. In order to make optimum use of the hydrocyclone washers and work out the most effective combination of unit operations, it is important to have careful flowsheet analyses corresponding to the given feed and product requirements. Analyses of this kind are now possible by means of computer simulation of flowsheets and other operation research tools. INTRODUCTION Before proceeding with the detailed treatment and evaluation of our results, it will be useful to review the fundamental aspects of cyclone separators and also restate the experimental procedures and data handling employed in these studies. Review of Cyclone Fundamentals: AS shown in Fig. 1, the basic components of cyclones commonly used

Jan 1, 1970