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By M. S. Rashid, C. J. Altstetter

Allotropic transformations in cerium have been studied by dilatometric, resistometric, X-ray diffraction, and metallographic techniques. The dilatometric study indicated that, on cooling below O°C, the high-temperature fcc phase, y, transforms partly to the hexagonal phase, ß, and, on further cooling, to the collapsed fcc phase, a. The amount of $ phase present at room temperature is increased by repeated cycling through the a-y transformation. It has been shown metallograPhically that the y-ß transformation has many characteristics of a martensitic transformation. In contrast to the y-ß transformation the ?-a transformation does not give the manifestation of a shear transformation. Small cellular ? domains of random shape and size collapse to a in a short time with no apparent coordination with neighboring domains. The considerable confusion in the literature over the existence of more than one high-temperature fcc phase is discussed. Two such phases have been reported in the literature and an attempt is made in this study to clarify the situation. Twelve fcc and two hcp structures have been shown to be easily reproduced or eliminated. It is proposed that the two "additional" allotropes reported in the literature and fourteen of the phases detected here are not allotropes of cerium but are due to contamination. CERIUM exists in several allotropic forms, but there is some disagreement over what the forms are. Furthermore, the conditions favoring the presence of a particular allotrope and the nature of the transformations from one form to another are uncertain. The objectives of this research were 1) to ascertain the allotropic forms of cerium, 2) to establish the conditions under which the allotropes exist, 3) to study the effects of annealing and thermal cycling on the allotropic transformations, and 4) to study the transformation mechanisms. Dilatometric, resistometric, metallographic, and X-ray diffraction techniques were employed. The form of cerium commonly found at room temperature is fcc and is designated ?. A complex hexagonal phase, 8, forms when y is cooled to slightly below room temperature. At still lower temperatures the y fcc structure transforms to an fcc form with a much smaller lattice parameter, termed a cerium. A bcc form, 6, which exists just below the melting point (800°C), will not be considered further in this work. There is a substantial body of experimental evidence (reviewed by Gschneidnerl) which favors the acceptance of these four allotropes, though some investigators have tried unsuccessfully to observe the ß hexagonal form.'-' There is disagreement, however, over the phase-transformation temperatures, due, in part, to broad hysteresis and overlapping of the transformations between the a, ß, and ? forms. The transformations are also sensitive to prior thermal and mechanical treatment. The differing purity of cerium used by different investigators is undoubtedly a factor. Cerium is difficult to separate from other elements and is quite reactive, igniting spontaneously when it is filed in air. The highest purity of cerium to date is reported to contain several hundred parts per million by weight of impurities, and early investigations were carried out on cerium containing several percent of impurities. There have been reports of more than one fcc allotrope at room temperature. Gschneidner, Elliott, and McDonald5 obtained diffraction patterns of an fcc phase with a lattice parameter about 1 pct less than that of the ? phase, instead of the y phase, on slowly cooling cerium filings from 23° to -198°C and warming them back to room temperature. However, when the sample was heated to 447°C and cooled to room temperature it consisted of only the ? phase. They have designated this new fcc phase "a-? intermediate", and say it is quite sensitive to impurities. After prolonged high-temperature treatment of a powder specimen, Weiner and Raynor2 obtained a diffraction pattern of an fcc phase of lattice parameter about 1 pct less than the ? phase. This they called the y' phase. It could not be reconverted to the y phase and is claimed to be different from the a-? intermediate phase.5,6 Dialer and Rothe3 reported two fcc phases* after cycling their powder specimens between room temperature and -192°C. Gschneidner, Elliott, and McDonald5 suggested that one of the fcc structures obtained by Dialer and Rothe was equivalent to their "a-? intermediate" phase. Table I presents some pertinent data on the proposed allotropes. For the ?(fcc)-ß(hexagonal) transformation

Jan 1, 1967

By R. D. Carnahan, J. E. White

A study of dispersion strengthening in TD-Nickel (nickel plus 2 vol pct Tho2) was conducted employing microstrain techniques at ambient room temperature. It was found that optimum strength was due primarily to the incorporation of stored energy developed by a variety of thermal-mechanical treatments. The relatively low strength of the recrys-tallized condition implies that the dispersed particles themselves offer only token resistance to deformation. The development of resistance to large-scale recovery or recrystallization at temperatures near the melting point requires a more extensive sequence of strain-anneal cycles than does the development of optimum strength. A micro-Bauschinger effect was observed which appears to be related to the lattice resistance to the movement of free dislocations. The effect was nearly identical to that in pure nickel indicating that the presence of the dispersed phase and considerably increased dislocation density (stored energy) only alters the number or effectiveness of barriers. THE early stages of deformation of engineering materials can be conveniently studied by utilizing strain-gage techniques which permit resolution of strains less than 5 X 10-7 in. per in. for testing in four-point bending (Carnahan and white1). The present investigation, part of a continuing study on the very early stages of deformation, was designed to reveal the true role of a dispersed phase in promoting high strength in a commercially available dispersion-strengthened alloy. Although this technique has been used for some time to study microdeformation in pure metals and alloys, it has just recently received attention as a means of investigating dispersion strengthening. Studying the very early stages of deformation in alloys which depend upon a finely dispersed inert phase for strength may prove to be a very important method for a better understanding of these materials. It is essential to obtain considerable clarification of actual dislocation movement and the kinds of deformation barriers which exist before optimum properties can be designed into this type of material with any degree of confidence. Considerable research on a variety of dispersion-strengthened materials has resulted in two different schools of thought regarding the strengthening mechanism. One faction2-4 favors the idea that the particles themselves resist the motion of dislocations. The criterion for yielding is the fracture of the dispersed second-phase particles due to an array of piled-up dislocations. Other invesfigators5-a have shown that particles are effective primarily by allowing a greater buildup of stored energy or dislocation density through thermal-mechanical treatments in the composite than the pure matrix material. The particles themselves, then, are not exclusive obstacles, but the complex network of particles, dislocation tangles, subboundaries, and grain boundaries are strength determining. The development of such a complex dislocation network in SAP has been studied recently in some detail by Goodrich and Ansell. The ability of dispersion-strengthened alloys to resist softening or recrystallization is also of considerable importance; however, the criteria for maximum stability may not necessarily be those for maximum strength. In this study, in addition to the evaluation of the microstrain properties of TD-Nickel, it is felt that considerable clarification of the true dependence of strength and stability on the dispersed phase is shown. I) MATERIAL AND PROCEDURE TD-Nickel is a dispersion-strengthened alloy developed by the E. I. DuPont de Nemours Co., which contains 2 vol pct thoria (Tho2) in a pure-nickel matrix. The average ThO2 particle size is approximately 0.1 p and the interparticle spacing is less than 1 u. The material was supplied by DuPont in two conditions: hot-extruded bar stock, and stress-relieved cold-rolled sheet 0.025 in. in thickness. The bar was extruded at 2200°F from a cold-pressed and sintered billet. The sheet stock was prepared from the extruded material by a process involving ten or more 50-pct cold reductions by rolling with intermediate anneals at 1800° to 2000°F. Test specimens used in this study were prepared in the form of rectangular parallelepipeds measuring 0.375 by 1.375 in. in thicknesses ranging from 0.025 to 0.040 in. Samples prepared from sheet and extruded stock were mechanically polished before heat treatment and were handled with extreme

Jan 1, 1964

By B. F. Oliver, F. Garofalo

Gas-metal heterogeneous reactions and zone-lrelting were sinultarneously employed to produce several high-purity irons with low interstitial contents in a levitating- zone melter. Successive zone-tneltitzg pusses were made in carious sequences of atmospheves which included prepuvified tank hy-drogeta, water vapor hydrogen, palladiuril-purified hydrogen, and vacuunm of 2 x 10-6 Torr. Different irons ranging in purity from 99.89 to 99.996 pct with residual curbon contents of 17, 8 to 10, and 3 to 5 ppm have been Drepared. No measuvable gradient in the residual carbon content was observed along the entire zone-melted length (6-10 in.) in I-ilz.-diameter bars. The absence of a carbon-concentration gradient in the solid indicates an apparent distvihution coefficient of 1, an unusual condition. Internal friction, solid-state extraction, and hot-hardness results indicate that the level of mobile carbon in a iron depends on the gas-metal heterogeneous reactions employed. Purification under an oxidizing atmosphere resulted in the immobilization of nearly all of the carbon present at leuels of 10 ppm or less. Continuation of purification in a reducing atmosphere veturued the carbon to a state of mobility which was aguin reversed by further purification in all oxidizing atmosphere. The immobilization of curbon at "vesidual levels " is believed to be associated with a strong interaction between carbon and oxygen atoms. frons with low carbon and nitrogen contetzts which did not exhibit a hot-hardness peak were produced after zone ynelting in vacuum. CARBON, nitrogen, and oxygen have strong and well-known effects on many properties of iron. These effects persist even at concentrations of 5 to 20 ppm. The intent of the present investigation was to establish procedures for the preparation of high-purity iron with concentrations of these elements in the range of 5 to 20 ppm and lower. The results reported here deal with the procedures employed to prepare high-purity iron, and with observations on the behavior of certain elements at "residual levels": particularly carbon. The details of the (levitating) zone melter in which the final purification steps are performed and the necessary control of the pertinent solidification variables have been described previously.1,2 MATERIALS AND PROCEDURES Commercial electrolytic iron was induction vacuum-melted and cast into 30-lb ingots. Melt additions and ingot analyses for carbon, oxygen, and nitrogen are noted in Table I. All ingots were melted in stabilized zirconia crucibles conditioned with one iron wash heat. Middle sections of the ingots were forged to 1-1/4-in. rounds, machined to 1-in.-diameter bars, then cut to 36-in. lengths. The zone-melting operations were performed on six iron bars (A to F) at a freezing velocity of 2 in. per hr with the freezing interface rotating2 at 200, 300, or 400 rpm. Liquid zones were passed through the bars in various sequences of atmospheres, Table 11, including prepurified tank H2, palladium-purified Hz, wet H2, and system vacuum of 2 x 1018 Torr. Wet-Hz atmospheres were obtained by bubbling palladium-purified Hz through water exhibiting a resistance of 3 megohms. This water was heated with a platinum-immersion heater and was degassed prior to use. Zone melting in a wet-HZ atmosphere resulted in oxidation of the elements which are oxi-dizable with respect to iron. Fine oxide particles were observed on the surface of the liquid zone, and were encased in the bar surface with the passage of the molten zone. Between each zone pass, the surface of the bar was removed by filing and deep etching; this was continued until the oxide formation ceased. The filings were magnetically separated and the residues analyzed by optical spectroscopy. These were especially high in silicon and manganese. Samples were removed from the iron bars, with few exceptions, following each zone-melting operation. A 0.08-in.-thick disc was cut with an Al2O3 cut-off wheel at a point 1/2 in. above the beginning of freezing. Material from each disc was used for hot-hardness measurements, resistivity-ratio measurements, and carbon, nitrogen, and oxygen analyses. Analyses for most other elements were

Jan 1, 1965

By P. Beardmore, B. W. Howlett, B. D. Lichter, M. B. Bever

The heats of formation at 273°K of the compounds Mg2Ge, Mg2sn, and Mg2b, the heats of fusion and melting points of Mg2Sn and Mg2Pb, and the heats of solution of magnesium, germanium, and lead in liquid tin have been measured. The excess free energies of the liquid alloys and the free energies of formation of magnesium-Group IVB compounds at their melting points and their standard free energies of formation at 298°K have been calculated. The stability and bonding of the compounds are discussed with reference to these properties. Some thermodynatnic aspects of the liquid phases in the systems Mg-Sn and Mg-Pb are also considered. THE compounds of magnesium with the Group TVB elements, silicon, germanium, tin, and lead, have often been considered to constitute a nearly ideal homologous series. In particular, their thermodynamic stability has been assumed to decrease with increasing atomic number of the Group IVB element.' The binary-phase diagrams of the magnesium-Group IVB elements given by Hansen and Anderko2 have the same form. Each system has a single con-gruently melting compound of limited homogeneity range. The structures of these compounds, which have the formula Mg2X, are anti-isomorphous with the calcium fluoride structure. A recent investigation has found evidence of a second compound in the system Mg-Pb.3 The solid compounds Mg2Si, Mg2Ge, and Mg,Sn are semiconductors, while the conductivity of Mg2Pb approaches that of a metallic conductor. This difference suggests that other properties may also show a discontinuity. The investigation reported here is concerned with the thermodynamic properties of magnesium-IVB compounds and particularly their variations with the period of the Group IVB element. The heats of formation at 273°K of the compounds MgzGe, Mg2Sn, and Mg2Pb and the heats of fusion and melting points of Mg2Sn and Mg2Pb have been measured. The results, combined with published data, are interpreted in relation to the stability and the bonding characteristics of the compounds. Some thermodynamic aspects of the liquid phases in the systems Mg-Sn and Mg-Pb are also considered. In the course of the investigation the heats of solution of magnesium, germanium, and lead in liquid tin have been determined. 1) EXPERIMENTAL PROCEDURES 1.1) Samples. Samples of the compounds Mg2Ge, Mg2Sn, and Mg2Pb, supplied by Professor P. Aigrain, Compagnie Générale de Télégraphie Sans Fils, were used in measuring heats of formation, heats of fusion, and melting points. Samples of Mg2Sn and Mg2Pb, supplied by Dr. V. B. Kurfman, Dow Metal Products Co., samples of Mg2Sn, prepared at the Air Force Cambridge Research Laboratories, and samples of MgzPb, prepared in this laboratory, were used for additional measurements of the heats of fusion and the melting points. The samples were stored in evacuated Pyrex capsules or under nonreacting liquids. 1.2) Heats of Formation. The heats of formation at 273°Kof the compounds Mg2Ge, Mg2Sn, and Mg,Pb were measured by tin-solution calorimetry. In this method, samples of the compound and of a mixture of the constituent elements are added alternately from 0°C to a tin-rich bath. The difference between the heat effects, corrected for the change in composition of the bath, is the heat of formation of the compound. Details of the method have been given elsewhere. 4 The bath was maintained at 350°C for the dissolution of the compounds MgzSn and Mg2Pb. Since at this temperature the dissolution of Mg2Ge was too slow, a bath temperature of 400" or 450°C was used with this compound. At least three calorimetric runs, each of approximately six additions, were made with each compound. 1.3) Heats of Solution. The determination of the heats of solution of magnesium, germanium, and lead in tin was included in this investigation because they were not well-established at the time this work was started. To obtain the heat of solution, the difference

Jan 1, 1967

By R. W. Smith, K. H. Lee

Bond type simulated closed-circuit grindability tests and batch grindability tests were run on six pure minerals plus a limestone and a taconite ore. The simulated closed-circuit tests were made at five different meshes of grind. The minerals tested varied widely in hardness and breakage pattern. For all simulated closed-circuit tests both Bond and Holmes work indices were calculated and compared. The Bond grindability testlm6 has been widely and quite successfully used for predictions of such items as ball mill power requirements and as an aid in plant comminution equipment selection. The test is interesting in that although run as a series of batch tests it is over-all a simulated closed-circuit test with a circulating load of 250%. The simulated closed-circuit feature is probably the primary reason for the notable success of the test. Perhaps the major criticism that can be brought against the test is that it is time consuming, since it normally takes a trained technician about an eight-hour shift to perform it.4 For many purposes this is an acceptable time requirement. However, if a grindability test is to be used for mill control purposes it should be performed in as short a time interval as possible, preferably under an hour. Sometimes in industry strictly batch tumbling mill tests are run and an attempt is made to correlate such batch tests with plant mill operation. Then an attempt is made to adjust operating tumbling mills based on data from the tests. The tests, however, frequently do not correlate well with operating data. The purpose of the present work was to explore some of the similarities and differences between a simulated closed-circui.t grindability test and a batch type test. Six different minerals plus a limestone and a taconite ore were tested in the experimentation. These materials varied widely in hardness, breakage characteristics, etc. Standard dry Bond grindability tests were mn on all materials at 48, 65, 100, 150 and 200 meshes of grind. Feed material was prepared by stage cmshing to -6 mesh. Initial feed volume was 700 cc. Care was taken to maintain the standard constant weight (about 20125 gm) and number of balls (283) during all the tests. Rotational speed was 70 rpm. Table I lists the materials studied along with pertinent data regarding the materials and Bond grindabilities obtained. In addition, dry batch tests were performed on all materials. These tests were made in the same mill as was used for the Bond tests. An identical ball charge and an identical feed volume were used. After rotating the mill for a predetermined number of revolutions at the same rotational speed as for the Bond test, the material was removed and separated from the ball charge. A screen analysis was performed on this product. Knowing the original size distribution of the feed and the size distribution of the product, it was possible to calculate the grindability or grams of a particular mesh produced per revolution of the mill. After the screen analysis of the product, the various fractions were recombined and placed back in the mill for further grinding. After grinding for additional revolutions of the mill the procedure was repeated. Thus, it was possible to obtain grindabilities for each material at a number of meshes of grind and for various revolutions of the mill. Grind-abilities obtained from batch tests are shown in Table 11. COMPARISON OF BOND AND BATCH GRINDABILITIES Figs. 1A through 1D show relationships between batch and Bond grindabilities. Figs. lA, lB, 1C and 1D show respectively graphs indicating the relationships for batch tests run for 100, 300, 500 and 700 revolutions of the mill. For a particular material on each graph, points are shown for 200, 150, 100, 65, and 48 meshes of grind except for several missing coarse meshes of grind for galena which did not fall conveniently on the figures. For each material and graph the point nearest the origin is for 200 mesh, the next for 150 mesh, the next for 100 mesh, etc. Considering Fig. lA, it is interesting to note that all relationships shown are essentially straight lines. There are, however, considerable differences

Jan 1, 1969

By Eugene A. Mizikar

A mathetnatical model of heal transfer in continuously cast steel slabs is described. The model, consisting of a unidimensional transient conduction equation and boundary condition equations, has been pvogrammed for computer solution. Temperatuve and solidification profiles calculated for a 6-in. slab, being cast under several conditions of secondary cooling, are presented and compared. Calculated solidification profiles are in agreement with reported expevinle~ztal values. For the mold zone, the predicted slab shell thickness can be described by: Resuilts of the study indicate that multibank spray cooling followed by radiant cooling should be employed when solidifying thick slabs with minimum surface temperature of 1600°F. Under these conditions, a 6-in. slab can be expected to solidify in about 8.3 min. Computer results also indicate that radiant cooling can replace spray cooling during solidification of the final 30 pct of slab with little increase in overall solidification time. CONTINUOUS casting has come to the forefront of the steel industry in recent years because of economic advantages resulting from increased yields and elimination of several processing steps. Considerable work, however, remains to be done regarding modifications to the process and operating procedures. Both a lack of operating plants in this country and the experimental difficulties associated with direct measurements on moving castings have made determination of solidification rates and temperature distributions difficult. An alternate approach is to mathematically simulate heat transfer in a continuously cast section, and then calculate the temperature distributions as a function of the controllable variables of the process. Simulation of heat transfer during solidification requires that a nonlinear mathematical problem be solved. As pointed out by Ruddle,' there are two mathematical approaches to the problem- the analytical approach and the numerical approach. While the analytical approach is certainly the more elegant of the two, it does require a number of inexact assumptions because of the complexity of the problem. For example, noteworthy analytical treatments of heat transfer in continuous casting have been developed by Savage Hills,3 and pehlke4 only by making one or more simplifying assumptions such as invariant thermophysical properties, constant heat-transfer coefficients in the mold, and linear temperature profiles in the shell. Simplifying assumptions such as these can introduce considerable uncertainty in the validity of results calculated with analytical solutions. Numerical solutions, which are considerably more versatile, appear to be better suited for solving solidification problems. Complex variations in the boundary conditions and variable thermophysical properties can be handled readily with this technique. Whereas numerical computations can be long and tedious when done by hand, results can now be obtained quite rapidly with the use of either the digital or analog computer. Several numerical models of heat transfer in continuous casting have been published. In 1963, Adenis, Coats, and Ragones published a numerical model used to calculate temperature distributions in direct-chill-cast magnesium billets. More recently, Donaldson and Hess 6 presented results obtained with a numerical computer model of heat transfer in continuously cast steel billets. In the present study, a model of unidimensional heat transfer in continuously cast slabs is presented. The method of solution on a digital computer is also included. Calculated temperature distributions and solidification profiles for various schemes of secondary cooling along with attempts to verify the model are also discussed. MATHEMATICAL MODEL The schematic representation of the slab continuous casting process in Fig. 1 illustrates that the slab passes through three distinct zones of cooling. Accordingly, the mathematical model consists of three parts: 1) solidification in the mold; 2) solidification in the spray cooling zone ; 3) solidification in the radiant cooling zone. Heat-Transfer Equations. The model was developed bymaking a heat balance on a horizontal slice of slab over the time period required for the slice to proceed from the liquid metal meniscus in the mold to the cutoff station. As shown in Fig. 2, the imaginary slice extends from the center line to the surface of the slab. As the slice moves downward, heat is conducted from the center line to the surface of the slab at a rate governed by the surface boundary condition and thermophysical properties of the metal in the slice. The following partial differential equation describes the conduction of heat in a medium moving at velocity U in direction Z:

Jan 1, 1968

By G. M. Schwartz, J. N. Gundersen

Utilization of magnetite-bearing taconite from the great Mesabi range of Minnesota is fast becoming a major industry in the state. The planning and early development stages of taconite processing projects have been de-scribed1-3 and an excellent discussion has appeared recently4 concerning the current mining, crushing, concentrating, and pelletizing techniques of the Reserve Mining Co., whose operations lie entirely within the Eastern Mesabi district. The present paper will deal only with some of the geological aspects of taconite utilization in the district, with emphasis placed upon some of the common mineralogical and textural features of the tacon-ites currently being mined or stripped and how these factors generally affect the potential recovery of the iron from the metamorphosed Biwabik iron-formation. The generalized geologic setting of the Eastern Mesabi district is presented in Fig. 1. The small circles on the geologic map, adapted from Grout and Broderick,3 mark the location of drill holes that were available for inspection during this study through the courtesy of Reserve Mining and Erie Mining Cos. The cores from these holes were divided into stratigraphic units and examined for their mineral content. Typical mineral associations and grain fabrics were also determined from hundreds of thin and polished sections. Available metallurgical tests made it possible to determine the probable response of a given variety of taconite to magnetic concentration. The longitudinal section of Fig. 1, projected along the strike of the iron formation, presents the simple stratigraphy of the area. It also shows the uniformly thick nature of the iron formation members in the district as well as a somewhat abrupt thickening of the formation to the west of the probable fault. The stratigraphy of these precambrian rocks has been described5-' elsewhere and need only be briefly reviewed. Historically, the oldest rocks unit, the Giants Range granite (Algoman) was covered by the Animikie group of sediments (Middle Huronian?), consisting of the Pokegama, Biwabik, and Virginia formations. Outcrops of the Pokegama quartzite are locally distributed along the northern limit of the Biwabik iron formation, but they are too limited to depict on the geologic map of Fig. 1. The effects of the intrusion of several small diabase sills within the Virginia and Biwabik formations are obscure because all of these rocks have been subsequently highly metamorphosed, mainly by the Duluth gabbro. The emplacement of the transgressing Duluth gabbro (Middle Keweenawan) and that of numerous peg-matitic veins in the iron formation8 has resulted in extensive contact and metasomatic metamorphism which has locally reconstituted the previously existing minerals of the Biwabik formation, in large part quartz and magnetite, into a wide variety of silicate mineral assemblages9 that have a profound effect upon the re coverability of the remaining magnetite. The entire region has subsequently been eroded and largely buried beneath Pleistocene glacial deposits. Structurally, the strike of the gently dipping Animikie group generally parallels the elongate outcrop pattern of the Biwabik iron formation on the map of Fig. 1. The Animikie group most commonly dips from 5" to 15" to the south-southeast. In this area, the Duluth gabbro pluton is somewhat sill-like, dipping about 30" to the southeast. Projecting these present structures upward, it seems probable that the gabbro once extended over the underlying Animikie group in the Eastern Mesabi district. SELECTION AND PRESENTATION OF DATA Because of the locally intense metamorphic activity in the district, mineralogical variations within the magnetite-bearing taconites are commonly abrupt, both vertically and laterally. Consequently it is difficult to select a single hole or small group of holes whose cores will be entirely representative of all of the district. Two holes have been selected, however, that in a general way represent mineralogical and textural variations that are likely to be encountered in both the eastern and western parts of the district. These recently drilled holes were chosen for discussion because it was possible to log the core and then to place the sample intervals at stratigraphic boundaries prior to preparation of the core for magnetic tube tests.

Jan 1, 1961

By C. S. Simons, G. Major-Marothy, M. A. K. Grice, D. A. Dahlstrom

The vacuum filter operating variables that influence cake moisture are discussed. The influence of temperature control, particularly through application of steam to the cake, is emphasized. Results of pilot plant studies on filtration of fine hematite concentrates are presented and discussed, and are shown to support the theoretically-derived conclusions. Results on fine magnetite concentrates are also used to support the argument. The relative merits of disc and drum filters from the standpoint of cake moisture are discussed. Moisture content has always been recognized as one of the most important properties of concentrates used as pellet plant feed. Most iron ore concentrates are produced by wet methods, and are finally de-watered on filters. Obviously, a real economic advantage accrues to the ability of control the moisture content of the filter cake within the range required for optimum pellet production. Another consideration, also, has been receiving increasing attention recently. Transoceanic shippers of concentrate cargoes are critically assessing the hazards of excess moisture. The nature and magnitude of these risks have been described, ' and it appears that their elimination may require that residual moisture be somewhat lower than the limit for proper pelletization. Coarse, very free-filtering materials, such as the products of spirals, are usually best handled on top-feed types of machines. The moisture content of the cake may be held at a specified value by proper design and operation, taking into account cake thickness, air-flow rate, and drainage time. Fine-grained concentrates, with which we will be concerned here, must be filtered on Drum or Agidisc machines. With many of these materials, it is possible, by proper design, to meet cake moisture requirements with a conventional filter station. The first installations to produce high-grade pellets from magnetic taconites fell in this class. In fact, the design criteria were developed in connection with operations of Reserve Mining Co. at Silver Bay, inn.,2 and these have been verified repeatedly in other mills. The trend today, however, is toward the production of more difficultly dewatered concentrates. This is due on the one hand to the increasing attention being given to non-magnetic ores, which tend to be far slimier, and therefore much more retentive of moisture, than the magnetites. On the other hand, the pressure to improve the grade of the magnetic ores is leading to finer grinds, which also are more difficult to dewater. In the latter case, the decision to improve grade in an existing operation by finer grinding for better liberation may lead to two unattractive alternatives: 1) substantially higher bentonite consumption, plus the risk of poorer quality pellets, from high cake moisture, or 2) installation of a thermal dryer. There is, however, a third alternative. In recent papers by two of the authors3,4 it was shown that for many materials a significant decrease in cake moisture can be obtained by applying live steam to the cake face during the drying part of the filter cycle. Further, this limited drying appears to have distinct economic advantages compared to thermal drying. It is the purpose of this paper to explore the third alternative. To do this, the results of an extensive pilot study of steam filtration of a hematite flotation concentrate will be critically examined. This study was sufficiently broad so that a number of alternate suggestions (besides steaming the cake) for reducing moisture content were tested, and comparative data for both Drum and Disc filters were obtained. The work was particularly interesting since the concentrate has a high Blaine surface, and is therefore particularly difficult to dewater to the levels required. FILTER CAKE MOISTURE The significant difference between concentrate filter cake as discharged from the filter, a cargo of that same filter cake during or after shipment, and a green ball formed from that filter cake is in the relative volume of voids, or porosity. In every case, the material is a collection of small solid particles held together by the cohesive forces of a liquid. The physical properties of the aggregate are determined by the

Jan 1, 1967

By H. F. Ramstad, F. D. Richardson

The equilibria (a) SiOz +Hz =SiO +H20 and (b) Si + SiO, = 2Si0 have beet1 studied at temperatures of 1425"to 1600°C ad 1310°to 1485°C respectively. The stattdard free energy changes for the tzrro reactions are given by the equatiotts Combination of the results for both equilibria leads to tiotz removes certain anomalies in existing high-terlzperature data for equilibria involving silica and silicon in iron. In many metallurgical processes and in many laboratory investigations silicon monoxide undoubtedly plays an important role. It is unfortunate therefore that wide differences exist between the results obtained by different investigators1-7 in their studies of such equilibria as In an attempt to put our knowledge of SiO on a surer basis, an exhaustive study has been made of equilibria [I] and [2] at temperatures ranging from 1300" to 1600°C. Reaction [I] was studied by measuring the amounts of silica which could be condensed from streams of Hz or Hz + HzO which had previously been brought into equilibrium with silica at temperatures ranging from 1425" to 1600°C. Reaction [2] was studied by measuring the material that could be condensed from streams of Hz or argon which had been brought into equilibrium with mixtures of silicon and silica at temperatures ranging from 1310" to 1485°C. EXPERIMENTAL Materials. The silicon was "superpure" grade and contained less than 0.1 pct impurities. The silica was prepared from pure mineral quartz; this was crushed and treated with concentrated hydrochloric acid to remove particles of iron, washed with water, and finally dried at 120°C. For the hydrogen + silica reaction, the silica was sized to —20+100 mesh. For the silicon + silica reaction, the two materials were ground to a fine powder in an agate mortar. The hydrogen and argon were commercial oxygen-free gases. The gas streams were controlled with capillary flow meters and the volumes were measured by wet gas meters. After passing through the meters, the gases were partially dried by silica gel. The hydrogen for the HZ + SiOz reaction was then passed through palladised asbestos at 300°C and dried with magnesium perchlorate. The efficiency of oxygen removal was checked throughout the experiments by passing the gas over an electrically heated strip of nichrome, used as an indicator as described by Rathman and de itt.' When mixtures of HZ + Hz0 were required, the partial pressures of water vapor (1.8 to 22 mm) were obtained by passing the hydrogen through oxalic acid dihydrateg' lo held at various controlled temperatures, O.l°C, by means of a water bath. The hydrogen for the Si + Si02 reaction was purified by passing it over a mixture of 3 parts of magnesium to 5 of lime heated to 600°."l1 u The argon for this reaction was passed through titanium powder (-3/16 in. + 100 mesh) heated to 900°C. The nitrogen used to prevent the reaction products escaping from the condenser (see later), was deoxidized by copper or iron at 600°C. All these gases were finally dried with magnesium perchlorate. Furnace, Temperature Contr01, and Measurement A molybdenum resistance furnace was used for both sets of experiments. The reactions were conducted inside a high-grade alumina tube, 36 in. long and 1 in. in diam as indicated in Fig. 1. With this arrangement an even temperature zone (2"C) 4 cm long was satisfactorily obtained. The temperatures were kept constant by means of a proportional controller actuated by a Pt-Pt 13 pct Rh thermocouple. This was placed between the two alumina tubes, so that the temperature at the junction was 1400" to 1450°C. Up to 1485"C, the temperatures were measured with Pt-Pt 13 pct Rh thermocouples. For higher temperatures an optical pyrometer was used, this being sighted (through the glass window 1 in Fig. 1) on the end of the alumina tube, that held the SiOz or Si +SiOz mixture, 10 in Fig. 1. The optical pyrometer was recalibrated whenever a change was made in any part of the apparatus situated in the hot zone. Successive readings with the optical pyrometer were reproducible to within 1"C. Equilibrium Apparatus and Procedure. Hydvogen and Silica Reaction. The apparatus is shown in Fig.

Jan 1, 1962

By G. L. Tufford, R. L. Bleifuss

Low-grade manganiferous iron ores of Minnesota's Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite with subsequent magnetic separation and flotation have not given satisfactory results because, in many instances, concentrate grade and manganese recovery are low. Metallization of iron and concurrent reduction of higher manganese oxides to MnO, as in the R-N process, followed by recovery of iron by magnetic separation and manganese by leaching, seems to be a technically feasible process. High-temperature x-ray diffraction studies show that solid-state reactions between iron and manganese, with the formation of intermediate iron-manganese oxides, occur during reduction and affect recovery of both iron and manganese from the final product. Solid state reactions also occur between FeO, MnO, and SiO, at temperatures as low as 900°C. The kinetics of these reactions are such that they become an important factor in the treatment of ores by the R-N process. These investigations suggest a temperature and gas composition cycle that would maximize both iron and manganese recovery. During the past ten years, iron ore shipments from the Cuyuna Range of Minnesota have decreased sharp1y. Because of adverse grade, structure, and cost, many Cuyuna ores are no longer competitive with high-grade foreign ores and domestic pellets. The low-grade manganiferous iron ores from the Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite for subsequent magnetic separation and flotation has not given satisfactory results because concentrate grade and manganese recovery are often low. However, a technically feasible process appears to be metallization of the iron and concurrent reduction of manganese oxides to MnO with recovery of metallic iron by magnetic separation and extraction of manganese from the tailings by leaching. In 1962 the R-N Corp., with a grant from the Area Redevelopment Administration, conducted an amenability study of the metallization of manganiferous iron ore from the Cuyuna Range. The results of this preliminary investigation were sufficient to interest the Economic Development Administration in sponsoring further studies of the process with emphasis on secondary recovery of manganese from the nonmagnetic tailings. Inasmuch as the metallization process has considerable influence on the final form of the manganese - its texture and distribution between the magnetic concentrate and nonmagnetic tailings-the investigation included a study of metallization of the ore as well. Therefore, the investigation conducted at the Mines Experiment Station covered three interrelated phases: (1) laboratory R-N roasting studies and magnetic separation tests, (2) laboratory chemical extraction experiments of the nonmagnetic tailings, and (3) a mineralogical study of the crude ores and their various roast products. High-temperature x-ray diffraction investigation of the Fe-Mn-Si0,-0, system is the main topic of this paper and an extension of the mineralogical work. GENERAL GEOLOGY The Cuyuna Range is known for its complicated geologic structure, complex orebodies, and generally indifferent response to attempts at conventional beneficiation. Several geologists have made intensive studies of the Cuyuna Range, including Leithl (1907), ~darns' (1910), Zapffe3 (1925), Grout and Wolff4 (1955), and schmidt5 (1963), whose study was the most comprehensive of all. The Range is covered with glacial deposits - till, out-wash, and lake sediments -up to 250 ft thick. Bedrock stratigraphic units of the Cuyuna Range consist of three tightly folded Precambrian sedimentary formations. The lower unit is the Mahnomen formation, composed of 2000 or more feet of argillite, slate, siltstone, and quartzite. The middle unit is the Trommald formation, which varies from 45 to 500 ft in thickness and comprises the major iron-bearing formation. The upper unit is the Rabbit Lake formation, consisting of over 2000 it of argillite, slate, and interbedded lenses of lean iron formation. In the central part of the Cuyuna Range, the units have been folded into a series of

Jan 1, 1969

By S. R. Balajee, I. Iwasaki

The interaction between British gum 9084 and dode-cylammonium chloride (DAC) at quartz and hematite surfaces was established from coadsorption studies and streaming potential measurements. The cationic DAC interacts with the somewhat anionic British gum 9084, leading to the formation and adsorption of a binary complex of DAC-British Gum 9084 at the interface. The parallel ability to depress quartz along with hematite as a result of the interaction between DAC and British gum appears to be the main reason for the ineffective depressant action of starches and starch derivatives in the cationic flotation of iron ores. Amines are not particularly selective collectors for the flotation' of siliceous gangue from iron ores and, therefore, a suitable iron oxide depressant is needed for a satisfactory separation. Various starches and their derivatives have been extensively tested with oxidized iron ores,'-3 and it has been empirically established that British gums and dextrins are preferable. However, for the flotation upgrading of magnetite-taconite concentrates from 8 or 8.5% Si O2 to about 5% Si 02, British gums, which have been used so successfully on oxidized iron ores, have been found to have no effect and oftentimes are actually deleterious.4 In previous articles,5-7, starches were shown by adsorption measurements, flotation tests, and floccula-tion tests to interact with calcium ions in solution, and it was thought that a study on the interaction between starches and dodecylammonium ions would be able to shed some light on the anomalous flotation behavior described above. In fact, starches are known to interact markedly with paraffin-chain-type surface active agents and, thereby, to precipitate the starch or inhibit the iodine-starch reaction.8 From X-ray diffraction studies and viscosity measurements, the formation of a helical complex between mylose and a surface active agent has been postulated.9 The interaction with other types of hydrophilic colloids, such as synthetic polymers and proteins, has also been investigated and is usually explained in terms of van der Waals' force interaction and/or ion-ion interaction. In the present investigation, the interaction of British gum and dode cylammonium chloride on quartz and hematite was studied by adsorption and streaming potential measurements in an attempt to establish the mutual adsorption behavior of British gum and dode-cylammonium chloride on mineral surfaces and to clarify the anomalous depressant activity of British gum in the cationic flotation of iron ores. All the measurements were carried out at a natural pH of near 7 because dodecylammonium chloride gives maximum selectivity of flotation separation at this pH2 and to avoid any third parameter in the system. EXPERIMENTAL MATERIALS AND METHODS Minerals: The quartz and hematite samples used for the adsorption tests were prepared as described in a previous paper,"J except that the specific surfaces of the samples were increased to 5,860 and 16,000 Sq cm per gm, respectively. For the streaming potential measurements, the 48165-mesh fractions screened out of the original samples were etched with hydrochloric acid, washed repeatedly with water, and stored under water in Pyrex bottles. Reagents:DodecyIammonium chloride (DAC) was prepared1 1 by bubbling dry hydrogen chloride gas through a benzene solution of high-purity dodecylamine supplied by Armour and Co. British gum 9084, received from Corn Products Co., was solubilized by first dispersing it in water to produce a 0.05% solution and then homogenizing it in a blender for 5 min. Distilled water was used in the preparation of the samples and the solutions and for all test work. Adsorption Measurements: The procedure for the adsorption density determinations was also the same as that described in the previous paper.1° The residual concentrations of the British gum and the DAC in the supernatant solution were analyzed colorimetrically by the phenol-sulf uric-acid and amine-picrate methods, respectively. The validity of the mine-picrate method for the colorimetric analysis of DAC in the presence of British gum and the analysis of British gum in presence of DAC were checked by establishing calibration curves between optical density and concentration. Streaming Potential Measurements: The cell assembly for the streaming potential measurements was similar to that described by Fuerstenau.' The streaming potential

Jan 1, 1970

By J. F. Martin, J. E. Friedline, L. M. Melnick, G. E. Pellissier

A method has been developed for determining gases in steel in which the gases are extracted by vacuum fusion and analyzed by mass spectrometry. This method is especially applicable for determining small amounts of oxygen and nitrogen. The lower limit of detection for both oxygen and nitrogen is 0.0001 pct with an average deviation of about 0.0001 pct for oxygen and 0.00008 pct for nitrogen. Hydrogen analyses by this method are in good agreement with analyses by vacuum tin-fusion. A complete analysis of all gases extracted from a steel sample can be accomplished in 40 min. It has long been known that certain of the gaseous elements exert particular effects on the physical and mechanical properties of steel. With the recent advent of new experimental steelmaking practices it is now possible to obtain steels with extremely low contents of such elements as oxygen and nitrogen. Present methods for determining these two gases are of insufficient sensitivity as applied to steels made by these newer practices, and therefore a new technique was considered necessary. A review of the literature showed that the conventional vacuum-fusion method1 was the procedure most suitable for modification to obtain a sensitive method for determining the gaseous elements present in steel simultaneously. However, for trace amounts of gases it is impractical to increase the sample size because of the physical limitations of the apparatus and the increased degassing time which would be necessary. Also, when only one of the desired gases is present in trace amounts, quantitative separation by conventional vacuum fusion is almost impossible. Since small analytical mass spectrometers are now commercially available, it was decided to use this instrument in conjunction with conventional vacuum fusion for both qualitative examination and quantitative determinations of the gaseous elements in steel. This technique has already been used with success for the analysis of copper and lanthanum.2"4 APPARATUS A vacuum-fusion unit was first designed and built, Fig. 1. This unit was designed especially for the determination of small amounts of nitrogen and/or oxygen in steel since an acceptable method (vacuum tin-fusion)5 was already in use for the determination of hydrogen in steel. The vacuum system was con- structed of Pyrex glass throughout. Mercury check valves were used in place of stopcocks in the high-vacuum section of the system. Ferromagnetic samples are normally introduced into the vacuum system through a mercury lift. In case of a break in the lift, the mercury is prevented from entering the furnace by a self-locking, mercury safety check valve, Fig. 2. This check valve, developed at our laboratory, is a modified T/S ball-and-socket joint placed in the sample inlet system between the mercury and the furnace. A sudden entry of mercury or air pushes this valve into the closed position, completely blocking the top of the mercury lift. The check valve is held in the closed position by the vacuum of the apparatus. A separate entrance tube also was placed in the system, so that samples which would amalgamate with mercury, or which are nonmagnetic, could be introduced into the furnace. A slightly modified Guldner-Beach furnace is used in this system.8 The optical flat was connected to the system by a ground-glass joint to facilitate cleaning, a quartz delivery tube was substituted for Pyrex, and the crucible was used uncovered. Fusion takes place in a high-purity graphite crucible insulated by — 200-mesh high-purity graphite powder. The crucible set (crucible and funnel) is suspended in a quartz crucible. The furnace envelope and the sample inlet system are exhausted by 2 single-stage, mercury-diffusion pumps in series. The first of these is a high-speed pump, which will work only with a very low backing pressure. This pump is used to exhaust the gases from the furnace as rapidly as possible. The second mercury-diffusion pump is used as a backing pump for the first; the capacity of this pump is much lower. However, it will work efficiently against a back pressure of 3 mm of mercury. To assure positive pumping, a modified Naughton and Uhlig condenser7 is used. With the use of proper valving the second pump is also used as a circulation pump in the catalyst system.

Jan 1, 1959

By M. E. Wadsworth, T. L. MacKay

Sintered UO, samples were leached in sulfuric acid solutions of various concentrations. A pressurized system was used so that it was possible to investigate the kinetics of the reaction to 270°C with oxygen overpressures as high as 900 psi. The rate was observed to be a function of the concentration of hydrogen ions and directly proportional to the partial pressure of oxygen. Evidences are presented which indicate that a UO2 surface site reacts with a molecule of water to form a hydroxyl complex which in turn can dissociate with the characteristics of a weak acid. A rate determining step has been proposed which involves the reaction between an oxygen molecule and the hydroxyl complex on the surface of UO,. ThE 2 principal methods for uranium dissolution are carbonate and acid leaching. The sulfuric acid leach is the more popular and is used for the treatment of the majority of the ores of Africa, Canada, and the United States. Low recoveries in basic leach circuits led investigators at the University of British columbia1 to study leaching of uranium ores in pressurized vessels. Early in the study of dissolution of uranium it was found that only uranium in the hexava-lent state could be leached in acid or basic circuits. Therefore, the use of oxygen over-pressure in an autoclave offered an interesting approach to solving the low recovery problems of carbonate leaching. UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. A pressurized system was used to provide a means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The mechanism for the dissolution of UO2 should be similar for any of the uraninite type minerals. At the present all of the kinetic studies that have been conducted have been in carbonate media. Peters and Halpern2 carried out a kinetic study of the leaching of pitchblende. Their specimens were pitchblende ores selected on the basis of high grade and homogeneity. Pearson and wadsworth3 conducted a kinetic study of the dissolution of UO2 in carbonate solutions with results very similar to those obtained by Peters and Halpern. EXPERIMENTAL The UO2 as received* was found by spectroscopic *Mallinckrodt reagent, supplied by the Atomic Energy Commission. analysis to have a purity of 99.94 pct 0.03. It was ground in a mechanical agate mortar and screened through a 400-mesh sieve. Thin flat disks of UO2 were prepared by pressing the sized powder in a specially constructed die at a total pressure of approximately 25 tons per sq in. The pressed disks were approximately 0.25 cm thick, 1.6 cm diam, and 3.5 g in weight. As pressed, the samples were approximately 65 pct of theoretical density. It was essential that a binder such as poly-vinyl alcohol be added before pressing to prevent formation of cracks when fired. It was found by trial and error that pressed disks sintered close to 1870°C in a hydrogen atmosphere, reach densities between 91 and 91.5 pct of the theoretical density. At this density the samples had no measurable porosity based upon a 2-hr emersion in boiling water. An X-ray examination of these sintered UO2 disks showed them to be identical with the original UO2 received. Reaction of UO2 with the alundum furnace core was prevented by placing molybdenum between the samples and the core according to the method of Corwin and Eyerly.4 Leaching studies were carried out in a specially designed autoclave, the details of which have been presented e1sewhere.6 The main features of the equipment as applied to a kinetic study are: 1) solution samples may be removed during the course of a single run; and 2) temperature and agitation are carefully controlled. Two-ml samples removed from the autoclave during the course of a run were analyzed for U3O8 content with a Beckman model DK-2 spectrophotometer by the method of

Jan 1, 1959

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

A simple and inexpensive mercury-tracer method has been develohed to study rates and Patterns of gas flow in blast furnaces. A Pulse of mercury is injected into the hot blast, and its arrival at the sampling Point is recorded by an electronic circuit that measures resonant absorbtion of ultraviolet light by mercury vapor in the gas aspirated .through the detecting. cell. A rapidly developing interest in blast-furnace technology in recent years has created a strong demand for precise knowledge of the rates and patterns of gas movement through the stock column. Classical fluid-flow theory cannot supply the desired information because the complexity of the blast-furnace situation precludes the accurate determination of many of the parameters required for solution of the equations. In fact some of the terms employed in fluid-flow treatments become almost meaningless under blast-furnace conditions. The void fraction of the stock column, for example, varies widely from place to place and is affected by the segregation of charge materials, attrition of lumps during descent, and channeling. Gas density varies with changes in local pressure, temperature, and composition, while viscosity varies with temperature and composition. Even if mean values for these functions were acceptable, they would be either impossible or extremely difficult to determine with a high degree of accuracy since the value of the mean for all gas properties would depend upon the flow distribution itself. Attempts to study gas movement by the pitot-tube determination of kinetic pressures have met with little acceptance. Reproducibility of results is extremely difficult to achieve in a situation where alignment of the tube orifice with respect to the flow direction in tortuous channels cannot be guaranteed. Because of these difficulties it would appear that progress can be achieved only with a direct method of measuring gas velocities and determining the shape of flow paths through the stock. The establishment of such a method is described in this paper. SELECTION OF METHOD Direct measurement suggests the use of a tracer by means of which the progress of a "parcel" of gas can be followed through the furnace. Several requirements must be met before any selected material can be considered a suitable tracer. First of all, it must be a substance not normally present in blastfurnace gas or dust; otherwise its presence in a gas sample will have little significance. It should be volatile at temperatures normally existing within the furnace, to ensure that it will travel with the gas, as a gas. It should possess special properties enabling its presence in the gas to be detected readily, and it should not undergo exchange reactions with any material normally present within the furnace, including refractories and coke as well as all components of the metal and slag. Radioactive materials naturally are considered because their radioactivity renders them susceptible to detection. However, of the many radioactive materials available, almost all are eliminated from final consideration by their unsuitability in terms of other properties. Radioactive silicon, carbon, calcium, phosphorus, and many others have been considered and discarded, either because they are not volatile over the whole range of significant temperatures, or because they could be expected to undergo exchange reactions with burden or refractory materials. Others which might be suitable in terms of these properties are eliminated because of a low activity, short half life, or the necessity for fragile counting apparatus. Of the many elements available in radioactive form, perhaps radon is the only one suitable for blast-furnace gas-flow studies. This has been used in several investigations1-4 with considerable success. The use of radiotracers has certain inherent disadvantages. One is the cost. An appreciable sum must be allowed for materials each time a test is made. Also, special methods of handling must be employed, and very often the progress of an investigation must be governed by the availability of isotopes and the delivery arrangements that can be made for them. An advantage is immediately gained if the tracer material can be a substance which can

Jan 1, 1960

By Ralph Hultgren, Prodyot Roy

Manganese vapor pressures from 1250° to 1500°K were measured by conventional Knudsen and torsion-effusion methods in twelve Fe-Mn alloys with compositions from 9 to 80 at. pct Mn. The Knudsen re-sults agveed approximately with previous measurements found in the literature which indicated the solutions were nearly ideal. However, except for the higher manganese compositions, the initial torsion readings indicated much (up to 50 pct) higher vapor presszcres than the Knudsen method. These high readings decreased steadily with time. The results are interpreted as due to depletion of surface concentration of manganese during evaporation. Thus the initial torsion readings are the most nearly correct and Knudsen methods on alloys are to be regarded with suspicion unless it can be demonstrated that diffusion rates are rapid enough to replenish surface concentrations depleted by evaporation. For the lowest manganese contents and highest temperatures, depletion causes initial torsion readings to be too low. FEW thermodynamic data are available for alloys of the high-melting transition metals due primarily to experimental difficulties at the high temperatures involved. Measurement of vapor pressure is one of the most promising techniques to be applied to this problem. From the vapor pressure of a component of an alloy phase, its activity or its partial molar Gibbs energy can be directly calculated. From measurements over a sufficient range of temperatures and compositions the partial and integral Gibbs energies, enthalpies, and entropies may be determined through Gibbs-Duhem integration. For solid phases of variable composition, which commonly are found in alloys, measured vapor pressures are low because of depletion of the surface concentration of the more volatile component as it is selectively vaporized. Diffusion from the interior tends to restore the depleted concentration. The seriousness of the effect depends on the relative rates of diffusion and vaporization. Although depletion has been recognized as a factor,' direct measurements of its rate are lacking and quantitative estimates of its effect on measurements are uncertain. In the present work the vapor pressures above a series of Fe-Mn alloys have been measured by the torsion-effusion method. This method permits a measurement of the vapor pressure of manganese as soon as the sample comes to temperature and continuously throughout the run. The rate of decline of the apparent vapor pressure measures the rate of depletion and the torsion reading at zero time should be correct. At high manganese concentrations (70 and 80 at. pct Mn), the torsion reading remained nearly constant; surface depletion was negligible. There was a slow drop in measured pressure due to bulk loss of manganese from the sample. However, for lower manganese contents, especially at high temperatures, the depletion effect was considerable and the apparent vapor pressure decreased steadily with time. For these alloys the Knudsen method should give pressures which are too low. The measurement of pressure in the Knudsen method cannot be made until enough manganese has been vaporized to be weighable. The Knudsen result is therefore an integrated average between the initial and final vapor pressures. To verify this, conventional Knudsen measurements were also made with results in approximate agreement with previously published Knudsen measurements for these alloys. As expected, for the lower manganese contents the initial torsion readings of pressure were as much as 50 pct higher than the Knudsen. THE APPARATUS The apparatus, shown in Fig. 1, is capable of operating to temperatures up to 2000°K. A vacuum of 5 x 10"6 mm Hg can be maintained. Temperatures were measured to +3° by a W-Re thermocouple placed in the dummy cell, N. The torsion cell consisted of two alumina crucibles with holes in their covers. They were placed in the molybdenum holder shown suspended from the torsion wire. Rectangular torsion wires (1 by 4 mm) were found to have superior sensitivity and less residual distortion than circular (2-mm-diameter) wires. The precision of angular measurement was found to be *0.025 deg; the variation is no doubt due to temperature fluctuation and vibration. For the Knudsen experiments the alumina cell was set on the support, N. SAMPLE PREPARATION 800-g samples were prepared by melting together electrolytic iron and electrolytic manganese and pouring the melt into a water-cooled copper mold. Melting and pouring were done under a helium at-

Jan 1, 1965

By D. A. Flanagan, P. B. Crawford

A study has been made of the feasibility of storing liquid meihane at low pressures in undergrohd caverns. Methane liquefies at — 258°F at atmospheric pressure. It is shown that the methane evaporation rates will rapidly decrease and cool the surrounding rock so that at the end of one month they would be between 50 Mcf/hr for a cavern of 25-ft radius and 700 Mcf/hr for a cavern of 100-ft radius. At the end of 10 years, the evaporation rates would be 18 and 100 Mcf/hr, respectively, for caverns of the same radii. The evaporation rates may be reduced by a factor of 2 to 10 by the application of insulation. The cost for mining the caverns is estimated to be $.75 to $1.25/Mcf of storage. This is substantially less than surface storage; it is believed to be safer and to result in lower maintenance, savings in space and savings in strategic materials. INTRODUCTION During the past few years, there has been an increasing interest in the economic feasibility of liquefying methane. Methane liquefaction is being considered for tanker transport; in addition, liquefaction is being reconsidered for shaving peak gas demands. Several articles have described natural gas liquefaction and the progress of the tanker in making trial runs from the United States to Great Britain to determine the feasibility of tanker transport. At the present time, pipelines are not designed to supply peak gas loads during extremely cold periods such as are oiten encountered in the North and Northeast. Gas is being stored in underground reservoirs en-route to its destination, but in many instances satisfactory storage in porous reservoirs has not been practical, especially along the Eastern seaboard where few petroleum reservoirs have been found. In England and other foreign countries, it is unlikely that satisfactory porous structures could be found, and it may be desirable to mine or excavate the rock to obtain storage. By storing the methane near the consumption point, product availability can be increased during periods of need. Methane liquefies at - 258OF at atmospheric pressure, and 1 cu ft of liquid methane will make about 600 cu ft of gaseous methane. Methane liquefaction for shaving peak gas demands was conducted in Cleveland, Ohio in the early 1940's. The Cleveland plant was designed to liquefy 4 MMcf/D of natural gas.' Development of several low-temperature processes has resulted in some improvements in the design of low-temperature storage vessels. Liquefied-methane storage vessels can be designed for various evaporation rates. The desired rate will depend on the reason for liquefaction. For shaving peak gas demands, the desired evaporation rates would be low, possibly between 0.2 and 1.5 per cent/day. For methane tanker transport and supply, the evaporation rates must be high and must equal the total daily rate of supply. It is apparent that the cost of storage facilities will depend on the objective and will vary appreciably. Surface storage of methane may cost between $3,000 and $20,000/MMscf, depending on the size and design. The failure of the surface storage vessels at Cleveland, with the resulting injury and loss of many lives, has caused considerable emphasis to be placed upon developing new, safer and improved methods of storing liquid methane. Storage of liquefied propane and butane in underground salt domes has been very satisfactory. The per-barrel cost of underground storage for any sizeable capacity is very small compared to the cost of surface storage for LPG mixtures. The larger the capacity of the underground storage, the less is the per-barrel cost. Numerous advantages appear to exist if liquefied methane could be satisfactorily stored underground, the principal advantages being increased safety, lower initial cost, lower maintenance cost, savings in space and savings in strategic materials. The purpose of this paper is to determine the feasibility of storing liquid methane underground in mined caverns. If a large spherical cavern is dug underground and is filled instantaneously with liquid methane, the surface of the sphere may approach the liquid methane temperature almost instantaneously. The temperature distribution for a sphere of radius r. in an infinite medium, initially at one temperature with spherical surface kept at T, from time t = 0, is given by Eq. 1.'

By M. M. Rao, P. G. Winchell

The growth rates of bainitic plates were measured at 400°C in Fe-Ni-C alloys containing 0.10 atom-fract~on nickel and 0.0012 to 0.0075 atonz-fraction carbon. The growth rates are adequately represented by where xc is nearly the atom fraction carbon of the bulk austenite and PXCy is nearly the carbon atom fractlon in the ferrlte of radiids p In equilibrium with austetzite. The form of the equation is that predicted by a model in which carbon diffusion in austernite controls the gvowth, but the numerical constatnt is two orders of magnitude below that suggested by the model. THE growth of bainitic plates in steel is often assumed to be controlled by the diffusion of carbon away from the advancing plate tip. This hypothesis predicts that the growth rate will increase as the carbon content of the austenite, xCz, is reduced toward the carbon content of the saturated ferrite comprising the plate tip, PxCY The growth rate should vary approximately as (xCg- pxCy)-1. Experimental observation of the growth behavior at low carbon levels should provide a significant test of this model. An alloying element in addition to carbon is required so that low-carbon austenite can be experimentally observed while undergoing bainitic transformation. Nickel was selected. The presence of nickel complicates the interpretation of the data in two ways: First, diffusion of nickel during the transformation would make analysis very difficult. Nickel is assumed immobile during the transformation. Second, nickel affects the solubility of carbon in ferrite and austenite in equilibrium. This effect has been evaluated.' At the completion of our experimental work Goode-now et al.2 published data in essential agreement with the observations to be reported here. Since their discussion is abbreviated and their data are scanty in the region of interest, we believe the present work is of significance. I) THE MODEL OF BAINITIC PLATE GROWTH The rate of lengthening of a plate is assumed to be controlled by the diffusion of carbon from the advancing ferrite-austenite interface into the surrounding austenite. The precipitation of carbides is assumed to be a secondary process. For ease of analysis the carbon-atom ratio,* pxCy, of austenite in equilibrium with ferrite which is convex with minimum curvature radius p, and the carbon-atom ratio, PxCY, of that ferrite in equilibrium with austenite are assumed independent of location on the ferrite-austenite interface. Since these carbon contents vary with the radius of curvature of the ferrite, p, their assumed positional independence must be held as an approximation. The consequences of these assumptions have been developed approximately by zener3 and Hillert,4 and the resulting equation for a platelet has been applied to bainite by Speich and cohen5 and Kaufman, Radcliffe, and Cohen.8 The Zener-Hillert equation* for plates is: The analysis of Hillert is supported by that of Hor-vay and cahn7 which involves no mathematical approximations but does include the assumption that the a/y interface coincides with an isoconcentration line. The solutions of Horvay and Cahn for elliptic paraboloids are replotted in Fig. 1. The shape of the paraboloid is expressed in terms of the ratio of the principal radii of curvature at its tip, A =p1/p2, which is also the ratio of the minor to the major axis of the elliptic cross section. The Zener-Hillert equation for plates is also plotted. The agreement is within a factor of two for (pxyaCr - xyC )/(xyC - PxCaY) between 0.5 and 100. This is the range of interest here and in most other work on bainite. The original form of the Zener-Hillert equation was the form given above with the right-hand side replaced by (pxCya -xCy)/(PxCya). This replacement is not appropriate here. 11) THE EXPERIMENTAL PROCEDURE Alloys were prepared and three kinds of experiments carried out. Continuous-cooling-transformation experiments were carried out on wires by measuring temperature and resistance during continuous cooling. Isothermal-transformation experiments were carried out on wires by measuring electrical resistance as a

Jan 1, 1968

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

By S. L. Lopata, E. B. Kula

A variation of yield and tensile strength with direction has been noted in heat-treated 4340 steel which had been warn-worked by rolling in the austenitic condition prior to quenching. Measurements by X-rays showed a preferred orientation of martensite crystals. Various ideal preferred orientations of martensite were calculated by assuming a preferred orientation for austenite and transforming this to martensite by the Kurdjumov -Sachs and Nishiyama relationships. Comparison with the measured preferred orientation showed that the ideal rolling texture for austenite in 4340 steel could be expressed as a (112) [111] texture with a component of (110) [112]. No evidence was found for any fiber axis in the rolling direction, or fop- a (123) [412] texture. The observed martensite pole figures can be adequately accounted for by these ideal austenite textures and by the Kurdjumou-Sachs or Nishiyama transformation relationships between austenite and martensite. ALTHOUGH preferred orientations are found in cold-rolled steel sheet and in many nonferrous metals, they are not generally encountered in wrought, heat-treated high-strength steels, since such steels are generally not cold worked sufficiently to develop a strong texture, and any texture that is present is removed during heat treatment by the phase transformations taking place. This report gives details on a preferred orientation found in warm-rolled and hardened 4340 steel. In a recent study, a special combination heat-treating and working technique was used in which 4340 steel was deformed in the austenitic condition, and before re crystallization of the austenite could occur, quenched to form martensite.' Since the austenite was unrecrystallized, it was cold worked and hence could have contained a preferred orientation which could be transmitted to the martensite on quenching, and this in turn could be manifested as a directionality of mechanical properties. Such a directionality of properties was found as a result of working, and this prompted an X-ray study of the preferred orientation. Literature Survey— Rolling Texture in Face-Cen-tered-Cubic Austenite—M a preferred orientation is found in a rolled and hardened steel, it is first appropriate to consider what texture existed in the austenite as a result of the rolling but prior to the transformation to martensite. The changes taking place as a result of the austenite-martensite transformation are then considered. In view of the instability of austenite in 4340 steel at low temperatures, no direct determination of the austenite texture was made. However, an estimate of the texture for austenite in 4340 steel may be made by considering the textures found for other face-centered-cubic metals. Barrett' has reviewed the rolling textures for many materials. The most common orientation in face-centered-cubic metals has the (110) planes parallel to the rolling plane and the [112] directions parallel to the rolling direction, or (110) [112]. Other orientations found are (112) [111], as well as (100) [001], (110) [001], and others. Beck and his co-workers, using quantitative pole figures, report that (123) [121],3 later corrected to (123) [412],4 better describes the ideal orientation. smallman5 reported that the ideal preferred orientation for high-purity face-centered-cubic metals is (123) [121], but that there is a transition to (110) [112] as solid solution elements are added. The latter texture tends to occur more readily at lower temperatures. This transition between the two textures was explained by differences in the slip characteristics with concentration or temperature. More recently, Jones and Fell6 concluded that the (123) [412] texture for face-centered-cubic metals could equally well be represented by a mixture of (110) [112] and (112) [111] textures, and hence it had no physical reality. From the above results it can be seen that there is no agreement on the "ideal" texture for fcc metals and, hence, no firm basis for assuming a texture for austenite in 4340 steel. Therefore, the orientations (110) [112], (123) [412], and (112) [111] have been considered in the following.* *The (123) [4121 is identical to the (123) [121] rotated 90 deg. Orientation Relationship between Austenite and Martensite—When martensite forms from austenite, certain crystallographic planes of the martensite are parallel to planes in the austenite. This orientation relationship was first determined by Kurdjumov and

Jan 1, 1960

By John M. Tinsley, Calvin D. Saunders, H. K. van Poollen

In the past few years much con-sideration has been given to the evaluation of the effect of hydraulic fracturing on the productivity of wells. Generally, these studies included the evaluation of fracturing materials, fracture extension and formation damage due to the use of various fracturing fluids. Only little consideration has been given to the characteristics, and in particular the flow capacity, of the fracture itself and its effect on well productivity. This paper presents the results of laboratory investigations pointed toward fie evaluation of the efficiency of various fracrures with special emphasis on the flow capacity of these fractures. Data presented in this paper are the results of both an electrical model study and physical testing. Under consideration are (I) effect of overflush, (2) premature production of well after treatment, (3) "tailing-in" with coarse sand near the end of the treatment, (4) effect of propping agent size and concentration, (5) reduction in effective frac-ture permeability caused by formation caused by formation fines, silt and clays, and (6) effect of various fluids on formation strength and competency. The results of this investigation indicate that the flow capacity of a fracture is affected by any or all of the various parameters mentioned above. The authors believe that a better understanding arid utilization of these factors should result in more efficient formation fracturing. INTRODUCTION Hydraulic fracturing has become almost a standard practice of many companies for stimulating production from old and new wells. Although most companies utilize this service, techniques of application vary widely between companies and areas. Probably too often when a well in an area responds favorably to a particular technique all future wells in the same area are treated in a similar manner. Possibly a modification of the technique would result in a further production increase. Variables, of which many are extremely difficult to evaluate from field results, hamper the selection of procedure changes. Attempts are being made by a number of organizations to analyze statistically treating techniques from production data. This is a very worthy and necessary approach but very possibly laboratory investigations may aid in evaluating some of the variables which tend to affect the results of a fracturing treatment. Some of the factors cannot be studied from practical field experience and only laboratory tests can show the possibilities which might exist. One of the factors which appears to be of major concern today is the flow capacity of the created fracture and how it can be changed. Papers on this general subject have been primarily concerned with the size of propping agent and the extent of fracture. Papers have also been written on the possible permeability damage to formations by fracturing fluids. In addition, it might be possible that another type of flow restriction is prevalent. This would be a restriction of flow through a sand-packed frac- ture caused by foreign materials integrating within the propping agent. This paper presents preliminary data obtained in an attempt to evaluate the effect of some factors affecting flow through sand-packed fractures. No attempt is being made to offer a fracturing technique adaptable to all areas and conditions, but to furnish data tending to show the possible effects which might be caused by variations in procedures and materials. PROPPING AGENT PERMEABLLITIES A hydraulically induced fracture containing sand as a propping agent may theoretically be classified as a packed-sand system. The flow of fluids through such packed systems has been the subject of much research. Although there have been numerous methods proposed for the evaluation of such systems, most writers agree on the general properties affecting their flow capacity or permeability. These properties include porosity, particle size, sphericity and the roughness of the particle. In some methods of evaluation . the particle size and sphericity terms are combined to produce an equation which is a function of the surface area of the particles. In this study the permeability of various fracturing sands was both measured and calculated. The apparatus for the permeability measurements consisted of a 52-in. Lucite tube with a 2.5-in. ID. A screen and drain plug were fitted in the bottom of this tube to retain and hold the sand in place while allowing fluid flow. Two pressure taps consisting of thin, highly perforated