Search Documents

By G. Bruggeman, K. G. Kreider

Grain boundary dij]usion coefficienls were measured in tungsten between 1400° and 2200° C and can be expressed by the equation sq cm per sec This activation energy confirms some eavlier estimates made .from tungsten sintering experiments. Grain boundary diffusion was found to occur in sub-bozrndavies having -misorientations of less than 10 deg. The actiuation energy for this subboundavy diffusion is equal to that for dijjusion in incoherent grain boundaries with in the limits of error. This is shown to be consistent with the dislocation model of Low-angle boundaries wheve diffusion occlcvs along- the dislocation 'YPipes" comprising -tile boundary. RECENT investigations of the sintering of tungsten powders all report activation energies which are considerably less than the activation energy for tungsten volume diffusion. Kothari' reports a value of 100 * 5 kcal per mole, Hayden and Brophy' obtained 90 kcal per mole, and Vasilos and smith3 found 110.7 kcal per mole from their sintering studies. Since most determinations of the activation energy for volume diffu-sion4-' fall between 120 and 160 kcal per mole (the true value seems most likely to be nearer 150 kcal per mole), the conclusion is drawn that the mass transport leading to densification during sintering is accomplished by grain boundary diffusion. This interpretation is consistent with various diffusion models of the sintering process. 10-12 Vasilos and Smith calculate diffusion coefficients from their data which fit the equation D * 1.36 x 10* exp(-llO,700/HD However, no direct measurements of tungsten grain boundary diffusion have been made. Furthermore, considerable disagreement exists between the directly measured values of tungsten volume diffusion.'-' In order to corroborate the inferred results of the sintering experiments concerning grain boundary diffusion and to provide accurate diffusion data essential to the analysis of the kinetics of creep, oxidation, precipitation, and so forth, the present work was undertaken to measure self-diffusion in single-crystal and polycrystalline tungsten between 1400" and 2200°C. It is within this temperature range that tungsten sintering is done, the re crystallization of tungsten occurs, and the widest application of tungsten as a high-temperature material will probably be made. EXPERIMENTAL PROCEDURE Radioactive WlE5 was produced by irradiating tungstic acid in a neutron flux of 1.2 x 1012 neutrons per sq cm per sec for 36 hr. A 2-week waiting period was allowed for the decay of w"~ also produced by the irradiation. (w"~ has a half-life of 24 hr.) The half-life of the remaining isotope was determined to be 75 days confirming the presence of w lE5 and the absence of any undesired radionuclide. Specimens 4 in. in diam and $ in. thick were cut from polycrystalline swaged tungsten rods (recrystal-lized) and from Linde single-crystal rods. Chemical analyses of these materials appear in Table I. Actually upon closer examination, the single-crystal specimens were found to consist of several subgrains separated primarily by tilt boundaries in which the misor-ientation ranged from 3 to 10 deg. Thus, it was possible to measure boundary diffusion coefficients in these low-angle subboundaries as well as in the incoherent boundaries of the polycrystalline specimens. The two faces of each specimen were ground flat and parallel within 0.0001 in. The radioactive tungstic acid was dissolved in concentrated ammonium hydroxide, placed on the ground flat of the specimen, and evaporated to dryness. The oxide was then reduced in hydrogen at 1000°C resulting in a layer of wlE5 approximately 1 p thick. The diffusion anneals were performed in vacuum in a tantalum resistance furnace. Time at temperature ranged from 10 hr at 1400°C to 2 hr at 2200°C. The penetration profile was determined by measuring the residual activity after successive removal of surface layers by grinding on metallographic polishing paper. Extreme care was exercised to insure that sections were always taken normal to the diffusion direction; this was verified repeatedly by checking that front and back surfaces of the specimen remained parallel. The activity was measured with an end-window Geiger-Mueller counter. The sides and edges of the specimen were well-shielded to eliminate possible effects due to surface diffusion. The weight of the

Jan 1, 1968

By G. S. Cole

The temperature has been measured ahead of stationary solid-liquid interfaces under conditions approximating luzidirectional heat flow and therefore unidirectional solidification. Natural convection flow patterns may be deduced from the temperature distributions , temperature fluctuations, and shape of the interface. Fluid flow increases with the height and the rate of heat transfev through the interface and this is further manifested by a deviation of the interface from aflat vertical plane. The influence of fluid flow on solute inhomogeneity during alloy crystal growth can be inferred from the observed temperature distributions. A buoyancy force exists in the liquid ahead of a vertical solid-liquid interface, caused by a difference in density between cold fluid near the interface and warmer fluid in the bulk liquid. When the viscous and inertia forces in the melt exceed this buoyancy force, a flow of fluid takes place, termed natural or free thermal convection. Natural convection in purely liquid systems has been extensively studied for many years. 1"u On the other hand, fluid flow during horizontal crystal growth has oniy recently been the subject of experimental investigation."-25 The requirements for horizontal crystal growth differ from other heat flow systems. The small aspect ratio (ratio of height of cold wall to length of fluid) has never been considered. The uniform furnace gradient which supplies heat radially (and not necessarily symmetrically) differs from previous boundary conditions of uniform heat flux at the cold and hot ends. And most important of all an isothermal s/l interface is present which can adjust its shape and position to conform to heat and fluid flow. All of these boundary conditions involve complexities which cannot be readily solved analytically. Preliminary observation has demonstrated the penera1 shape of the natural convective flow pattern in transparent media.20'24'25 The flow is circulatory, directed toward the interface at the surface of the liquid, down and away from the interface at the bottom, and then up at the hot end of the melt. During crystal growth such a flow may interact with the solute boundary layer at the s/l interface to affect solute incorporation.M'1B|28'i!T Evidence has also been presented recently to show that thermal convective flow will affect the structure of ca~tin~s.~~-~~ The rate of heat transfer (conduction plus convection) in a given fluid system is a function of the temperature difference between the hot end of the liquid and the s/l interface and the height of the interface. At the lowest values of these variables* all heat is *It has been shown' that adverse temperature gradients as low as O.OOS°C oer cm are sufficient to cause convection. transferred by conduction. When the temperature difference or interface height are increased, laminar fluid flow commences and heat transport takes place by laminar convection as well as by conduction; turbulent heat transfer takes place at higher values of these variables. In the transition region between laminar and turbulent flow, boundary layer separation takes place; fluctuations in temperature are also noted and increase in amplitude and frequency as turbulence becomes dominant. In this paper, fluid flow patterns in the melt ahead of a stationary interface are deduced from observations of temperature distribution and fluctuations, heat flow rate, and interface shape. The fluid flow ahead of advancing interfaces and the effect of such flow on solute incorporation may be inferred from these measurements on stationary interfaces. Observations during enforced fluid motion will also be considered. EXPERIMENTAL PROCEDURE The metal was contained in a lava boat 10 cm in length, 1+ cm in width, and 2 cm in height, as shown in Fig. 1. A water-cooled, molybdenum block heat-sink is at one end of the boat; surrounding this assembly is a slotted stainless-steel tube noninductively wound with a nichrome heating element. Temperature was measured by 38-gage Chrome1 vs Alumel thermocouples sheathed in 0.05-cm-diam graphite-coated stainless-steel tubing, which were moved longitudinally and vertically through the melt by means of a two-dimensional motorized micrometer stage. In some experiments the thermocouple junction was exposed, but in the majority of experiments the junction was welded to the sheath tip; no significant difference

Jan 1, 1968

By W. D. Forgeng, R. L. Folkman, D. C. Hilty

The solubility of oxygen in molten Fe-Cr alloys has been determined at 1550° , 1600°, and 1650°C for alloys containing up to alloyshasbeenabout 50 pct Cr and found to decrease as chromium increases to 6 pet and then to increase gradually. Phase relations in the Fe-Cr-0 system at steelmaking temperatures have been evaluated and two previously unreported oxides have been identified. OPERATIONS in the melting and refining of chromium steels are dependent to a major degree on the reactions of chromium and iron with oxygen and are primarily directed toward controlling and modifying these reactions to secure maximum advantage in the utilization of chromium. Although fairly effective practices have been developed empirically, understanding of the specific reactions is limited. Moreover, the ability of molten steel to dissolve oxygen that subsequently precipitates as oxide inclusions during solidification is well known, so that clarification of the effect of chromium on the nature and mechanism of formation of these inclusions is desirable. Study of the problem indicated that increased knowledge of the fundamental Fe-Cr-0 system is essential to further technical and economic improvement. Consequently, an investigation of the influence of chromium on the solubility of oxygen in molten iron and of phases and phase relations in the Fe-Cr-0 system was undertaken at the Metals Research Laboratories of the Electro Metallurgical Co. as part of a general program on the effective utilization of chromium in chromium steel production. Experimental Procedure All of the experimental runs made during this investigation were carried out in the rotating crucible induction furnace which has been described in detail in a previous publication.' In review, the principle underlying this furnace is that rotational forces in the crucible cause the molten metal to assume a concave shape in such a manner that the slag is contained in the molten metal cup, thereby minimizing slag/crucible contact and subsequent reaction. Practically all of the heats were melted in commercial-quality magnesia crucibles of the type usually furnished for laboratory induction furnaces. All of the runs were made under an argon atmosphere after the furnace chamber had been degassed. Bath temperatures were controlled by Pt—Pt-10 pct Rh thermocouples. The basic furnace charge consisted of a premelted 12 to 15 lb electrolytic iron slug which had been cast to a shape convenient for fitting into the rotating furnace crucible. A typical analysis of the electrolytic iron slugs is given in Table I. For certain runs, it was desirable to melt down charges containing high initial chromium contents. In these cases the chromium was added to the electrolytic iron during the premelting operations. Chromium was added to the rotating furnace bath in the form of electrolytic chromium of the analysis given in Table 11. In all of the constant temperature runs, the standard procedure was to melt down the electrolytic iron or alloy slug under vacuum, admit argon to slightly greater than atmospheric pressure, and adjust rotational speed to develop a well formed "cup" on the bath surface. The melt was then saturated with oxygen by an addition of ferric oxide and the temperature of the bath adjusted to within +5°C of the desired level. At this point the heat was permitted to come to equilibrium prior to sampling or further addition. This time interval was varied from 15 min to 2 hr but generally was about 20 min. After sampling, the desired chromium addition was made and the bath again equilibrated prior to subsequent sampling. This cycle of addition and sampling continued for the duration of the run which lasted from 4 to 8 hr. At the end of this period, power was shut off and the bath allowed to solidify in the furnace. Quenched metal samples were taken from the equilibrated melts by means of the "Taylor sampler" which has been described by Taylor and Chipman.' Before being submitted to chemical analysis, all samples were carefully examined for surface slag occlusions and cold shuts. Later in the study, each sample was radiographed and examined metal-lographically in cross-section to determine the presence of internal defects. On the basis of these examinations, sound and apparently clean specimens were selected from the Taylor samples for chemical analysis.

Jan 1, 1956

By L. E. Murr, P. J. Smith

A study has been made by transmission electron microscopy of thin foils of 304 stainless steel fatigued external to the electron microscope in reversed bending, and of thin foils fatigued directly within the microscope in alternating tension. The build-up of stacking faults in the thin foils during fatigue zoas correlated with the dislocatirm structures found in thin films prepared fror fatigued bulk specimens. The performance of the special devices designed for fatigue of thin foils so outlined and the importance of alternative methods of preparation of more uniform fatigue specimens bY vapor deposition are emphasized. INVESTIGATIONS on fatigued bulk aluminum1,' and stainless stee13j4 have revealed the existence of dislocation substructure on examination by transmission electron microscopy of electrolytically thinned foils representative of these bulk specimens. While this technique has proved extremely valuable, it has several shortcomings. First, the method of fatiguing bulk specimens and then thinning to foil for electron-transmission observation allows only one observation of internal structure at any one portion of the fatigue life. Second, thinning the bulk fatigued specimens to foil results in the loss of at least one original surface. Thus, what one sees in the remaining electron-transparent sections is an internal dislocation or fault structure which in many cases cannot be correlated with the original surface markings. This is an undesirable feature, since it is well-known that metal surfaces play an important part in the fatigue process.5 An obvious third undesirable feature of the thinning-from-bulk technique is the fact that static observations have difficulty (in the case of fatigue) explaining the mechanism of a dynamic process. What is required then is a method whereby a selected thin area can be continuously observed either while undergoing cyclic deformation or at various fixed stages of fatigue deformation. While Murr and wilkov6 have reported some success with an apparatus designed to fatigue thin metal foils directly within the electron microscope, the nature of the specimen-mounting procedure and the mechanical features involved in the adaptation of the fatigue device to the electron microscope make this method difficult to operate. It was not possible, for example, to make frequent observations of a selected area because of difficulty in maintaining a chosen area in a stable viewing position inside the electron microscope. Except for the build-up of a dislocation substructure and what are commonly referred to as "slip striations", little else has been reported from observations on thin-foil sections prepared from bulk fatigue specimens. segal17 has found "slip striations" in stainless-steel fatigued specimens which were electropolished from both sides, but gave no explanation as to their origin or identity in terms of lattice imperfections. The research to be reported in this paper was undertaken with the following objectives in mind. First, an attempt was made to devise a technique or techniques whereby thin metal foils could be fatigued and repeatedly observed by transmission electron microscopy. Second, it was hoped that some correlation could be made between deformation striations found in fatigued thin transmission specimens and thin foils prepared from bulk fatigued specimens. These investigations illustrate quite convincingly that a feasible method is available for the direct study of the fatigue mechanism and similar dynamic phenomena in thin transmission specimens inside the electron microscope. I) EXPERIMENTAL METHODS Three modes of specimen fatigue and observation of fatigue damage were used. These involved fatigue of thin-foil specimens in a special arrangement external to the electron microscope and observation of a selected area at various stages in the fatigue life, the fatigue of thin-foil transmission specimens inside the electron microscope, and the fatigue of bulk specimens external to the electron microscope followed by thin-foil preparation for direct observation at predetermined stages. Design of the External Fatigue Clip and Specimen Holder for the Hitachi H.U.11 Electron Micro-scope. The purpose of the fatigue clip was to provide a reversed bending fatigue stress to a thin-foil transmission specimen outside the electron microscope. In order to accomplish this, a flat-bottomed, U-shaped brass clip was made as shown

Jan 1, 1965

By N. S. Stoloff, R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-Co and Fe- V alloys containing up to 25 pct solute have been studied in the temperature range 25° to - 196°C. The microyield stress is independent of temperature for all alloys studied, while the temperature dependence of the ordinary yield stress is large and comparable to that for unalloyed iron. An alloy-softening phenomenon is observed for many alloys relative to unalloyed iron, and appears to be a consequence of removal of inter-stitials from solution and their subsequent agglomeration. The ductile to brittle transition temperature is increased markedly by both cobalt and vanadium. Transmission electron microscopy observations reveal that cross slip and cell formation are restricted with increasing solute, which can account for many aspects of yielding and fracture behavior. IRON and other metals of bcc structure slip on many planes of the (111) zone at moderate and elevated temperatures, giving rise to wavy glide. At low temperatures, however, there is a tendency for slip to be restricted to planes of only one or two crystallographic types; in the case of Fe-Si alloys for example, (110) glide predominates, giving rise to planar slip bands."' Restriction of cross slip at low temperatures in iron has been linked by Brown and Ekvall3 to increased strain hardening in the preyield microstrain region, leading to an apparently large temperature dependence of the yield stress. Support for this view has been provided by Lawley and Gaigher4 from a transmission electron microscope study of molybdenum. They concluded that dislocations at lower temperatures, by virtue of their inability to change planes readily, are unable to interact and annihilate, leading to an increase in internal stress and work-hardening capacity. Restriction of cross slip at low temperatures has also been suggested to be an important factor in determining the ductile to brittle transition of single-phase solids, including metals of bcc structure.5 It is pertinent to note that most solute elements tend to raise the ductile to brittle transition temperature of poly crystalline ferrite,6,7 although in some cases, e.g., Fe-Cr7 and Fe-Al,8 the dilute alloys may actually yield at lower stresses than unalloyed iron. It appears, therefore, that solute elements may have an effect analogous to lowering the test temperature with regard to restricting cross glide. Such an effect has indeed been observed in the ionic alloy system KCl-KBr,9 in which bromine atoms, although causing little misfit and consequently little effect on the yield stress of KC1, have a pronounced effect in restricting wavy glide and inducing brittleness. The purpose of the present investigation was to determine the effects of selected solute atoms on the yield stress and fracture behavior of iron, and to elucidate in turn how the slip character was related to these properties. Since it is known that interstitial atoms exert a strong influence on the mechanical behavior of iron, the solute elements chosen for study were vanadium, which reacts strong with interstitials,10 and cobalt, which does not form highly stable interstitial compounds." EXPERIMENTAL PROCEDURE Four-pound ingots of each of the following alloys were vacuum-melted in zirconia crucibles: Fe-1, 5, 10, 25 at. pct Co, and Fe-1, 4, 10, 20 at. pct V. An ingot of unalloyed iron from the same original stock as that used for the alloy was remelted under similar conditions to eliminate variations in interstitial content arising from differing thermal histories. Chemical analyses of the iron, cobalt, and vanadium melt stock are listed in Table I. All ingots were rolled and swaged, commencing at 850°C, to 1/4-in.-diameter bar. The bars were then annealed at 850°C for 1 hr (except that the 10 and 20 pct V alloys were heated for 2 hr) to give a uniform equiaxed grain size of about 0.05 mm. Tensile samples of 0.125 in. diameter by 0.8 in. gage length were utilized for studies of the ductile to brittle transition. A second set of tensile samples were utilized for microstrain experiments in which strain sensitivity of 1 x 10"6 was achieved by a capacitance method.3 Cylindrical compression samples 0.250 in. diameter by 0.4 in. long also were prepared to study the influence of composition on the macroscopic yield stress, and for metallographic analyses of defor-

Jan 1, 1965

By D. W. White

The kinetics of isothermal transformation of ß-to-u uranium have been studied over a broad temperature range in alloys containing from 0.3 to 4.0 atomic pct Cr. Two modes of transformation are indicated by the existence of two C-curves in the TTT diagram. The upper temperature mode is regarded as a nucleation and growth mechanism, whose rate is controlled by diffusion of chromium in the ß phase matrix. The lower temperature mode is martensitic in nature. The M, temperature increases with decreasing chromium content, suggesting that the two transformation processes become synonymous in unalloyed uranium. URANIUM metal undergoes two allotropic transformations in the solid state. The a phase, orthorhombic in crystal structure,' is stable from room temperature up to about 665°C. The ß phase, characterized by a complex tetragonal structure,' prevails from 665" to about 770°C. The y phase is body-centered-cubic3 and is the stable modification from 770°C up to the melting point (about 1130"). In uranium of reasonable purity, neither of the two high temperature phases can be retained by quenching. However, the addition of certain alloying elements to uranium makes it possible to retain either the y-uranium phase or the ß-uranium phase at room temperature. Chromium alloyed in small amounts with uranium will permit retention of the ß-uranium phase in a metastable state at room temperature upon quenching from a ß-phase temperature.' From available information' on the equilibrium phase diagram for the U-Cr alloy system (Fig. I), it is to be expected that, however sluggish in its rate, the ß phase in such alloys should decompose eutectoidally to a phase and elemental chromium. It was the aim of this investigation to measure the rate and study the nature of this decomposition as a function of temperature and of chromium content. The investigation was reported in classified literature about five years ago and has recently been declassified for publication. In the meantime, there have appeared the papers of Holden,5 Mott and Haines,".' and Butcher and Rowe8 ealing with the metallography and the crystallography of the ß-to-a transformation in U-Cr alloys. These investigators have confirmed several of the phenomenological observations that will be described in the present paper and have examined in considerable detail certain aspects of the transformation and its mechanism. Although all of these investigations have concerned themselves experimentally with U-Cr alloys for the most part, an important consequence has been a clearer understanding of the nature of the ß-to-a transformation in uranium metal itself. Experimental Procedure This investigation dealt with a series of uranium alloys varying in chromium content from 0.3 to 4.0 atomic pct (0.066 to 0.90 weight pct). On five of the alloys, rates of isothermal transformation from the ß to the a phase were measured over a wide temperature range, leading to the development of TTT (time-temperature-transformation) diagrams. Transformation rates were measured over certain narrow temperature ranges on additional alloys. The alloys were prepared by vacuum melting and casting, using zircon or magnesia crucibles and graphite molds. Electrolytic chromium was used as the alloying addition, and the uranium was Mallin-ckrodt biscuit metal that had been vacuum remelted and cropped to remove many of the nonmetallic impurities that had floated to the top of the ingot. The ingots, 3/4 or 1 in. diam, were reduced in size by swaging. Alloys containing less than about 2 atomic pct Cr were swaged at 250° to 275°C, with initial and intermediate anneals at 550°C after every 75 pct reduction in area. Alloys with higher amounts of chromium were swaged at 550" to 600°C, although at the smaller sizes some of them were reduced by the procedure used on the more dilute alloys. Before use as test specimens, the swaged rods were annealed at 700" to 720°C for several hours, followed by slow furnace-cooling. The purpose of the anneal was to achieve the maximum amount of solution of the available chromium into the ß phase, as well as to remove extensive preferred orientation. The isothermal transformation rates were measured dilatometrically, using a quenching dilatometer and an experimental technique similar to those employed by Davenport and Bain in their original work on the transformation kinetics of austenite in

Jan 1, 1956

By K. Tangri, B. Swaroop

Simultaneous measurements of lattice (elastic) strain by X-ray line shift method and total strain with an electrical strain gage have been carried out on polycrystalli,ne nickel with the help of a specially designed tensometer attachment for the X-ray dif-fractometer. During the initial stages of deformation, the rate of increase in lattice strain closely follows the total strain until the plastic strain sets in. From then onwards, the two strains deviate from each other and with further increase in afiplied stress the rate of increase of lattice strain eventually decreases. Depending upon the mode of unloading, both compressive and tensile strains have been observed in nickel deformed up to 0.29 pct strain. These results have been explained on the basis of the effects of clustering of dislocations and also the production and behavior of point defects during loading and unloading, respectively. POLYCRYSTALS deformed plastically in a uniaxial tension test show residual lattice strains (hereafter referred to as RLS), which broaden the X-ray line profiles and shift their peak positions.''4 It is known that uniform straining of a crystal lattice (macrostrain) produced movement of ddfraction line peaks, whereas nonuniform straining (microstrain) causes line broadening.= Though the nature and origin of RLS in deformed metals is not yet clearly understood, these are believed to be due to the presence of some form of a locked-up stress system. Several possible detailed interpretations6'" of the stress system have been proposed by various workers and common to all these interpretations is the assumption that different parts of the aggregate have different tensile yield stresses; e.g., that a part A yields under a lower applied stress than a part B. Therefore, during the deformation process, the elastic strain in A will be less than that in B, and, after completion of deformation, B will tend to contract further than A but will be prevented from doing so by the restraining influence of A. Thus, when equilibrium is reached, A will be in compression while B is in tension. Although there is general agreement on the correctness of this argument, controversy still exists as to the exact nature of the parts A and B in a deformed metal. In an alternative approach to the creation of parts A and B, many other investigators have assumed that the RLS observed in unloaded specimens are in some way connected with the lack of proportionality between lattice strain and applied stress in the region above the yield stress." cullity13 has prepared a schematic summary of the results of previous workers, mainly Smith and Wood,2'11 which suggests that, above the elastic limit, the lattice strain may increase less rapidly with respect to strain, or may even decrease with increase in applied stress. If the applied stress is then decreased, the lattice strain would decrease along a line parallel to the loading line in the elastic region and thus produce a compressive residual lattice strain after unloading. At equilibrium, to balance these compressive stresses? there would have to be regions under tensile stress which may well be the grain boundaries or the substructure walls formed during deformation. The present investigation was undertaken to gain a better understanding of the nature and origin of RLS and also to experimentally verify the salient features of this hypothesis. EXPERIMENTAL Stress and strain determinations were made with a specially constructed tensometer attachment for the X-ray diffractometer, Fig. 1: which permits the following measurements simultaneously on a sheet specimen under uniaxial tension at various stress levels during loading and unloading: a) lattice strains, E=. in a direction perpendicular to the direction of pulling (x direction) from shifts in X-ray line peak positions; b) the total strain, ex, in the direction of pulling. with the help of an electrical strain gage affixed to the back of the specimen directly below the area irradiated by X-rays: and c) the applied stress, with the help of a load cell which consisted of a calibrated stainless-steel sample of dimensions identical to those of the specimen under investigation, and to which it was coupled. Because of its high stacking fault energy.I4 nickel

Jan 1, 1970

By P. S. Kotva

Dislocation substructures in superalloy matrices of varyzng co)npositions have been studied. In general, it has been found that the alloys can be classified into ''high", ''medium", and "low" stacking fault energy classes based on the type of dislocation substructure observed in the matrix and that the substructure can be correlated to the stacking fault energy. The effect of different types of dislocation substructure and dislocation reactions on the intragranulur precipitation of carbide phases has been studied. In a Ni-Cv-Mo-Fe matrix, precipitation of MC carbides in association with stacking faults has been observed. In most superalloys, solid-solution strengthening and precipitation hardening are the chief mechanisms employed to achieve strength. The latter contribution to strength is usually achieved by the precipitation of / in certain wrought alloys. Insufficient attention has been given to the problem of obtaining strength in su-peralloys by controlling precipitation of carbides on imperfections within the matrix. The present work was undertaken to investigate the dislocation substructure in various superalloy matrices, to study the effect of such substructure on subsequent precipitation of carbides in the matrix, and to investigate whether certain modes of precipitation of carbide phases found in austenitic stainless steels2"4'6 would occur in nickel-base alloy matrices with dislocation substructures of the same type as those found in austenitic steels. 1) EXPERIMENTAL TECHNIQUES Five-pound heats of the various alloy compositions reported here were vacuum-cast. The ingots were given light deformation by rolling to break up the as-cast structure and then homogenized for 24 hr. HASTELLOY alloy X (nominal composition: Ni-2OCr-17Fe-8Mo-0.05C) was homogenized at 2150°F and In-cone1 625 (nominal composition: Ni-20Cr-5Fe-8Mo-3.5Cb-0.05C) was homogenized at 2280°F. Fabrication of 0.004-in. sheet was achieved by cold rolling with intermediate annealing treatments being carried out at the same temperature as those used for homogeniza-tion. Each solution anneal was followed by quenching. The aim of this procedure was to redissolve as much of the primary carbide phase as possible. Samples of the 0.004-in. sheet were cut and encapsulated in quartz capsules and then heat-treated in the tube furnaces. Thin foils were prepared using an ethanol-10 pct perchloric acid bath at 32°F and at a voltage of 22 v. A "window" technique was employed. Observations were made on a JEM-7 electron microscope operating at 100 kv. 2) EXPERIMENTAL RESULTS a) Types of Dislocation Substructure. Fig. 1 shows a schematic correlation between stacking fault energy, SFE, and the type of dislocation substructure observed in various matrices of nickel- and cobalt-base alloys. A precise quantitative determination of stacking fault energy is not implied in the figure but the correlation between stacking fault energy and the type of dislocation substructure obtained allows alloys to be divided into three classes in analogy with the classification employed by Swann and ~uttin~' for binary alloys of copper. Class I alloys are associated with a "high" SFE and show a cellular substructure of dislocations as typified by the micrograph of a thin foil of pure nickel deformed 4 pct at room temperature in Fig. 2. With decreasing SFE the tendency toward cell formation is lessened and dislocations tend to be arranged in coplanar groupings. Examples of this class of alloys with "medium" SFE are provided by the mi-crostructure of solution-heat-treated, quenched, and deformed thin foils of HASTELLOY alloy X, "Waspaloy" (prior to any aging), and Inconel 625. Fig. 3 shows a thin-foil micrograph of an alloy of Inconel 625 composition, solution-heat-treated, quenched, and deformed 5 pct at room temperatures. No evidence of any cell structure can be obtained in materials of "medium" stacking fault energy, Fig. 3, even after severe deformation. The stacking fault energy of the alloy shown in Fig. 3 is, however, not low enough to make the dissociation of dislocations visually obvious. As stacking fault energy decreases further, with successive addition of solute in the matrix, there is an increased tendency toward dissociation of dislocations and cross slip becomes progressively more difficult. Eventually, when the stacking fault energy is "low" enough, complete dissociation of dislocations is seen to occur as shown in Figs.

Jan 1, 1969

By G. B. Thomas

Several methods of analyzing pressure build-up data in wells have been presented by various authors. This paper reviews the theory and method of D. R. Horner and presents example calculations performed on data obtained by testing several different types of wells. These calculations include, (1) graphical estimation of final static pressure, (2) determination of the productive capacity of the pay away from the well bore and. (3) the degree to which the formation adjacent to the well bore has been damaged by completion or other causes. The methods of testing and precautions which should be taken to assure the best data possible are discussed. Limitations and reliability of calculated results are also treated. INTRODUCTION Pressure testing of wells is generally limited to the determination of producing and static mean formation pressures. The so-called "static" pressure determination.. along with PVT, electric log and production data, enable the reservoir engineer to determine, within reasonable limits, the drive mechanism of the reservoir and in some cases. the amount of edge water encroachment. Producing pressure tests enable calculation of productivity indices and allow the engineer to plan the systematic production of a pool for optimum conservation of suhsurface energy. The radial flow formula advanced by Muskat' has been based on the assumption of incompressible radial fluid flow. It has been known that reservoir fluids do not behave in an ideally incompressible manner. For example, incompressible flow theory indicates a simple logarithmic relationship between the difference of the instantaneous and static well pressures when plotted against time. 'The latter stages of this type of plot of pressure build-up data generally show a marked devia-, tion from the earlier straight line trend. which deviation may be shown to be due to the compressible flow of fluids toward the well bore. Shut-in times of 24, 48. 72. or at most 96 hours are currently in wide use for determining so-called "static" reservoir pressure. Due to the continuation of compressible flow of fluids into the well bore long after this arbitrarily taken shut-in time, the determination of static pressures has almost invariably resulted in lower than equilibrium values. Materials balance calculations made early in the life of a reservoir often result in a calculated reserve which later observations prove to be too low. Failure to obtain reliable "static" reservoir pressures within the prescribed 24 or 48-hour build-up period has undoubtedly been a major factor in obtaining these low estimates. Comparison of theoretical and actual productivity performance has indicated that formation damage and not being able to attain true static pressures have been partially responsible for the observed discrepancies. Research into the theory of compressible flow behavior has resulted in methods of applying these theories to the testing of wells. Application of the developed theories to pressure build-up performance indicates that in many cases the following can be estimated. 1. The static reservoir pressure. 2. The in-place effective formation permeability away from the well bore. 3. The degree or extent by which the formation has been damaged adjacent to the well bore, either through completion methods or subsequent damage due to fluid entry. REVIEW OF THEORY Horner2 has shown that the pressure build-up within a "point source" well is approximated by the following formula: Equation (1) is the approximate "point source" solution to the radial compressible flow equation advanced by Muskat. The solution assumes the following: 1. A point source well is producing at constant rate from the center of an infinite reservoir with a constant pressure at its external boundary. 2. The fluid flowing is present in one phase only. 3. The compressibility and absolute viscosity of the fluid remain essentially constant over the range of temperature and pressure variation encountered. 4. The well i.; shut-in at the sand face arid there is 110 after production into the well bore. 5. The formation permeability is homogeneous in the direction of flow. From Equation (1) it can be seen that if an ideal well were shut-in while producing from a reservoir under the conditions assumed, the pressure build-up would be a logarithmic func-

Jan 1, 1953

By D. M. Schuster, E. Scala

The elastic effects occurring in the matrix of a composite reinforced by discontinuous fibers were studied by means of photoelastic techniques. A hirefringent plastic was employed as the matrix material with high-strength a Al2O3 whiskers as the reinforcing fibers. It was found that for whiskers aligned parallel to the tensile load direction: (I) Matrix reinforcement occurred along the length of the whisker to within about 5 diameters of the whisker tip for a length to diameter ratio, L/D, of 40. (2) Significant stress concentrations were created in regions immediately surrounding the tips; the fine as-formed tapered ends exhibited the minimum stress concentration whereas the square-ended whisker produced relatively high values, K r 2.5 for L/D = 40. (3) The axial and radial stress distributions could he determined quantitatively; the stress distribution at the whisker-matrix interface was in general agreement with theoretical calculations. (4) The highest source of stress concentration occurred at points of fracture in whiskers which had ruptured after incorporation into the composite. Whiskers aligned perpendicular to the load direction neither reinforced nor caused appreciahle stress concentrations in the matrix. ThE properties of composites have generally been formulated empirically on the basis of macroscopic tests. There are still many questions concerning the mechanical and chemical interactions occurring at the interface between the reinforcing fiber and its matrix. Continuously reinforced plastics and dispersion-hardened metals represent the two extremes of composite reinforcement. Whether artificially produced or formed in situ, the whisker composite falls between these two extremes and is an example of discontinuous fiber reinforcement. The effect of fiber shape, size, surface condition, and end configuration on the stress distribution in the matrix is important since the presence of stress concentrations, especially in any high-strength, thin-wall structure, could become the cause of catastrophic failure. DOW,' in his theoretical discussion of discontinuous fiber reinforcement, has pointed out that appreciable stress concentrations occur at the tips or ends of the reinforcing fibers. It is the purpose of this study to examine directly, by means of the photoelastic technique, the stresses which occur in the vicinity of a discontinuity or whisker tip and to measure qualitatively and quantitatively the effects of whisker geometry when embedded in a birefringent matrix material. The use of sapphire (a A1,O3) whiskers was decided upon as the reinforcing agent because of their high elastic modulus (E- 60 X 106 psi) and in some cases strengths in excess of one and a half million psi. Sapphire whiskers are of further practical interest since they retain large fractions of their strength up to temperatures approaching the melting point (3720oF).2 The whiskers were grown, by the vapor-phase reaction commonly employed,3 as part of this study to insure a physically uniform supply. Tensile and bend tests were performed to verify that the whiskers were of the expected ultra-high strength. The high-strength whiskers can be identified and selected from the combustion boats by surface perfection, shape, and size; otherwise, strength values can vary by a factor of ten or more. Macroscopic defects are quite common on the surface of large bladed whiskers and the principal experiments were conducted with hexagonal whiskers of about 0.002 in. diameter and lengths ranging from 0.1 to 0.4 in. Upon completion of these two phases of the experiment, several birefringent resins were evaluated. A plastic, developed by Zandman,4 which is supplied by the Budd Co., was found most suitable and was used as the matrix material for the whisker composite throughout the study. It has a sensitivity of 60.5 lb per in. order, calibrated in tension and cures without introducing residual stresses. Young's modulus for this matrix material is 430,000 psi in the fully cured condition. Since good wetting and bonding between the sapphire and the matrix material is essential to the interpretation of the results, a wettability test was performed. The contact angle was measured to be 168 deg where perfect wetting is defined as 180 deg; therefore, the Budd Plastic wets the sapphire

Jan 1, 1964

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.' and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~' have reported the structure of

Jan 1, 1965

By D. Turnbull, J. H. Hollomon

THERE is a large body of evidence'" indicating that solidification during the liquid-solid transition is usually induced by heterogeneities present in the liquid. By dispersing liquid metals into small droplets, the impurities responsible for catalyzing solidification are isolated within a small number of these droplets. The effect of the foreign body therefore is restricted to a single drop by this technique. Thus upon cooling below the melting temperature, solidification is initiated by homogeneous nucleation in the majority of the droplets that do not contain impurities. In the case of solidification of liquid metals, the activation energy for nucleation is so great that its rate changes by orders of magnitude for a change in temperature of only several degrees centigrade.' Effectively homogeneous nucleation occurs at a critical temperature upon continuous cooling. Thus by microscopic observation of single particles during cooling, a temperature at which the rate of homogeneous nucleation becomes sensible can be determined.3 since at the temperatures at which nucleation occurs in the absence of impurities the rate of crystal growth is extremely rapid, the temperature at which the entire particle solidifies is very nearly the temperature at which the nucleation of the solidification occurs. Thus for liquids that freeze at high temperatures the onset of nucleation can be established by simply observing the temperature at which the marked heat evolution and increase in brightness of the particle occur. For liquids that freeze at lower temperatures the onset of nucleation can be determined by a rumpling and change in shape of the particle resulting from its solidification. The microscopic technique for observing the solidification of small particles has already been described." In earlier papers the nucleation of solidification of pure metals 5,6 and of alloy systems7 showing complete liquid and solid solubility have been described. In the present paper, the observations are extended to a simple eutectic system (Pb-Sn) where the possibility of the formation of two solid phases exists. Metals for the investigation were obtained from the American Smelting and Refining Co. in the form of pure lead and pure tin, 99.8 and 99.9 pct purity, respectively. An ingot of each of the pure metals was made into shot by heating the metals at a temperature about 50 °C in excess of the melting point and pouring the liquid slowly into a container of water at 15°C. Samples of the shotted pure metals were weighed out to make alloys containing 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, and 90 atomic pct Pb. Samples of each alloy were then melted in separate beakers. Each melt was poured through a pyrex funnel into a cylindrical mold (% in. ID). The casting solidified in 10 to 20 sec. The inside of the mold as well as the funnel through which the metal was poured were coated with graphite to eliminate adherence of the metal. Analyses were performed on some of the compositions and are given in Table I. The compositions also were checked for these samples and for those that were not analyzed by determining the spread between the liquidus and the solidus upon melting the small metal particles. These measurements agreed as well with the nominal compositions as the analyses listed above. Results The results of the supercooling experiments for the several alloys are summarized in Table II and plotted on the constitution diagram in Fig. 1. Data for the pure lead and pure tin were taken from earlier investigations. The values for the maximum supercooling of the several alloys are the average of several determinations on a number of drops of each alloy. The maximum value in any determination was within about 2 pct of the average. For the alloys containing from 20 to 60 atomic pct Sn, inclusive, two marked changes of the surface structure were observed upon cooling. At the higher temperature, after the first appearance of the solid phase it continued to grow slowly at a constant temperature and then stopped. At the lower temperature the alteration of surface structure was abrupt. For the alloys containing from 70 to 95 atomic pct Sn, inclusive, an abrupt change in surface structure was observed at a single critical temperature.

Jan 1, 1952

By C. A. Siebert, S. H. Bush

Isothermal temper-embrittlement studies were conducted on a 5140 steel at various temperatures for times as long as 3000 hr. Specimens from the embrittled steel were subjected to impact tests, metallographic examination, microhardness, and lattice-parameter measurements. SEVERAL of the steels in the low alloy group are subject to a pronounced decrease in impact energy if held within, or cooled slowly through, a range of temperatures below the lower critical. This phenomenon, known as temper embrittlement, is quite pronounced in the chromium steels of which AISI 5140 is typical. This study considered the response of one heat of 5140 steel when embrittled isothermally at various temperatures for times as long as 3000 hr. Excellent reviews of the work done in the field of temper embrittlement have been written by Hollomonl and Woodfine.' Both authors list the various theories which have been advanced to explain temper embrittlement. Some of the mechanisms considered were: 1—a transformation below 700°C; 2—an allotropic modification of iron; 3—precipitation from the ferrite of such compounds as carbides, nitrides, phosphides, or chromium oxides; 4—decomposition of retained austenite; 5—modification of special carbides; 6—grain-boundary segregation; and 7—selective distribution of carbides. The present study investigated the changes in hardness, Meyer's number, impact properties, micro-structure, and lattice parameter which occurred on embrittlement. Previous studies considered the influence of microstructure and of prior austenitic grain size3 on the response of 5140 steel to temper embrittlement. Equipment and Procedure All samples were taken from one heat of 5140 steel; the chemical composition of this steel was: 0.43 pct C, 0.86 pct Mn, 0.020 pct P, 0.019 pct S, 0.27 pct Si, 0.84 pct Cr, 0.10 pct Ni, 0.06 pct Mo, 0.10 pct Cu, and the remainder Fe. The material was received as % in. rounds. This stock was cut down to blanks measuring approximately 0.425~0.425~2.196 in. Heat Treatment: The rough blanks were normalized at 1600°F (870°C) for 1 hr, then austenitized at 1600°F (870°C) for 1 1/2 hr, and quenched into an agitated oil bath. The specimens were tempered at 1275°F (690°C) for 5 hr and water quenched. These tempered specimens were designated as the toughened state. Embrittling Treatments: The tempered bars were divided into sets and subjected to the various embrittling treatments listed in Table I. Temperatures from 750" to 1050°F were investigated for times of 1 to 3000 hr. Special tests to determine the effect of heating a short time at a higher temperature after long-time embrittlement at some lower temperature were also conducted. All specimens were water quenched at the end of the embrittling cycle, then ground and notched to obtain standard Charpy V-notch specimens. Impact Tests: The bars were fractured in a 260 ft-lb Charpy impact unit; specimens were fractured at temperatures ranging from —315°F to room temperature. Fixed temperatures used consisted of —315°F with liquid nitrogen, —115°F with dry ice and acetone, and 32°F with ice and water. Intermediate temperatures were obtained by suspending the bars in a jig over the liquid nitrogen, dry ice and acetone, or ice and water.

Jan 1, 1955

By F. C. Bond

SIZE of grinding media is one of the principal factors affecting efficiency and capacity of tumbling-type grinding mills. It is best determined for any particular installation by lengthy plant tests with carefully kept records. However, a method of calculating the proper sizes, based on correct theoretical principles and tested by experience, can be very helpful, both for new installations and for guiding existing operations. As a general principle, the proper size of the make-up grinding balls added to an operating mill is the size that will just break the largest feed particles. If the balls are too large the number of breaking contacts will be reduced and grinding capacity will suffer. Moreover, the amount of extreme fines produced by each contact will be increased, and size distribution of the ground product may be adversely affected. If the balls added are too small, grinding efficiency is decreased by wasted contacts that are too weak to break the particles nipped; these largest particles are gradually worn down in the mill by the progressive breakage of corners and edges. Ball rationing is the regular addition of make-up balls of more than one size. The largest balls added are aimed at the largest and hardest particles. However, the contacts are governed entirely by chance, and the probability of inefficient contacts of large balls with small particles, and of small balls with large particles, is as great as the desired contact of large balls with large particles. Ball rationing should be considered an adjunct or secondary modification of the principle of selecting the make-up ball size to break the largest particle present. Empirical Equation In 19521,2 the author presented the following emerical equation for the make-up ball size: B - ball, rod, or pebble diameter in inches. F = size in microns 80 pct of new feed passes. Wi - work index at the feed size F. Cs - percentage of mill critical speed. S — specific gravity of material being ground. D == mill diameter in feet inside liners. K - 200 for balls, 300 for rods, 100 for silica pebbles. Eq. 1 was derived by selecting the factors that apparently should influence make-up ball size selection and by considering plant experience with each factor. Even though Eq. 1 is completely empirical, it has been generally successful in selecting the proper size of make-up balls for specific operations. But an equation based on theoretical considerations should be used with more confidence and have wider application. The theoretical influence of each of the governing factors listed under Eq. 1 was accordingly considered in detail, as described below, and a theoretical equation for make-up ball sizes was derived. Derivation of Theoretical Equation Ball Size and Feed Size: The basis of this analysis is that the largest ball in a mill should be just sufficient to break the largest feed particle into several pieces, excluding occasional pieces of tramp oversize. In this article the size F which 80 pct passes is considered the criterion of the effective maximum particle feed size. The smallest dimension of the largest particles present controls their breaking strength. This dimension is approximately equal to F. As a starting point for the analysis it is assumed that a 1-in. steel ball will effectively grind material with 80 pct passing 1 mm, or with F- 1000µ or about 16 mesh. The breaking force exerted by a ball varies with its weight, or as the cube of its diameter R. The force in pounds per square inch required to break a particle varies as its cross-sectional area, or as its diameter squared. It follows that when a 1-in. ball breaks a 1-mm particle, a 2-in. ball will break a 4-mm particle, and a 3-in. ball a 9-mm particle. This is in accordance with practical experience, as well as being theoretically correct. Confirmation of this reasoning is supplied by the Third Theory of Comminution," which states that the work necessary to break a particle of diameter F varies as F. Since work equals force times distance, and the distance of deformation before breaka4e varies as F it follolvs that the breaking force should vary as F½ These relationships are expressed in Table I, with a 1-in. ball representing one unit of force and breaking a 1-mm particle. This establishes theoretically the general rule used in Eq. 1 that the ball size should vary as the square root of the particle size to be broken. Ball Size and Work Index: The work input W required per ton" varies as the work index Wi, and the

Jan 1, 1959

By Shiou-Chuan Sun

THIS paper presents the design and operation of a frothmeter capable of measuring the frothing characteristics of pine oils and other frothing reagents. The experimental data show that the frothability of pine oil is governed by: 1-rate of aeration, 2-time of aeration, 3-height of liquid column, 4-chemical composition of pine oil, 5-pH value of solution, 6-temperature of, solution, and 7-concentration of pine oil in solution. The effect of mineral particles on the behavior of froth also was studied, and the results can be found in a separate paper.1 The results also show that the relative frothabilities of pine oils in the frothmeter generally correlate with those in actual flotation, provided that other factors are kept constant. In addition to pine oils, the other well-established flotation frothers were tested, and the results are included. In this paper, compressed air frothing is the frothing process performed by means of purified compressed air, whereas sucked air frothing is the frothing process accomplished by purified air sucked into the glass cylinder by a vacuum system. The term vacuum frothing denotes that froth was formed by degassing of the air-saturated liquid under a closed vacuum system. Apparatus The frothmeter, shown in Fig. 1, is capable of reproducibly measuring the volume and persistence of froth as well as the volume of air bubbles entrapped in the liquid and is capable of being used for compressed air frothing, sucked air frothing, and vacuum frothing. Fig. la shows that for compressed air frothing, the apparatus consists of an airflow regulating system, 1-3; a purifying and drying system, 4-8; a standardized flowmeter to measure the rate of airflow from zero to 500 cc per sec, 9; and a graduated glass cylinder, 13; equipped with an air regulating stopcock, 10; an air chamber, 11; and a fritted glass disk to produce froth, 12. The fritted glass disk, 5 cm in diam and 0.3 cm thick, has an average pore diameter of 85 to 145 microns. The pyrex glass cylinder has a uniform ID of 5.588 cm and an effective height of 63 cm. The inside cross-sectional area of the glass cylinder was calculated to be 24.53 sq cm, or 3.8 sq in. For sucked air frothing, Fig. lb shows that the apparatus for compressed air frothing is used again, with the following modifications: 1-compressed air and its regulating system, 1-3, are eliminated; and 2-a vacuum system, 16, equipped with a vapor trap, 15, and a vacuum manometer, 17, is added. The vacuum system can be .either a water aspirator or a laboratory vacuum pump. Any desired rate of airflow can be drawn into the glass cylinder, 13, by adjusting the opening of the air regulating stopcock, 10. The sucked air stream is cleaned by the purifing and drying system, 4-8, before entering the glass cylinder, 13. When this setup is used for vacuum frothing, the air regulating stopcock is closed. The frothmeter has been used for almost 3 years and has proved to give reproducible results, as illustrated in Table I. With a magnifying glass and suitable illumination, the frothmeter also can be used to study the attachment of air bubbles to coarse mineral particles.2 Experimental Procedures Except where otherwise stated, the data presented were established by means of the compressed air method. The volume and persistence of froth were recorded respectively at the end of 4 and 6 min of aeration at a constant rate of airflow of 29.3 cc per sec which is equivalent to 71.6 cc per sq cm per min, or 462.6 cc per sq in. per min. The aqueous solution for each test, containing 1000 cc of distilled water and 19.2 ± 0.5 mg frothing reagent, was adjusted to a pH of 6.9 ± 0.2. The volume of froth is expressed as cubic centimeter per square centimeter and is equivalent to the height of the froth column (the distance between the bottom and the meniscus of the froth). The volume of froth was obtained by multiplying the height of froth by the cross-sectional area of the glass cylinder, 24.53 sq cm. Before each test, the glass cylinder, 13, was cleaned thoroughly with jets of tap water, ethyl alcohol, tap water, cleaning solution, tap water, and finally distilled water. The cylinder with stopcock,

Jan 1, 1952

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1'2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

By L. R. Raymond, G. G. Binder

One primary purpose of hydraulic fracturing as a well stimulation technique is to overcome formation damage. The literature provides ways of designing fracture treatments and evaluating their results but not of incorporating formation damage in vertically fractured wells. Results of an investigation of this problem are presented in this paper. Prediction of stimulation ratios in vertically fractured, damaged wells is accomplished with a mathematical model relating stimulation ratio to relative conductivity of fractures whose lengths are not more than about half the drainage radius of the well. Comparison of results from the new model to results in published predictions verify its utility; these results also show that the range of stimulation ratios that can be predicted for undamaged wells is extended to include relative conductivities of less than 300. This extension is important when using fracturing to stimulate wells with high production rates and high native formation permeabilities. For example, large increases in daily oil production rate can be obtained with stimulation ratio increases as low as 1.25. The importance of complete fracture fill-up (uniform proppant packing) is shown through use of the mathematical model. If, at the mouth of a fracture, only a small fraction (1/2 percent) of the total fracture length is not packed with proppant, nearly all the polential stimulation increase is lost. Proppant crushing, compaction and embedment have been shown in laboratory studies to be responsible for low fracture conductivities in wells producing from highly stressed formations. Equipment and methods for testing the effect of stress (overburden) on conductivity of fructures in consolidated and unconsolidated sands are discussed in this paper. Laboratory tests with simlilated fractures in cores from both types of formations showed that crushing, compaction and embedment seriously affect conductivity. Results indicate that similar laboratory tests should be made when accurate knowledge of fracture conductivity is needed to assure good stimulation results for important wells. The chief factor in stimulation ratio reduction was found to be overburden pressure, but the size and type of proppant and the hardness of the formation have significant effects. Fracture conductivity reductions of up to 50 percent were observed with sand propping fractures in consolidated cores; a reduction of 83 percent was measured for an unconsolidated core. The range of effective overburden pressures for which conductivities were measured was from 100 to 5,000 psi. An example fracture design and evaluation problem indicates the usefulness of considering formation damage in planning well stimulation jobs. When damage exists, but its extent and the degree of permeability reduction are not estimated from diagnostic tests, the formation permeability used in planning the job may lead to under-designing. As the example shows, too low a target stimulation ratio can lead to much lower production rates (by half) than could be attained otherwise. Solutions of equations representing several special cases of the mathematical model are presented in graphical form and details of the derivations of the equations are given in the Appendix. INTRODUCTION Since its inception in 1947, hydraulic fracturing has proven to be an effective and widely accepted stimulation technique. In the past 18 years the ability to execute a successful hydraulic fracturing treatment has been substantially increased. The development of design and evaluation procedures1,2 has been one of the major contributions to this increased skill. However, as the art of hydraulic fracturing has moved closer to a science, new problems concerning the design and evaluation of the optimal hydraulic fracturing treatment have arisen. Three questions are pertinent to these problems. I. How is a fracturing job evaluated in a damaged well? 2. What is the effect on the stimulation ratio of not filling the fracture in the vicinity of the wellbore? 3. What is the effect of overburden pressure on fracture conductivity and, consequently, the stimulation ratio? A primary objective of fracturing a well is to stimulate production by overcoming wellbore damage. Presently. however, there is no rational basis for designing or evaluating the optimal fracturing treatment in a damaged well. All present fracture design and evaluation techniques assume that proppants can be uniformly placed in fractures. This assumption may be in serious error, particularly for the portion of a fracture directly adjacent to the wellbore. In this area, turbulence of the injected fluid can cause the proppant to be swept farther into the fracture. Also, loss of fluid from the fracture to the

By S. S. Arentz

PLANNED health and safety programs have become an essential part of American industry because such programs lead to increased operating efficiency, improved labor relations, better public relations, and to substantial savings in compensation insurance. Those of you who have had the unpleasant duty of informing the wife or widow of one of your men of his serious injury or death while on the job, know that all the benefits of a successful safety program do not show on the balance S. S. ARENTZ, Member AIME, is General Superintendent, Nevada Operations, Combined Metals Reduction Co., Pioche, Nevada. AIME San Francisco Meeting, February 1949. TP 2741 A. Discussion of this paper (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Jan. 6, 1949. sheet. These programs are of particular importance to the mining ,industry because mining's reputation as an unusually hazardous industry and the commonly isolated location of mining operations tend to focus attention on these problems. Description of Operations: Before proceeding with a discussion of our health and safety programs at Pioche, it may be proper to give a brief description of Pioche and of our operations there. Pioche is one of the early Nevada mining camps. It was founded shortly after the discovery of high grade silver ore in 1863 and mining has continued with more or less regularity to the present day. In an era of lawlessness, Pioche was notorious. The story persists that 75 men died with their boots on before one died a natural death, and old payroll records show that nearly as many gunmen were employed to stand off claim jumpers as there were miners working the mine. That was probably as close to a safety program as the times permitted. Pioche is situated in southeastern Nevada on the main highway between Ely and Las Vegas. The camp is on the flank of "Treasure Hill," near the original silver discovery, at an elevation of about 6000 ft. The present day population of about 2000 is primarily dependent upon the mines of the area, although Pioche also serves as the county seat of Lincoln Couqty and as the center of the surrounding livestock industry. The camp is served by a branch of the Union Pacific Railroad and receives power from the generators at Hoover Dam. The Pioche operations of the Combined Metals Reduction Co. were started in 1923 when the first complex lead-zinc ore was shipped to the company's mill at Bauer, Utah. The modern mill at Pioche was completed in 1941. The operations are medium sized in the nonferrous field, employing an average of 350 men in the mine, mill, and related works. The complex lead-zinc ore is mined from replacement deposits in a comparatively flat, extensively faulted, limestone horizon. Mining methods vary from stull-supported open stopes to filled square-set stopes. The thin bedded limestone and shale overlying the ore is allowed to cave as areas are mined out and caving frequently follows closely upon ore extraction. The relatively heavy ground and the numerous faults add to the problems of safe mining. The mine is well mechanized and the mill and surface plant are modern and well equipped. Labor is organized in a C.I.O. union and labor-management relations have been unusually harmonious. During most of the period since 1923 a competent supervisory staff worked to reduce safety hazards but the primary responsibility for safety rested on the individual workman. Accidents happened and all too frequently they were regarded by all concerned as unavoidable. In October 1939, the late Robert L. Dean became superintendent at Pioche. Most of his previous experience had been in the fields of iron and coal mining and from that experience he brought the concept that no accident is unavoidable. Many of the features of our present health and safety programs were initiated by Mr. Dean during his term as superintendent. Health Program: Our health program centers in Dr. Q. E. Fortier and his new, well-equipped, and well-staffed, modern hospital in Pioche. The program starts with a thorough pre-employment physical examination and is followed by yearly re-examinations at the expense of the company. The Pioche Mutual Benefit Association, to which all Pioche mine operators and employees belong, pays benefits covering hospitalization and surgery expense incurred by employee members and their families. The Association is governed by a board of directors elected by its members. The mine operators of the district donated the original capital and pay the monthly dues of the employee members. The employees pay the dues covering members of their families. Though not strictly a part of the

Jan 1, 1951

By S. S. Arentz

PLANNED health and safety programs have become an essential part of American industry because such programs lead to increased operating efficiency, improved labor relations, better public relations, and to substantial savings in compensation insurance. Those of you who have had the unpleasant duty of informing the wife or widow of one of your men of his serious injury or death while on the job, know that all the benefits of a successful safety program do not show on the balance S. S. ARENTZ, Member AIME, is General Superintendent, Nevada Operations, Combined Metals Reduction Co., Pioche, Nevada. AIME San Francisco Meeting, February 1949. TP 2741 A. Discussion of this paper (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Jan. 6, 1949. sheet. These programs are of particular importance to the mining ,industry because mining's reputation as an unusually hazardous industry and the commonly isolated location of mining operations tend to focus attention on these problems. Description of Operations: Before proceeding with a discussion of our health and safety programs at Pioche, it may be proper to give a brief description of Pioche and of our operations there. Pioche is one of the early Nevada mining camps. It was founded shortly after the discovery of high grade silver ore in 1863 and mining has continued with more or less regularity to the present day. In an era of lawlessness, Pioche was notorious. The story persists that 75 men died with their boots on before one died a natural death, and old payroll records show that nearly as many gunmen were employed to stand off claim jumpers as there were miners working the mine. That was probably as close to a safety program as the times permitted. Pioche is situated in southeastern Nevada on the main highway between Ely and Las Vegas. The camp is on the flank of "Treasure Hill," near the original silver discovery, at an elevation of about 6000 ft. The present day population of about 2000 is primarily dependent upon the mines of the area, although Pioche also serves as the county seat of Lincoln Couqty and as the center of the surrounding livestock industry. The camp is served by a branch of the Union Pacific Railroad and receives power from the generators at Hoover Dam. The Pioche operations of the Combined Metals Reduction Co. were started in 1923 when the first complex lead-zinc ore was shipped to the company's mill at Bauer, Utah. The modern mill at Pioche was completed in 1941. The operations are medium sized in the nonferrous field, employing an average of 350 men in the mine, mill, and related works. The complex lead-zinc ore is mined from replacement deposits in a comparatively flat, extensively faulted, limestone horizon. Mining methods vary from stull-supported open stopes to filled square-set stopes. The thin bedded limestone and shale overlying the ore is allowed to cave as areas are mined out and caving frequently follows closely upon ore extraction. The relatively heavy ground and the numerous faults add to the problems of safe mining. The mine is well mechanized and the mill and surface plant are modern and well equipped. Labor is organized in a C.I.O. union and labor-management relations have been unusually harmonious. During most of the period since 1923 a competent supervisory staff worked to reduce safety hazards but the primary responsibility for safety rested on the individual workman. Accidents happened and all too frequently they were regarded by all concerned as unavoidable. In October 1939, the late Robert L. Dean became superintendent at Pioche. Most of his previous experience had been in the fields of iron and coal mining and from that experience he brought the concept that no accident is unavoidable. Many of the features of our present health and safety programs were initiated by Mr. Dean during his term as superintendent. Health Program: Our health program centers in Dr. Q. E. Fortier and his new, well-equipped, and well-staffed, modern hospital in Pioche. The program starts with a thorough pre-employment physical examination and is followed by yearly re-examinations at the expense of the company. The Pioche Mutual Benefit Association, to which all Pioche mine operators and employees belong, pays benefits covering hospitalization and surgery expense incurred by employee members and their families. The Association is governed by a board of directors elected by its members. The mine operators of the district donated the original capital and pay the monthly dues of the employee members. The employees pay the dues covering members of their families. Though not strictly a part of the

Jan 1, 1951

By D. I. Bardos, F. X. Spiegel, R. K. Malik, Paul A. Beck

Study of the occurrence of elongated ß-Mn phase fields and of their direction of extension in fifteen ternary systems indicates that the ß-,mn phases formed by manganese with other transition elements and with either silicon, germanium, or tin may be considered as electron phases. In these phases the alloying behavior of silicon on the one hand and of germanium and tin on the other shows a significant difference . Formally all observations can be satisfactorily described by attributing to germanium and tin an apparent electron concentration of nine electrons per atom. This behavior may be interpreted by assuming that germanium and tin exclude itinerant electvons because of a strong repulsive potential arising fromthe requirement that their wave junctions be orthogonal to those of- the closed d shells of these atoms. The absence of a d shell in silicon allows this atom to admit itinerant d electrons. The following new ternary phases of unknown structure were identified by means of their X-vay difjraction patterns: (Mn,Co,Si)I , (Mn,Co ,Si)Y, (Mn.Co,Si)Q , (Mn ,Ni ,Si)W , and (Mn, Ti ,Si)A. The X-ray data suggest that these phases have large unit cells and that to some extent they may he related structurally to the 0 phase. The a phase and certain other phases formed by transition elements are characterized by their preferred occurrence at a constant electron concentration. AS a result, these "electron phases" have relation to electron concentration. The tendency of the B phase to form elongated phase fields in ternary systems along the directions of constant electron concentration has been previously demonstrated. The occurrence of an elongated 0-Mn phase field in the ternary system Mn-Co-Si was schematically indicated by Cherkashin et al.l0 The present study includes fifteen ternary systems, each containing in addition to manganese a second transition element from the group Ti, V, Cr, Fe, Co, Ni and one of the nontransition elements silicon, germanium, or tin. In each system the boundaries of the B-Mn phase were determined in the 900°, 950°, or 1000°C isothermal section, the temperature being dictated on the one hand by the requirement of sufficient rates of diffusion to approach equilibrium conditions in reasonably short annealing periods and on the other hand by the need to avoid as much as possible the partial melting of alloys during annealing.

Jan 1, 1967