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By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525'C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine' and LOW.' Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468'C, hold 72

Jan 1, 1969

By B. K. Larkin, H. R. Bailey

A model Of heat flow in an underground combustion process is studied. This model includes convection effects and thus is more general than previous studies which considered conduction as the only mechanistn for heat transfer. Both linear (tube run) and radial (field application) geometries are considered. The effects of ignition heaters, vertical losses and finite source width are considered for the linear case. The results are in the form of equations and are presented in graphical form for a number of cases. Convection effects increase frontal temperatures about 25 per cent over those computed for conductive transfer for typical field operating conditions. This increase in temperature is a result of heat being transported toward the front by the injection gas. Even greater temperature increases are realized as the per cent oxygen in the injection gas decreases. It is well known that compression costs are of considerable importance in estimating the economic feasibility of underground combustion. By assuming an ignition temperature for the combustion fuel, predictions of limiting conditions on fuel density and injection rate necessary to sustain the combustion zone are made. For typical field conditions, at least 0.75 lb/cu ft of fuel are needed with air as the injection gas. If the injection gas is 10 per cent oxygen and 90 per cent nitrogen, this figure is 0.69 lb/cu ft. INTRODUCTION The possibility of increasing oil recovery by underground combustion has been considered for many years. Recent field tests indicate that the underground combustion process is technically feasible. The economic feasibility depends to a large extent on the amount of air which must be injected to sustain combustion. Prediction of the success of employing underground combustion in a particular reservoir must be based on existing field tests, laboratory tube runs"' and solutions of mathematical or analog models. Vogel and Krueger5 devised an electrical analog of the heat transfer problem in an underground combus-ion process. They considered the problem of heat conduction from a cylindrical source with increasing radius assuming no vertical losses. Bailey and Larkin and Ramey solved the corresponding problem including vertical losses by considering a mathematical model of the conduction process. Ref. 9, 10 and 11 also present information related to the subject study. The present paper generalizes these results to include both conduction and convection mechanisms for heat flow. A model of the conduction-convection process is described. The partial differential equations governing this model are written and solved for a number of cases of interest. The formulas are evaluated and the results are presented graphically. A CONDUCTION-CONVECTION MODEL Description of the Model A number of models are employed in this paper, each of which approximate a particular physical situation depending on the geometry, i.e., linear or radial flow, the type of vertical heat losses, the nature of the source, etc. The geometry for both the linear and radial case is shown in Fig. 1. A particular linear model is described in this section, and variations from this model are described in later sections of the paper. Consider a homogeneous, semi-infinite porous prism with lateral sides insulated as shown in Fig. 1. The left end, x = 0, is heated for a time t, with a plane heater supplying a constant heat flux and during this time; gas (nitrogen) is passed through the pores of the prism at a constant mass flux. At time t, the heater is turned off and air is injected in place of the nitrogen. This causes combustion to take place, and a uniform source of width 1 is formed which moves at a constant velocity v, to the right. The frontal velocity v, is related to the gas velocity v,, through stoichiometric considerations

By A. W. H. Morris, G. H. Laurie, J. N. Pratt

Using- galvanic cells of the form Sn(liq)/Sn" (LiCl-KC1-SnCl,)/Sn-Ag (alloy), measurements have been made of relative thermodynamic properties of the a, C, E, and liquid phases of the Ag-Sn alloy system. Partial heats of solution of the components in the liquid alloys lzave also been observed by direct cal-orimetric measurement in an isoperibol calorimeter. The thermodynanzic quantities are disczlssed in relation to structural and other properties and the existence of anomalous minor fluctuations in the partial heats and entropies of solution in liquid alloys is tentatively suggested. In the course of a recent electro motive-force study of the thermodynamic properties of Sn-Ag-Pd liquids,' some measurements were also performed on the Ag-Sn binary system. Most previous thermodynamic studies of this system have been concerned with the liquid state. Measurements confined to the limiting heat of solution of silver in liquid tin have been made by many calorimetric workers2 while high-temperature calorimetric measurements of the heats of formation of the full range of liquid alloys are reported in the early work of Kawakami~ (1323°K) and more recently by Wittig and Gehrin~(1248°K). Electromotive-force studies on liquid alloys have been made by Yanko, Drake, and Hovorka' (606" to 686°K; 86 to 99.4 at. pct Sn) and by Frantik and Mc Donald' (900°K; 30 to 90 at. pct Sn). The only known measurements on the solid state are of heats of formation of the a, £, and c phases; these values were obtained using tin-solution calorimetry, at 723"K, by Kleppa,~ whose investigation also yielded heats of formation of liquid alloys containing more than 64 at. pct Sn. The present experiments on the Ag-Sn alloys include a re-examination of the liquid phase and, because of the dearth of free-energy data for the solid state, attempted measurements on the a, c, and E phases. The principal new feature of electromotive-force results obtained for the liquid phase was an indication of anomalous fluctuations in the partial heats and entropies of solution of tin at certain compositions. However, since the values for these thermodynamic quantities were determined from the temperature coefficients of cell potentials, which are commonly subject to considerable error, confirmation by calorimetric measurements was considered desirable. A detailed investigation of the partial heats of solution of the components in the binary liquids was made using a liquid metal solution calorimeter. I) GALVANIC CELL STUDIES a) Experimental Details. Measurements were made, as a function of alloy composition and temperature, of the potentials of reversible galvanic cells of the form: ~n(liq)/~n++/~n-Ag (solid or liquid alloy) Details of the apparatus and experimental techniques have been given elsewhere.' so that a brief account will suffice here. Molten salt, 58 mole pct LiC1-42 mole pct KC1, containing small amounts (1 to 2 mole pct) of stannous chloride was used as the electrolyte. The salts were dehydrated by pre-electrolysis and vacuum -drying techniques. Cells were established under an argon atmosphere by immersing tin and alloy electrodes in the molten salt contained in a large silica tube, heated in a vertical resistance furnace. The tube was sealed at the top by a head plate provided with openings permitting the simultaneous insertion of six electrodes, a central thermocouple sheath, and connections to vacuum and argon lines. Temperatures were controlled to *0.2"C over prolonged periods, with maximum variation over the electrodes at any time of 0.l°C. Temperatures were measured with a standardized Pt/13 pct Rh-Pt couple. The electromotive force of this and the cell potentials were measured on a Cambridge Vernier potentiometer and short-period galvanometer. Alloys were prepared from Pass "S" tin (99.999 pct) and Johnson-Matthey high-purity silver (99.999 pct) by melting in evacuated silica capsules and quenching in cold water. For liquid phase experiments, pieces of the resulting alloys were remelted into prepared silica electrode units, while solid electrodes were prepared by remelting into 3-mm bore tubing, inserting a cleaned molybdenum lead wire, and quenching to produce uniform rods about 3 cm in length, with soundly attached leads. In all cases remelting was done under an argon atmosphere. The solid electrodes were subsequently annealed in evacu ated silica tubes for 14 days at about 20°C below the solidus and quenched. Analyses showed that these techniques produced uniform electrodes with no significant change from weighed out compositions. b) Results and Discussion. Measurements were made on about forty alloys in the solid and liquid states, over varying ranges of temperature between 550" and 1050°K. Stable, mutually consistent, and reproducible electromotive-force data were obtained with most liquid alloys and these are shown in Fig. 1. Investigations were extended below the liquidus tem-

Jan 1, 1967

By Donald E. Meyer

High current-low voltage EB-gun evaporation in an oil-free ultra-high vacuum system was found to be necessary, though not sufficient, for stability (300°C, 106 v per on) of aluminium gate MOSFET's and MOS capacitors not stabilized by a phosphorous glaze. five characteristics of the equipment used: 1) Vacuum purification of the aluminum charge, 2) Ionization of the evaporant by the electron beam, 3) X-ray formation, 4) Residual gases during evaporation, and 5) Metal film structure were studied as Possibly significant in MOS fabrication. EVAPORATION of contact metals common to the semiconductor industry historically has been accomplished with oil diffusion pump systems and various resistance heated evaporant sources as dictated by the type of metal evaporated. To meet a need for greater reliability of semiconductor devices, other metallization methods were developed. A good example would be application of the moly-gold contact system to integrated circuits with deposition by RF or triode sputtering.' More recently, fabrication of stable metal-oxide-silicon devices and circuits has put new demands on metallization. The purity of the thin metal films composing MOS structures is critical, particularly at the metal-oxide interface, and ultra-high vacuum metallization using sputter-ion pumping and electron beam gun (EB-gun) evaporation are well suited for the task. At this laboratory aluminum has been the most common contact-gate metal for both MOS capacitors and MOSFET's. In the earliest work with MOS capacitors, aluminum was evaporated from wetted tungsten filaments using both diffusion pump and ion pump vacuum systems. In spite of clean oxide techniques these capacitors were unstable under bias-tempera-ture stressing. Only after a switch to EB evaporation of aluminum were stable capacitors produced. Using the same techniques it was possible to make MOSFET's with equivalent stability. Stability data for a discrete MOSFET is shown in Fig. 1. This is a "clean" oxide gate (no phosphorus stabilization or no etch back of a thicker gate) having a thickness of lOOO? thermally grown on the (111) plane. Gate length after diffusion was 0.24 mils, and the devices were hermetically sealed. Stressing conditions were 300°C and 106 v per cm applied alternately as a positive and negative field for 10 min, 50 min, and 4 hr for a total stress time of 10 hr. An initial shift in turn-on voltage of 0.1 v was detected for 10 min of positive bias. All evidence at this laboratory indicated that while EB-gun evaporation of ultra-high purity aluminum was not sufficient for 300°C stability, it did seem to be necessary. There may well then be something inherent in the EB-gun deposition used which enhanced stability, and probably no single factor existed but rather a series of factors. It is the purpose of this paper to report on some of the investigations carried out to learn more about EB-gun evaporation in ultra-high vacuum systems. EXPERIMENTAL DESCRIPTION The EB-gun was self accelerated, had a maximum power rating of 10 kw, and used a water-cooled copper crucible able to hold a 20-g aluminum charge. The electron beam was bent 180 deg and focused by an electromagnet which also provided movement of the beam across the crucible. Normal power conditions in this work were 9 kv and 300 to 600 mamp. The gun can be described as high-cur rent/low-voltage and was quite different in its mechanism of operation from EB-guns with much higher acceleration potentials. An oil-free vacuum system capable of 5 x 10- l0torr, a quartz crystal rate and thickness monitor and a quadruple mass spectrometer completed the evaporation system, Fig. 2. A typical evaporation cycle consisted of a 3 to 4 hr pumpdown to the upper l0-9 range and evaporation at l0? per sec with the pressure in the bell jar not rising above 1 x 10"7 torr. Thickness control was 5 pct or less and could be automatically monitored and controlled. Five phenomena associated with the EB evaporation and considered as possible contributors to Ma performance included a purification effect, ionization of evaporating aluminum, X-rays, constitution of vacuum ambient during evaporation, and film structure dependence upon evaporation rate. These phenomena are now discussed. Vacuum Purification. The design of the EB-gun permitted purification of the aluminum charge by vacuum outgassing. Particular features included an efficiently water-cooled copper hearth with a capacity of over 20 g of aluminum and the capability for sweeping the beam across the charge. Such capacity meant that aluminum had to be added only after about every fifth evaporation. A new charge was not required each evaporation as is necessary with filament evaporation. An oxide "scum" which appeared on the charge could be completely cleared from the top hemisphere of the charge by sweeping with the beam prior to opening the shutter. An indication of the purifying effect was obtained by a series of analytical measurements on incoming aluminum, after melting but with little vacuum out-gassing, after 30 min outgassing, and the evaporated film itself. Either a solids (spark source) mass spectrometer or an emission spectrometer were used for analyzing the aluminum charge. Analysis of the evapo-

Jan 1, 1970

By A. W. Adamson

A model for transport processes in liquid mixtures is discussed which supposes that the elementary act involves a position exchange between two species and that the exchange is so confined by the solvent cage as to occur nearly isosterically. The rate-determining step, thus, is likened to a bi-molecular reaction and is so treated, using absolute rate theory. The cage model has been applied to diffusion, thermal diffusion, sedimentation and viscosity, but only the first and last of these phenomena are emphasized in the present paper. The model leads to semi-empirical relationships between the absolute value for a digusion coefficient and the activation energy for diffusion, between mutual and self-diffusion coefficients and for the variation of the viscosity of a binary mixture with composition. These are discussed in relation to experimental data for various systems, including hydrocarbon mixtures. It is shown that the proposed viscosity equation and seven other commonly used ones all may be regarded as special cases of a single general relationship; a brief critical analysis is made of the basis of selection of one or the other for data fitting or interpolation. INTRODUCTION AND GENERAL THEORY The present paper covers a brief discussion of a cage model for transport processes in liquid mixtures and how this model may be useful in treating the diffusional behavior and the viscosity of such systems. Since diffusion requires the more detailed treatment, it will be taken up first, and the model then applied to viscosity. There are two types of diffusion coefficients that may be measured experimentally, apart from thermal diffusion quantities. The first is the mutual or binary diffusion coefficient, D which may be defined in terms of Fick's first law. This states that the permeation, or flux P, is proportional to the concentration gradient. In the usual experiment, P is measured relative to a frame of reference fixed with respect to the medium (e.g., the diaphragm in a diffusion cell); as a consequence, the same value of D is obtained regardless of whether P and C refer to Component 1 or to Component 2; i.e., there is only one independent mutual diffusion coefficient for a binary system. In addition to D there will be various self-diffusion coefficients. defined in terms of the gradient in labelled species i and its permeation in an otherwise uniform medium. The thermodynamic approach to mutual diffusion supposes that the actual driving force is the gradient of the chemical potential, i.e., that In the case of a dilute solution of solute, Eqs. 1 and 3 lead to the Einstein equation, If the solution is ideal and the friction coefficient is taken to be then the familiar Stokes- Einstein equation results. Mutual and self-diffusion coefficients can not be related on general thermodynamic grounds; it is necessary to invoke some additional assumptions, i.e., a model; several such have been proposed. Hartley and Crank' supposed the existence of separate, intrinsic diffusion coefficients (Dl and D2) for each component, essentially corresponding to the two self-diffusion coefficients. The two flows can not be independent, however, but must be coupled through the usual restriction that there be no net volume flow. For an ideal solution. one then obtains' Glasstone, et al' treated diffusion in terms of absolute rate theory, but their approach otherwise resembled the previously mentioned one in that each species was considered to move with respect to the general medium in a manner determined by its individual jump distance and specific rate constant. For other than dilute solutions, a coupling of flows leading to an equation such as Eq. 6 would again be present. However, as required by Eq. 6, one does expect that the self-diffusion coefficient for the solute and the mutual-diffusion coefficient for the system become identical at infinite dilution. Lamm4 recognized that there should be three distinctive interactions in a two-component system-1-1, 1-2 and 2-2 — and, therefore, proposed three rather than two fundamental friction coefficients. Mutual diffusion resulted from 1-2 interactions only, and self-diffusion resulted from 1-2 plus either 1-1 or 2-2 interactions. Again, a collective coupling between all motions was imposed to meet the condition of no net volume flow. Laity' has shown how to convert the Onsager equations to a form very similar to Lamm's. Cage Model For Diffusion Work in this laboratory on diffusion in aqueous sucrose solutions made it apparent that three, rather than two, interactions were indeed needed," but considera-

By F. D. Hoyt, H. L. Hartman

The development of new processes and methods by The Pennsylvania State University to improve slate quarrying technology has centered in recent years on cutting and sawing stone in the quarry to eliminate a second cutting process in the mill. Two machines exhibit promise for this work: 1) a circular saw mounting diamonds or hard inserts to produce smaller sizes of stone and 2) a chain saw with insert cutting teeth to produce stone in the larger dimensions. Prototype machines have been constructed and tested in several Pennsylvania slate quarries, and one commercial installation has been operated for several months with a circular diamond saw. Other kinds of dimension stones may be cut by these saws. Research at Penn State has begun to study the fundamental cutting action of rotary tools or saws in slate and other dimension stones. A laboratory drill press is being instrumented to permit thrust-torque-rotational speed us penetration rate studies of single tooth cutting surfaces on stone. Machinability studies of slate conducted with tungsten-carbide inserts have been performed. The dimension stone industry generally accepts the rather basic premise that the larger the block removed from the quarry, the more practical and economical the operation. Thus, the concept of cutting to size any dimension stone while it remains in place in the parent bed would receive little consideration from the majority of members of the industry. However, the slate industry, which is usually considered a separate member of the dimension stone family, is pioneering in the development of an in-place sawing method. Before any final decision can be reached concerning a proposed new system, it is essential to take a long, hard look at the present method of operation in order to determine if the new system is indeed an improvement or even desirable. In the following section is a brief description of present quarry practice in the slate quarries of eastern Pennsylvania. PRESENT METHOD OF QUARRYING SLATE In the numerous slate quarries of Lehigh and Northampton Counties of Pennsylvania, the grain and cleavage of the slate are most often at right angles to each other; if a third surface is broken at right angles to these two natural planes of weakness, blocks of more or less rectangular shape can be separated.' In conventional quarrying a large calyx core drill prepares holes of 36-in. diam in which wire-saw standards are positioned. By wire sawing between strategically located core-drill holes, large sinks or benches of virgin slate are opened up. The sides freed by wire sawing will vary from quarry to quarry but generally are rectangular in shape with dimensions averaging 20 ft in length and about 15 ft in depth. Some quarries are fortunate in having a joint or natural parting to work to, which of course diminishes the amount of core drilling and wire sawing required. Once the various benches have been developed either through wire sawing alone or through a combination of wire sawing and natural jointing planes, the block removal proceeds in the following manner. A plug hole is drilled in the block with a compressed-air hammer and a feathering chisel is inserted in the hole to cause a fracture of the rock either with or against the grain as indicated by the positioning of the so-called feathers. This operation is referred to as sculping. After a block has been freed with and against the grain by means of wedging from the cross fracture with long bars or levers, the block is further freed along the cleavage plane by shimming it up with small wooden pieces in an operation known as styling. A large steel loading chain is wrapped around a block thus freed and the chain is attached to the wheel of an overhead cable. The block is then hoisted vertically to the cableway and moved along this cableway laterally to the lip or edge of the quarry. From here it is unloaded onto a rail car or truck for transportation to the processing mill. Except for occasional blasting to free stubborn blocks,

Jan 1, 1961

By R. D. Burlingame, T. L. Joseph, Gust Bitsianes

DESPITE almost fifty years of commercial practice, the sintering of iron ore has received little fundamental study. Much of the theoretical work1-'has dealt with the constitution of sinter produced under widely varying conditions. While these studies have broadened our knowledge of the changes that occur in the sintering zone and in the freshly formed sinter during the early stages of cooling, they provide little insight into the changes that precede the formation of sinter. These preliminary changes merit study as a part of the overall process. Hessle. working with beds of Swedish magnetite concentrates, was one of the first investigators to study the sintering process in its entirety. On the basis of temperatures observed at various levels of the bed during sintering, he postulated a number of distinct reaction zones to account for the chemical changes leading to the formation of sinter. A more direct method of attack is that of arresting the sintering zone after it has progressed part way through the bed. A study of a vertical cross section through such a quenched bed provides direct information on the changes taking place at various levels. This method was used by McBriar et al.' to show that several well-defined zones of chemical change existed within beds that were typical of British sintering practice. The same general method of attack was developed independently in the present investigation to study partially sintered beds typical of American practice. Experimental Sintering Equipment The sintering operation was carried out on an experimental scale with the equipment shown in Fig. 1. The refractory-walled sintering chamber A was 11 in. deep and averaged 9 in. in diameter. Air was introduced through a tapered flow section B, which contained the orifice C for accurate metering of the incoming air. This section was located directly above the square ignition housing D, which in turn rested upon the sintering chamber A. The bed was ignited with burner E. The required suction for the operation was furnished by a fan F, which had an air capacity of 500 cfm (stp). Hot exhaust gases from the sintering chamber were cleaned in the dustcatcher G before entering the exhaust fan. In the study of partially sintered beds, it was essential to find some technique for removing the entire charge from the sintering pot without disarranging the unsintered bottom portion. This problem was finally solved by sintering the charge in a removable basket, which snugly fitted the sintering chamber. This basket was constructed of two thicknesses of window screen and was lined with a 3/16-in. layer of asbestos paper. The bottom of the basket consisted of two thicknesses of wire screen, which were fastened to the basket wall. For high fuel mixtures, additional insulation was provided by a somewhat thicker layer of asbestos cement. Preparation of Partially Sintered Mixtures The moist feed was carefully placed in the sintering basket, to prevent segregation of the particles, which varied widely in size and composition. A thermocouple was placed in the center of the basket with the hot junction halfway down, and the mixture was evenly distributed around it. During ignition and throughout the sintering of the upper half of the bed, the hot junction temperature increased very little. When the sintering zone reached the halfway point, as indicated by the sudden increase in the hot junction temperature, the charge was quenched. During quenching the suction was turned off and the orifice was tightly stoppered to prevent further influx of air. At the same time, nitrogen was admitted to the sintering chamber through the orifice tap. As soon as the nitrogen had displaced the air and products of combustion, the charge was removed from the sintering pot for immediate dissection. It is impossible to preserve the exact zone structure of the bed at the instant that combustion is arrested unless the downward transmission of heat is also immediately stopped. Fortunately, heat transfer is very slow in beds containing a stationary fluid, especially if the particle size is small. It follows that the minimum quantity of nitrogen should be used to displace the air and that static conditions be established as soon as possible. A very steep temperature gradient across the combustion zone for some time after the quench was evidence of in-

Jan 1, 1957

By H. I. Kaplan, C. Laird

Pulsating contpresslon experiments have been carried out on coppev single crystals in order to test the adequacy of mechanisms which have been suggested for stage I cvack grouth when tension-compression loading is the mode of- applying stress. Although dejorrrzation continues slowly for many millions 01 cycles under Pulsating compression stresses both within slip bands formed in the first cycle and by the creation of new bands, the morphology of these bands is not typical of fatigue slip bands in general and neither initiation of cracks nor propagation of artificially induced cracks was observed. It is therefore concluded that 1) initiation and growth of cvacks in fatigue is a consequence of repeatedly reviersed, microplastic deformation rather than intermittent, unidirectional deforma-tion, 2) gvowth of- cracks in polycrystalline specimens FAILURE of a plain specimen subjected to cyclic tension-compression stresses is known to take place by two stages of cracking.1,2 The first stage is characterized by propagation along slip planes roughly at 45 deg to the stress axis, in the outermost layers of the specimen, and at a rate of the order of angstroms per cycle. The average macro orientation of a stage I crack is normally at right angles to the stress axis,3 however, except in a few cases, e.g., single crystals in suitable orientation, when both the micro and macro directions of propagation are at 45 deg to the axis. After a stage I crack has penetrated to such a depth that the stress on the remaining section of metal is significantly increased, stage II crack propagation succeeds stage I, at right angles to the stress axis both micro and macroscopically. Direct evidence of the processes occurring during a subjected to pulsating compression stresses is caused by the setting-up of local tensile stresses due to interactions between grains, and 3) both unslipping mechanisms and operation of the "plastic blunting process " within a single slip band are adequate descriptions 01- stage I growth, being fundamentally similar. The slip mode of a material, however, is considered to control whether unslipping or the plastic blunting process takes place. Thus materials of planar slip mode fauor unslipping while those hacing a wavy mode, and capable of cross slip, can fail in stage I by the plastic blunting process. Similarly, and perhaps more importantly, reversed torsion and tension-compression modes of applying stress may be expected to cause the unslipping mechanism and the plastic blunting process, respectively. single stress cycle4,5 shows that stage II crack propagation takes place by a repetitive plastic rounding and closing of the crack tip. This mechanism has come to be called the "plastic blunting process".6 On the other hand, the extreme smallness of the phenomena occurring in stage I growth prevents elucidation of its mechanism by direct observation. Many suggestions have been proposed for this mechanism,'"-" most of them involving some kind of random or systematic unslipping process. It is possible, however, that the mechanism of stage I growth is essentially the same as that of stage 11, but occurring on a much smaller scale.6 In this situation, it has been observed that cracks propagate along slip bands comprising dislocation cell structures and bounded on either side by regions of different dislocation density and distribution." Since there is evidence that such bands are softer than their matrix, * it may be expected that the plastic blunting process occurs within a single slip band during stage I growth, rather than on two gross bands as in stage 11, when the acting stress is greater.= The blunting of the crack tip allowed by coordinated

Jan 1, 1968

By F. Bonaccorso, G. Venturello, C. Antonione

A study of the effect of small amounts of interstitial impurities on recovery and re crystallization in high-purity iron (99.995 pct) has been undertaken. This paper gives results on the effect of carbon, introduced in small-dosed amounts @om 0.0005 to 0.0086 wt pct) by heating iron specimens of high purity m a static atmosphere of CO + ,. The materials prepared in this way, cold-worked 80 pct and subjected to a series of isochronal and isothermal annealings, were submitted to examinations by X-rays, micrographs, and hardness tests. It was observed that effect of carbon is remarkable in the sense of blocking recovery of mechanical properties up to the temperature at which re crystallization begins. On the contrary, carbon has a negligible effect on primary re crystallization temperature, when compared with the known effect of substitutional impurities. This is in agreement with the high mobility of interstitials. In effect, only a slight decrease, -20 pct, of the grain-boundary motion rate was noted, due to the interaction between the grain boundary and the carbon atoms. On the other hand, in the samples in which the carbon content is above the solubility limit at the temperature at which re crystallization occurs, a slight increase of nucleation frequency is noted due to the presence of precipitated carbides. ThE effect of purity on recovery and recrystalli-zation phenomena has been known for a long time; however, recently, new attention has been given to the problem since new methods for obtaining metals with extremely low impurity contents have become available. Most of this research work essentially concerns the effects of impurities which cause precipitates or give rise to substitutional solid solutions. The works of Bolling and winegard1 and Aust and utter' on lead, and Vandermeer and orddon' on aluminum, 01sen4 on nickel, and Abrahamson and Blakeney on iron should in particular be referred to. On the effect of this type of impurities a quantitative theory has been formulated by Detert and Lucke6 and has lately been discussed critically by Cahn7 and Gordon and vandermeer.' Interstitial solid solutions in iron have not as yet been studied. As the study of the effect of interstitials is of great interest both from a theoretical and practical standpoint, it was deemed useful to examine the effects of carbon, nitrogen, and boron on recovery and primary recrystallization of iron. There already is some work by Chaudron et al.,1-" on the effect of interstitials on iron; their work, however, mainly concerns secondary recrystallization. The present paper refers in particular to the effect of carbon. EXPERIMENTAL PART Preparation of Materials. The pure iron used for this research was obtained from FeCIS recrystal-lized and purified by extraction with isopropylic ether. From the ferric chloride purified in this manner, hydroxide was precipitated with a solution of very pure ammonia, and, by calcination in pure sintered alumina crucibles, oxide was obtained. Reduction of the oxide to iron sponge was performed in sintered alumina tubes with very pure hydrogen at 650°C; at the end of the operation temperature was increased to 900°C. Specimens for the experiments were obtained by sintering the sponge at 1480°C in pure Hz after a pre sinter ing treatment at 900° C. It is important to note that the treatment at 1480°C in Ha produces a further purification from more volatile elements such as zinc, cadmium, arsenic, lead, and tin. Details on the preparation and characteristics of this type of very pure iron are given in a previous work.'' Only the complete analysis performed by neutron-activation methodsz3 is given here, Table I. Some of the specimens prepared in this way were carburized in the 0 region with very low amounts of carbon by treating them at 700°C in a static atmosphere of Ha containing a definite amount of CO. The set-up used is described in Fig. 1. A gas-tight quartz tube containing the specimen to be carburized and an internal friction control specimen, after being evacuated, was filled with Hz

Jan 1, 1963

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 Hsun Hu

Three single crystal strips of a 3 pct Si-Fe alloy with approximately (110) [001], (210) [001], and (100) [001] orientations were rolled at room temperature to 30, 50, and 70 pct reductions in thickness. Their deformation and annealing textures were studied. In most cases, the change in texture upon recrystallization and subsequent growth can be described as rotations around the <I10 > axes. A < WO > rotational relationship was also observed. The temperature dependence of recrystallization textures was discussed. WhILE considerable data have been published on the rolling and annealing textures in silicon-iron crystals, very little study has been made on the texture formation at various stages of rolling deformation, and during the process of recrystallization. Dunn&apos; in some of his early works had studied the orientation of recrystallized grains in crystals cut out from lightly rolled (10 to 20 pct reduction) large grained sheets. He found that in most cases a third-order twin relationship exists between the crystal and the recrystallized grains. This orientation relationship actually corresponds to rotations around the <110> axes. The more recent studies of Dunn &apos; and of Dunn and Koh &apos;5 on the rolling and annealing textures in various silicon-iron crystals were concerned mostly with a cold-rolling reduction of 70 pct and annealing at 980OC for recrystallization. Reductions of similar magnitude were also employed by Walter and Hibbard in rolling columnar crystal aggregates of a silicon-iron ingot. A systematic study of the effect of rolling reduction on the deforma- tion and annealing textures is still lacking. Regarding the effect of annealing temperature on the texture formation, Dunn3 has observed a change in therecrys-tallization texture by annealing a 70 pct rolled (1 10) [001] crystal first at a low temperature then atahigh temperature. But the details of texture formation during the annealing treatments were not thoroughly investigated. The present investigation was undertaken to study the texture developments at various stages of rolling deformation and of the recrystallization process, so that a better understanding on the texture formation in silicon-iron crystals may be obtained. EXPERIMENTAL PROCEDURE The three single crystals used in the present investigation were selected from the group of single crystal strips previously prepared7 from a high grade commercial Si-Fe alloy with 3 pct Si. The thickness of these single crystal strips was 0.040 in. The orientations of the three crystals as determined by the X-ray back-reflection Laue technique are shown in Table I. Each of the three crystals was rolled at room temperature along the strip direction to 30, 50, and 70

Jan 1, 1962

By E. R. Haymaker, C. W. Binckley, F. R. Burgess

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well&apos;s actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2&apos;&apos; O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By J. L. Walter

Extra-low carbon iron sheet, when deformed and annealed, undergoes exaggerated or abnormal grain growth in the critically deformed regions of the sheet. This exaggerated pmth occurs, for low strains (3 to 6 pct), only in sheet which has a fine dispersion of precipitates in the subsurface region of the sheet and fewer and coarser precipitates in the sheet interior. These particles have been identified as manganese sulfides. Wing the anneal, grains near the surface are gvowth-inhibited by the fine particles but the grains in the interior are free to grow normally. With the additional driving force provided by the strain energy, the interior grains first grow into the small subsurface pains. Eventually, these growing grains grow completely through the sheet. Calculations of limiting grain sizes at various values of strain indicate that a volume fraction of precipitates in excess of 10-&apos; would be required to eliminate exaggerated growth in material strained to 10 pct. OPEN-COIL annealing has made decarburization of sheet steel both efficient and economically practical. Use of such material for porcelain-enameling stock is one of many possible applications of low-carbon iron since carbon in steel is deleterious to porcelain-enameling properties.&apos; However, the extra-low carbon iron presently available presents another problem, that of exaggerated grain growth in regions where the sheet has been deformed as by bending or stretching. In exaggerated grain growth a few grains start to absorb their neighbors and these may become very much larger than the average grains of the sheet. Other names for exaggerated grain growth are coarsening, critical grain growth, secondary recrystallization, abnormal grain growth, or discontinuous grain growth. While this grain growth does not affect the enameling qualities of the low-carbon iron sheet, their presence results in a marked reduction of tensile-yield strength in the region of the sheet containing the large grains. The loss of tensile yield strength may render the material unsuitable for many applications . This report describes the results of a study undertaken to determine the cause of the exaggerated grab growth in extra-1ow carbon iron and, if possi- ble, to prescribe practical procedures for its prevention. GENERAL THEORY The driving force for exaggerated grain growth is the grain boundary free energy. This driving force is proportional to (l/rl + l/r2) where rl and r2 are the mutually perpendicular radii of curvature of the boundary between the growing grain and the grain being consumed. Thus, the greater the difference in size between the growing grain and the matrix grains, the higher the driving force for grain growth. If, however, the matrix grains are free to grow simultaneously, the driving force for exaggerated growth will be diminished. Stability toward growth of the matrix grains may be caused by a) a strong single orientation texture (texture inhibition),&apos; b) a dispersed second phase,3"5 c) the thickness effect,&apos; or d) intergranular segregation.7"9 As exaggerated growth occurs when growth of the matrix grains has been slowed by the stabilizing processes mentioned above, there must be an additional factor acting to promote growth of a few of the grains to the point where they are enough larger than the matrix grains that boundary energy driving forces are sufficient to cause continued growth. For instance, at the annealing temperature, growth-inhibiting inclusions may slowly dissolve and coalesce. Eventually, a grain boundary becomes unlocked and migration occurs at the expense of neighboring grains. Or, an additional driving force may be supplied to some of the grains if the material is strained. Then, since some grains will be strained less than others, the difference in strain energy between adjacent grains may be sufficient to overcome boundary locking and allow growth of the grains with lower strain energies. In the present study, therefore, such factors as the presence or absence of dispersed phases, the nature of the exaggerated growth, and the effect of strain have been considered. EXPERIMENTAL PROCEDURE I) Material and Processing. Three types of low-carbon iron were used in this study; types A and B were commercial grades, each from a different supplier.* The precise details of the processing of

Jan 1, 1963

By J. Waldman, M. B. Bever, A. K. Jena

The heats of formation at 273°K of 6 silver-rich Ag-Cd solid solutions and the heat of formation at 78°K of one solid solution have been measured by tin solution calorimetry. The heats of formation are analyzed in terms of the quasichemical theory. If the enthalpy diffel-ence between a hypothetical fcc form and the hcp form of cadmium is taken into account, this analysis does not lead to the conclusion put forth in the literature that electronic effects make significant contributions to the heats of formation of silver-rich Ag-Cd solid solutions. The temperature dependence of the heats of formation is appreciable and negative near 78ºK, but decreases gradually to nearly zero abore 400°K. The relative partial enthalpies per grarn -atom of silver at 541°K and cadmium at 532" and 541°K in tin have also been determined. THE composition range of the silver-rich Ag-Cd solid solutions stable at room temperature extends to about 40 at. pct Cd. Heats of formation of these solid solutions at 308" and 723°K have been measured by solution calorimetry.1,2 Heats of formation for an average temperature of 800°K have also been calculated from vapor pressures.2,3 The heats of formation deviate from the values predicted by the quasichemical theory above about 30 at. pct Cd. This deviation has been attributed to electronic effects at the Brillouin zone boundaries.2 The heats of formation of Ag-Cd alloys are essentially the same at 308", 723", and 800°K; consequently the temperature dependence of the heat of formation d?H/dT = ?Cp is vanishingly small, although from the exothermic heats of formation a negative value would have been expected. In the investigation reported here the heats of formation at 273°K of 6 silver-rich Ag-Cd solid solutions and the heat of formation at 78°K of 1 solid solution have been measured by tin solution calorimetry. The results are analyzed in terms of the quasichemical theory and the dependence of the heats of formation on temperature is discussed. The relative partial enthalpies per gram-atom of silver in tin at 541" and cadmium in tin at 532" and 541°K were obtained in the course of this investigation. The values of the temperature dependence of the relative partial enthalpies per gram-atom of silver in tin derived from the data reported by various investigators2,4-9 are contradictory. The literature contains only a value for 517°K of the relative partial enthalpy per gram-atom of solid cadmium in tin.2 EXPERIMENTAL PROCEDURES Samples of Ag-Cd solid solutions were prepared by melting weighed amounts of silver (99.99 pct pure) and cadmium (99.95 pct pure) in graphite crucibles under a flux of molten potassium chloride.10 The solidified ingots were sealed in evacuated Vycor tubes and annealed at 775°K for 10 days. The ingots were swaged and drawn into wires. The wires, sealed in evacuated Pyrex tubes, were held at 725°K for 5 hr and cooled to 365°K at an average rate of 2.5ºK per hr, followed by furnace cooling to room temperature. Chemical analysis of samples taken from different parts of each ingot gave no indication of segregation. Metallographic examination showed the samples to be homogeneous. Samples of the solid solutions or of the component elements were added to tin-rich baths in a calorimeter." At the start of a run the bath consisted of pure tin. Silver was used in the form of wire of 0.01-in. diam as supplied and cadmium in the form of lumps. Gold (99.999 pct pure) was added with the samples in order to reduce the endothermic heat effect of additions of Ag-Cd solid solutions. Samples of only one composition were added in a run and the ratio of the weight of alloy to that of gold was the same in all additions of a given run. In each run several calibrating additions of tin were made from 273°K. The heat contents of tin were calculated from the following equation, which is based on published data:12 (HTºK- H279º) = 6.70 T - 72,300/T + 20 cal/gram-atom; 505°K < T < 650°K The heat effect of each addition was plotted against the average of the sum of the atom fractions of solutes in the solution before and after that addition. The total concentration of solutes at the end of a run was less than 2 at. pct. In this range the heat effect was a linear function of the atom fraction of the solutes. The heat effect at infinite dilution and the composition dependence of the heat effect were obtained from the plots. RESULTS AND DISCUSSION Evaluation of Data. The linear dependence on composition of the heat effects of additions suggests that in the dilute range the enthalpy interaction coefficients other than the first-order coefficients of silver, cadmium, and gold are negligible, as shown in a concurrent publication.13 The heat effects at infinite dilution and the values of the composition dependence of the heat effects are listed in Table I.

Jan 1, 1970

By AIME AIME

THE Seventh International Petroleum Exposition and Congress to be held in Tulsa, Okla., Oct. 4 to 11, inclusive, in true western spirit promises to be bigger and better than ever. The Exposition has become an established institution. It gives opportunity to petroleum engineers, technologists, and operators to see each year at one place what the tool makers and machinery manufacturers have to offer which is new or better. It has truly become a place "where men, methods and machinery meet." It is also a convenient focus for technical meetings of various kinds devoted to petroleum and natural gas problems. &apos;The Petroleum Division of the A. I. M. E. has for several years held its chief fall meeting at Tulsa just preceding the opening of the Es- position. This year our meeting will be on Oct. 2 and 3 and it will be held as usual at Hotel Mayo. The Mid- Continent Oil and Gas Association will, as usual, hold a meeting during the Exposition and this year the Petroleum Division of the A. S. M. E. will hold a three- day session, Oct. 6-8, in the auditorium on the Esposition grounds. In all, six technical sessions are planned by this Society, and aside from reports of committees some 20 technical papers are to be presented. Members of the Institute should attend its own meeting and stay over for as many days as possible for the other meeting at which they will hear and see much of helpful interest.

Jan 1, 1930

By Frank Firmstone

The material described below was made at Furnace No. 2, Longdale, Va., Oct. 28, 1907, during a sudden derangement of working, in the course of which the furnace became entirely bridged over and for some time no solid material whatever descended into the hearth. This caused the hearth to become so completely emptied that, at the tuyere-level, a pricker put in at one tuyere could be seen by looking in at the opposite one. The tap-hole was opened and the iron got out with some difficulty. It ran sluggishly, throwing many sparks, but was not too thick to run into the chill-molds. Naturally, the product was assumed to be white iron, which is almost always produced under similar circumstances; but on removal front the molds it proved to be very strong and tough, although full of blow-holes. Most of these blow-holes bad bright, unoxidized walls. The iron could be drilled by using a "special steel" drill, the drillings curling up similarly to those of steel. An analysis by P. W. Shimer of this unusual product gave: Si, 0.019; P, 0.228; S, 0,39; Mn, 0.042; C, 2.366; and graphite, 0:000 per cent. A cast of iron made just before the disturbance contained P, 0.98, and Mn, 1 per cent. The peculiar product seems to have been decarburized in the hearth and, at the same time, to have lost much phosphorus and manganese, either by the action of the blast in the empty hearth, or, more probably, by. contact with the cinder rich in iron which was formed at the time. Unfortunately, no specimen of the cinder was preserved, so its composition cannot be given. It seems very remarkable that, with the furnace in bad condition, the temperature should be high enough to keep such

Sep 1, 1908

By R. P. Alger, C. A. Doh, M. P. Tixier

The principle, the equipment and field operation of sonic logging are described. The tfio-receiver system produces logs independent of hole size and mud. Field experience is given and forms the basis for the interpretation of the log. The derivaiion of porosity values from measured velocities is discussed, according to the type of formations (hard formations, compacted sands, and unconsolidated formations). The time-average equation proposed by M. R. J. Wyllie, A. R. Gregory and L. W. Gardner is uscd as a basis for the computation of porosity in limestones, cemented sandstones and compacted sands. Variations in the lithologic character of limestones do not seem to change the porosity calibration markedly. The compaction of sands is related to the compaction of shale adjacent to them; and, thus, the shale velocity is used for the establishtnent of empirical relations for the computation of porosity in un-consolidated formations. Various forrnu.las are tentatively presented to account for shale and fluid content. Field experience demonstrates that considerable attenuation of sonic energy takes place in unconsolidated formations, particularly when gas bearing, and in fractrured formations. Unusually large attenuation produces skipped cycles, a feature easily recognized. The application of sonic logging to structura1 studies is featured, showing its possible integration with the dipmeter. Correlation and its application to the irrterpretation of seisrmic surveys are reviewed. The paper is illustrated with field examples. Sonic logging is the recording of the time required for a sound wave to traverse a definite length of formation. Sonic travel-times are inversely proportional to the speed of sound in the various formations. The speed of sound in subsurface formations depends upon the elastic properties of the rock matrix, the porosity of the formations and their fluid content and pressure. Below the "weathered" or low-velocity layer extending from 50 to 100 ft or so below the surface, sound velocities may range from about 6,000 ft/sec in shallow shales to as much as 34,000 ft/sec in dolomites. In hard formations (well cemented and/or compacted), the sonic log reflects the amount of fluid in the formations; hence, it correlates well with their porosity. In unconsolidated formations, which are usually of fairly high porosity, the sonic log gives an approach to porosity determination, when its readings are corrected for lack of compaction, shaliness, and fluid content. In such formations the sonic log may also indicate the presence of gas and may distinguish between oil- and water-bearing beds. Field experience with the sonic log in soft formations is more limited than that in hard formations. As a result, interpretation in soft formations is not as well developed at the present time. In all types of formations the sonic log is of considerable value for correlation and for the more detailed and accurate interpretation of seismic data. EQUIPMENT AND PRINCIPLE FIELD OPERATION The basic features of the sonic log" are a two-receiver system and two available short spacings. The log is recorded on film using a standard field unit. An SP curve is run along with the sonic curve to give a more interpretable log and to establish absclute depth control for comparison with other logs run in the same well. If desired, a gamma-ray curve may be recorded simultaneously with the sonic curve. Fig. 1 shows the sonic-gamma ray combination sonde. The sonic portion consists of a sound transmitter and three receivers mounted 3, 4 and 6 ft from the transmitter. When the first and second receivers are used, a sonic log of I -ft spacing (distance between receivers) is obtainea. Use of the first and third receivers provides a 3-ft spacing. The transmitter emits pulses at the rate of l0/sec. After the transmission of a pulse the first arrival of sound energy at each receiver triggers its response system. The differ-

By I. Javandel, P. A. Witherspoon

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

Jan 1, 1969

By W. K. Godfrey

The highest compressive strength cement has the highest bond strength in tests in which the cement is subjected to a confining pressure. After perforating, the bond strength is reduced to nearly zero when the pipe is supported by weak cement. Perforating does not affect the bond strength, however, when the pipe is supported by strong cement. Pipe supported by weak cement is damaged by perforating with expendable capsule jets, but is not damaged by perforating with the hollow carrier gun. High strength cements are recommended for oil wells that are to be perforated. Introduction The purpose of this work is to determine the effect of jet perforating on the bonding strength of oilwell cement at simulated down-hole conditions. Bond strength is a good criterion for determining the effectiveness of cement in performing its main function, i.e., that of isolating zones. According to the literature on the subject, the optimum cement strength for perforating is low and should not exceed 2,000 psi compressive strength. This conclusion was based on the appearance of bullet and jet perforations in neat and gel cements largely done in the absence of a confining pressure more than 15 years ago. Discussion Literature A relatively weak cement has been recommended in the literature as having optimum properties for perforating. In 1947, Oliphant and Farris tested bullet perforating of neat cements at various curing times.&apos; Some of the tests were made at down-hole conditions. They reported that the optimum cement strength for perforating was about 2,000 psi compressive strength. Enlarged holes occurred when strength was too low, and the cement shattered and cracked when the strength was too high. In 1951, Morgan and Dumbauld tested bullet and jet perforating of neat and gel cements at surface conditions.&apos; They reported that optimum cement has a compressive strength less than 2,000 psi. In their tests at atmospheric pressure, high strength cement shattered and cracked when perforated. Thus, the optimum cement strength was based on the appearance of neat and gel cement after perforating. In 1953, Clark showed a relation between cement strength and fluid shutoff.&apos; He concluded that a 500 psi compressive strength is required for good fluid shutoff and that maximum bonding ability is developed at approximately 1,000 psi compressive strength. In 1964, Bell and Shore invalidated most of the conclu sions by the previous authors when they demonstrated that atmospheric pressure tests cannot be used to determine casing deformation and damage that will result from perforating under down-hole conditions.&apos; They showed that the higher the hydrostatic pressure, the more restricted will be the expansion of gases generated by the charge. Less casing deformation and damage occurs under down-hole conditions than at atmospheric pressure. In recent work, Bearden et al. reported that jet perforating at surface pressure with the hollow carrier gun caused the cement sheath to shatter and crack.&apos; The perforating, however, did not seriously affect the pressure required to leak past the casing cement bond. Only three cementing mixtures were tested, and presumably they had strengths in excess of 2.000 psi. Bearden et al. also reported that the hydraulic bonding strength increased as the compressive strength increased. Their hydraulic test showed that approximately 1,000 psi pressure is sufficient to break the casing cement bond for a well aged neat Portland cement sheath. Unfortunately, the tests were not run with a confining pressure, so Bearden et al. were merely measuring the strength of their outer 8%-in. casing. In our investigation, we measured the hydraulic bond strength of cement to pipe under a confining pressure and found that the bond strength was not limited to 1,000 psi. Cement Bond The bond strength is a good criterion for measuring the effectiveness of cement in performing its main function, that of preventing interzonal communication of fluids behind the casing. Measuring bond strength after perforating should be a good quantitative method of determining optimum cement properties, and should be a better method than that used by previous investigators,11 &apos; who simply observed the appearance of the cement after perforating.

Jan 1, 1969

By G. R. Leverant, M. Gell

The high- and low-cycle fatigue poperties of MAR-M200 directionally -solidified into columnar-grained and single crystal forms were determined at 1400" and 1700°F. These results were compared with the corresponding properties of conventionally -cast MAR-M200. The low-cycle fatigue lives of the columnar-grained and single crystal materials were similar at both temperatures and were one to two orders of magnitude greater than those of conventionally-cast material. The variations in the fatigue lives among the three forms of MAR-M200 were related to the more rapid rate of intergranular muck propagation compared to that of transgranular propagation. In conventionally-cast MAR-M200, cracks were initiated in grain boundaries and crack popagation occurred rapidly along an almost continuous grain boundary path. In the columnar-grained material, crack initiation occurred on short transverse segments of grain boundaries, but crack propagation was transgranular. The fatigue lives of columnar-grained and single crystal materials were approximately the same because most of the life in both materials was spent in trans-granular propagation. For the directionally -solidified materials, the number of cycles to failure, Nf, can be related to the total strain range, , by: heT = K where n and K are 0.16 and 0.044 at 1400&apos;F and 0.29and 0.098 at 1700, respectively. In addition to intergranular crack initiation in the columnar-grained material, initiation also occurred at we-cracked MC carbides and micropores in both directionally-solidified materials. At 1400°F, fatigue life was reduced with increasing MC carbide size, but at 1700 there was no effect of carbide size. THE creep and stress-rupture properties of conventionally-cast nickel-base superalloys can be greatly improved by directional solidification into either single crystal or columnar-grained forms. The improvement in properties results from a reduction in intergranular cavitation and crack growth in the columnar-grained materials and the complete absence of this fracture mode in the single crystals. This paper describes the effect of grain boundaries on the elevated temperature fatigue properties of the nickel-base superalloy MAR-M200. The effect of cycling frequency on cracking arid fatigue life and the role of MC carbides and micropores on crack initiation are also emphasized. The fatigue properties of columnar-grained and single crystal MAR-M200 at room tem- perature,4,5 and the change in the mode of fatigue crack propagation with temperature6 have recently been described. I) EXPERIMENTAL PROCEDURE The material used in this study was the nickel-base superalloy MAR-M200, directionally-solidified into columnar-grained and single crystal forms. The columnar grains were approximately 0.5 mm in diam. The nominal composition of these materials in wt pct was 0.15C, 9Cr, 12.5W, loco, 5A1. 2Ti, lCb, 0.05Zr. 0.015B, bal Ni. They were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr. which resulted in 0.2 pct offset yield stresses of 150,000? 144,000, and 95,000 psi at room temperature? 1400°, and 1700°F, respectively. The corresponding elastic moduli parallel to the testing direction were 19.2. 15.0, and 12.5 x 106 psi, respectively. Specimen design, testing procedures and alloy mi-crostructure have been described previously and will only be summarized here. Following the 1600°F aging treatment. MAR-M200 contains an ordered, cuboidal, y&apos; precipitate 0.3 1 on edge, which is coherent with the 1 matrix. The y&apos; precipitate is quite stable; even after testing at 1700°F. the precipitate is only slightly enlarged and its corners somewhat rounded. The alloy also contains a small volume fraction of micropores, and MC carbides. some of which contain preexisting cracks5 formed during casting. These cracks are always parallel to the long dimension of the carbide. Measurement of MC carbide size has been described previously.5 Axial fatigue tests were conducted in air over a wide range of strain amplitudes in both the high - and low-cycle fatigue regions, with specimen lives varying from about 10&apos; to 10&apos; cycles. Low-cycle fatigue (LCF) tests were strain-controlled with strain varied between zero and a maximum tensile value at a frequency of about 2 cpm. High-cycle fatigue (HCF) tests were stress-controlled with the stress varied between 5000 psi and a maximum tensile value less than the yield stress at a frequency of either 10 cps or 0.033 cps (2 cpm). The temperature in the gage section was controlled to 52°F. Specimen axes were within 5 deg of the [001] growth axis of the single crystals and the common [001 ] growth axis of the columnar-grained material. Specimen gage sections were electro polished prior to testing. After the standard heat treatment, three specimens were coated with a typical aluminide coating applied as a slurry. An additional specimen was given the coating heat treatment without actually being coated. In all cases: specimens were reaged at 1600°F for 32 hr after receiving the coating heat treatment at 1975&apos;F for 4 hr.

Jan 1, 1970