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By C. L. Mantell

Although so common and well known a metal, tin is really a less abundant element than many of those less familiar and usually ranked with the scarce or rare elements, such as cerium, yttrium, lithium, beryllium, titanium, zirconium and vanadium. The color of tin is white, with a slightly bluish tinge. When it is compared with nickel, the latter metal is brown. When placed alongside of tin, chromium is definitely blue. Tin is whiter than silver or zinc. Exceedingly thin films of tin show various shades of brown by transmitted light. The metal has a brilliant luster, and when mirror-polished, has high light reflectivity. The luster depends to a large extent upon the pouring temperature at which the metal is cast. If the temperature be too high, iridescent colors may show on the surface. These are the result of oxide film formation. If the pouring temperature be too low, the surface is dull. Small amounts of foreign metals, such as lead, arsenic, antimony and iron, decrease the luster of tin and impart a yellowish tinge to the metal. The structure is decidedly crystalline. The cast metal is a mass of crystals. When a bar of tin is bent, it emits a characteristic creaking sound. This is called the "cry" of tin, resulting from the grinding of the crystals one against the other during the bending of the metal. Tin metal may lose its crystalline structure by cold working, but grain growth occurs rapidly under the influence of heat. Metal which has been cast at a low temperature may become amorphous as the result of mechanical work. If such material be heated to temperatures well below the melting point, say at 110° C. for a half hour or for a few minutes at 150" C. recrystallization occurs. If the surface of tinned plate, tin foil, or tin meta1 in cast form be etched with hydrochloric acid containing a little free chlorine, attack occurs at the intererystalline faces. The surface shows patterns resembling the frost flowers on window panes in winter. The etched appearance is called moire metallique. Fine dendritic surface crystals of tin may be obtained by casting the metal on a surface of polished steel. In commercial tin plate, the intercrystalline boundaries are shown by fine grooves or channels, .which result from the method

Jan 1, 1929

By R. H. Doremus, E. F. Koch

The first carbide phase that precipitates at 120°C from a iron containing about 0.02 wt pct, C was studied with the electron microscope. In both strained and unstrained material the carbide particles appeared to form on the dislocations in the iron, in agreement with the results of the kinetic study in part II. The structure of the carbide was tentatively identified as an expanded a-iron lattice (body-centered tetragonal) with about 0.7 wt pct C. This phase appeared to be metastable and apparently transformed into cementite or epsilon carbide when the iron was over-aged. WhEN a iron containing less than about 0.025 wt pct C is quenched from 700°C to room temperature the carbon is retained in solid solution and precipitates out slowly with time. The morphology and structure of the precipitating phase are still in doubt, two different carbide phases, epsilon carbide and cementite, have been identified, but there is considerable disagreement about the time and temperature at which they appear.1-4 Epsilon carbide seems to form at lower temperatures than cementite, although one group of investigators4 found only the latter phase over a wide range of aging temperatures. Usually these two phases have been identified after aging times much longer than needed to drain the carbon from supersaturated solution, at least for aging temperatures below 200oC. The precipitated carbides have been observed with the electron microscope,'-5 but again most results have come from samples aged much longer than necessary to reduce the carbon concentration in solution to a low value. In this study the carbide phases were observed in earlier stages of precipitation with the electron microscope, in order to learn more about the shape, size, and distribution of the carbide particles. Samples strained small amounts before aging, as well as unstrained samples, were studied, and the structure of the carbide phase was tentatively identified. EXPERIMENTAL "Ferrovac E" vacuum-melted iron, from which the wires for kinetic studies were also made (Refs. 6 and 7 and the following paper) was used for this work. An analysis of this material is given in Table I; it agrees well with the manufacturer's values. The number of inclusions in the iron was very small, as can be seen in the optical micrograph in the following paper. Pieces of iron about 1 mm thick and 5 to 10 mm in diam were used for all the studies except for those in which the sample was strained before aging; then the specimen was a rod 3 to 6 mm in diam and 20 cm long. The samples were held at about 700°C in wet hydrogen for at least an hour to remove residual carbon and nitrogen, after which they were heated to 950" (in the y region) and cooled to room temperature in the furnace. This treatment gave an average grain diam of more than 1 mm, so that the effect of grain boundaries on the precipitation process was negligible. The samples were carburized at 710°C for about 2 hr in hydrogen that had passed over toluene held at -30°C; then they were rapidly quenched into water. From chemical analysis this treatment gave a carbon concentration of from 0.012 to 0.016 wt pct, which is less than the solubility of carbon at this temperature. After quenching, the samples were aged at 120 "C in an oil bath for vari-

Jan 1, 1961

By George Krauss, Seth R. Thomas

One complete cycle, allstenite to martensite to aus-tenite, of Martensitic transformation was induced in a commercial 18 Cr-8 Ni stainless steel. Transmission electron microscopy showed that the reverse transfarmation, martensite to austenite, perpetuated the dense defect substructure of the martensite produced by the direct transformation, austenite to 'martensite, and reproduced the retained austenite matrix orientation. A general precipitation of lathlike M,,C, particles was noted to be present in, and is suggested as cause for, regions of martensite that Izad formed after a complete cycle of transformation. The habit plane of the precipitate particles was found to be within 5 a plane previously established as the habit of nitride precipitates of similar morphology in bcc iron. The direct transformation of austenite (y) to martensite (a) in metastable 300 series stainless steels has received considerable attention in the past,'-8 and the martensite product given special emphasis in recent years,9"*u but little information has been published about the reverse martensitic transformation during which bcc a martensite is converted to fcc y austenite."-" The reversal mechanism and the resulting crystallographic relationship between parent and product austenite are of fundamental concern. The reversal product, fully austenitic, and hereafter referred to as reversed austenite, exhibits a defect structure far different from its virgin counterpart. Some studies have been reported in which the structure of reversed austenite in iron nickel alloys is compared to annealed austenite with respect to austenite strengtheningM and Stabilization.' The martensite in these Fe-Ni alloys, however, shows a basic difference from that produced in stainless steels. Structurally, the Fe-Ni martensite is profusely twinned," while the (low-carbon) Fe-Cr-Ni martensite contains a high density of tangled dislocations and is apparently twin-free.I0 reediis" has recently shown in an Fe-16 Cr-12 Ni stainless alloy that this typical martensitic defect structure and the reverse transformation directly influence the structure of the reversal product. He found that much of the reversed austenite had returned to the orientation of the virgin austenite and that fine twins were formed in the austenite after the reverse transformation. This investigation was undertaken in order to describe as completely as possible the structural changes produced by a cycle of transformation in a typical 18-8 stainless steel. EXPERIMENTAL PROCEDURE The 301 stainless steel under investigation (17.44 Cr, 7.75 Ni, 0.80 Mn, 0.60 Si, 0.40 Mo, 0.40 Cu, 0.08 C, 0.03 N, bal Fe)was received as 0.060-in.-thick

Jan 1, 1968

By N. Albon, J. F. Miller, R. W. Coutant

The deposition of nickel from nickel carbonyl onto amorphous substrates has been studied, with attention being paid to the specific effects of the physical and chemical nature of the substrate and to the effect of oxygen on the crystal morphology. With substrates having microscratches or etch lines, nu-cleation was observed to occur preferentially at these surface features. Flame polishing of the substrate surfaces was found to remove any regularity in preferred nucleation sites. Nucleation was observed to occur less readily on substrates having relatively low surface energies, e.g., Teflon and carbon, than on materials having relatively high surface energies such as fused silica. At low oxygen concentrations [Ni(CO)4/O2 > 54 x 1031, apparently pure and well-formed nickel crystals were observed to nucleate and grow irrespective of the presence of oxygen. At higher concentrations of oxygen, a secondary growth process, dependent upon oxygen concentration and resulting in a gradual change in crystal morphology, was observed. It is concluded that the influence of oxygen on the nucleation and growth of nickel is determined by the relative kinetics of the various possible reactions, and that under the experimental conditions employed the 0-Ni interaction occurs at some nucleation or prenuclea-tion stage. THE purpose of the research on crystal nucleation in chemical vapor deposition as described in this paper has been twofold: 1) to examine some effects arising from the use of amorphous substrates, and 2) to study the specific effects of oxygen on the nucleation and growth of nickel in a nickel carbonyl-carbon monoxide system. The nickel-nickel carbonyl system was chosen for study for several reasons: 1) nickel films are of potential interest in electronic technology, and 2) the deposition can be carried out at moderate temperatures, thus making possible detailed study of the processes occurring and the use of a variety of substrate materials (including some which melt at relatively low temperatures). Fairly well-characterized chemical kinetics and a broad background of information are available on the py-rolysis reactions and on the mechanisms of Ni-O interactions. NUCLEATION AND GROWTH THEORY The theoretical background for the analysis of nucleation and growth by vapor deposition for a one-component system (physical vapor deposition) and the problems encountered therein have been reviewed by Hirth and pound.' More recently Mande12 has indicated the difficulties of applying such theory to chemical systems. One of the major problems involved is the possible multiplicity of chemical reactions and deposition routes. For example, those reactions which are probably of significance in a discussion of the pyrolytic deposition of nickel from nickel carbonyl under the conditions of the present experimental work are illustrated in Fig. 1. As is true with most cases of chemical deposition, many of the quantitative data necessary for a complete analysis of the system are either not available or not directly measurable. However, with the present system, sufficient data are available for a discussion of nucleation and growth on a qualitative basis. Classically, the rate of nucleation of a monatomic species being deposited from a vapor phase is given by

Jan 1, 1965

By F. I. Stalkup

Vapor-liquid phase equilibrium experiments have been conducted in a static equilibrium cell on mixtures of a light, 45 API stock- tank gravity reservoir fluid and a rich hydrocarbon gas containing approximately 55 mole per cent of intermediate hydrocarbons. Both apressure-vs-composition study of the gas and a simulated reservoir fluid, and a multiple-batch contact simulation of the condensing-gas-drive oil recovery process were performed. In the latter experiments equilibrium gas and liquid compositions were analyzed. Also, conventional, "condensing-gas-drive", long-tube displacement experiments of the reservoir fluid and gases of various richness were performed. The results of these experiments could not be satisfactorily interpreted by the conventional pseudo-ternary-diagram representation of multicom-ponent phase behavior. The results seem to be explained better by considering a bubble-point surface and a dew - point surface joined in a plait-point locus. Portions of the plait-point locus cannot be "seen" directly by the rich hydrocarbon gas because of curvature of the dew-point surface. In such a system, continuous injection of the rich gas over stationary reservoir fluid might form a zone of contiguously miscible compositions from pure rich gas to pure reservoir fluid by: (1) saturating the reservoir fluid with injected gas to the bubble-point surface; (2) creating by mass transfer with fresh injected gas a path of contiguously miscible compositions along the bubble - point surface to the plait-point locus; and (3) creating by mass transfer with additional injected gas a path of gas compositions along the dew-point surface up to the point where direct miscibility results between dew-point fluid and the injected rich gas. INTRODUCTION The use of the pseudo-ternary-phase diagram to illustrate miscible displacement phase behavior has been discussed by several authors.5,7 Such a representation of phase behavior is not rigorous, but the ternary diagram nevertheless gives a qualitative picture of what actually occurs in a miscible displacement process. Fig. 1 is a typical illustration of miscible displacement phase behavior by a ternary diagram. The multicomponent hydrocarbon system is divided into three pseudo-components: a light fraction containing methane and nitrogen, an intermediate fraction containing ethane through hexanes plus carbon dioxide, and a heavy fraction containing heptane and heavier components. A two-phase region is bounded by a dew-point curve and a bubble-point curve, which are joined at the critical point. The concept deduced from such a representation for miscible displacement by a condensing-gas-drive process is as follows: a rich gas G, which lies to the right of the limiting tie line through the critical point C, is injected into the reservoir and contacts reservoir fluid L, saturating the reservoir fluid to give bubble-point fluid L1 and equilibrium dew-point gas GI. Continued injection of rich gas changes the composition of the saturated liquid L1 through a series of liquid compositions lying along the bubble-point curve, until the critical composition C is reached, at which point direct miscibility with the rich gas is achieved. Some equilibrium gas with compositions lying along the dew-point curve from G1 to C is also formed in this process. Thus, continuous injection of rich gas forms a

Jan 1, 1966

By D. T. Peters, J. C. Bisseliches, J. W. Spretnak

The pain boundary relaxation phenomenon in high-purity copper, 0FHC copper, and a precipitation-hardenable alloy o-fCu-2 uit pct Co has been studied by internal ,friction and elastic aftereffect techniques. The data were analyzed by assuming the broad distribution of relaxation times observed obeys a lognormal distribution law which enables calculation of the relaxation strength. Grain size had no effect on relaxation strength, although the peak width increased with increasing grain size and decreasing temperature. A double grain boundary peak was produced in high-purity copper by annealing to produce secondary recrystallization. The activation energy measured for 99.999 pct Cu is 37.5 * 3 kcal per mol and 46.5 kcal per mole for OFHC copper. A small peak in the Cu-Co alloy at about 220°C at 1 cps was deduced to be the grain boundary peak. Its height increased and its activation energy decreased with increasing aging time. Except for erratic peak positions the observations were consistent with the theory of pain boundary sliding. BEFORE the mechanism of the grain boundary internal friction peak in metals can be satisfactorily explained, the detailed characteristics of the relaxation process must be documented. Of interest are the effect of grain size on relaxation strength, the high-temperature background, and peak width and position. The effect on the grain boundary peak of a precipitate at grain boundaries and of the change in distribution of the particles with aging time must also be explained by any existing or forthcoming theory. The model which has received the most attention was proposed by KG' and zener2 and proposes that the anelastic strain results from sliding of adjacent crystals at grain boundaries. The sliding is limited by the interlocking of grain corners. It follows, according to this model, that the relaxation strength is independent of and the relaxation time is proportional to the grain size. The proportionality between grain size, D, and relaxation time, t, has been confirmed by K&' and Bisseliches . In this case, the internal-friction peaks of various specimens can be superimposed by plotting Q-' as a function of the parameter vD exp H/RT where v is the frequency and H the activation energy. However, the data of Starr et 01.' and Leak6 fit better to a parameter containing D to an exponent near two. A meaningful relationship is not always deducible from the shift of peak temperature with grain size. KG7 demonstrated that a twofold variation in grain size obtained by varying the amount of cold work followed by identical recrystallization anneals will cause a peak shift that is too large to be accounted for even by an exponent of two. Since the decreased grain boundary area existing with a larger grain size is exactly compensated for by an increased sliding distance, the relaxation strength should not decrease with increasing grain size. The height of the internal-friction peak has generally been observed to be rather insensitive to grain size as long as the average grain diameter does not approach the specimen diameter. Exceptions have been reported by Koster, Bangert, and Lang8 for copper, and by Leak6 for iron. The observations for copper could well have been confused by the presence df 0.3 pct0. The possibility that the peaks may simply be increasing in width with increasing grain size and that the relaxation strength, which is proportional to the area under the peak, may remain constant was not examined. his point has been checked in this investigation using high-purity copper. Atomic mechanisms to account for damping by sliding at grain boundaries have been proposed by KG7 and Mott. KG predicts the activation energy to be identical to that for self-diffusion. Mott's "island" model suggests the activation energy is nL where n is the number of atoms in an island and L is the latent heat of fusion per atom. Other authors have felt that a value equal to the activa-

Jan 1, 1964

By V. A. Josendal, J. W. Wilson, B. B. Sandiford

Two radioactive tracers have been tested as a means of determining core saturation in multiphase flow studies. Cesium chloride was tried as a water-phase tracer, but complications in its use in low permeability cores resulted from sorption of cesium by the core or water-wet pads. IodoI3'ben-zene proved very satisfactory as an oil-phase tracer. The synthesis of iodobenzene from the sodium iodide as received from Oak Ridge is simple and direct. The tracer is insoluble in water and there was no evidence of sorption by any of the core materials used. use of the method to determine saturation profiles during capillary and dynamic desaturations and relative permeability measurements on oil-water and oil-gas systems is described. Comparisons of the dynamic and capillary methods of relative permeability determination were made using the tracer to check core saturation and saturation distribution. Other experiments are also described in which mobility of the oil phase at various saturations was measured by displacing labeled oil by flowing inactive oil. Similar experiments were made using water labeled with cesium 134. INTRODUCTION To be fundamentally sound. any laboratory method of determining relative permeability must meet, among others, the following requirements: (1) the core saturation between the pressure taps must be uniform, and (2) there must be uniform pressure difference between the phases in the region between the pressure taps. In practice it may eventually be shown that appreciable departure from either or both of these conditions may be permitted without introducing sensible error. but the magnitude of such error remains to be established. There is need then for methods of saturation determina- tion which will determine the saturation profile in a core as well as the overall average saturation given by the gravimetric or material balance methods usually employed. Methods which have received consideration include resistivity, X-ray absorption, gamma ray absorption, neutron diffraction, and radioactive tracers. The resistivity method has use in the determination of profile, but needs checking by independent means.' The X-ray method has been used successfully, but requires elaborate equipment and calibration.23 4 At present gamma ray absorption is practical only for very large cores. The neutron methodo does not appear adaptable to measurement of saturation variations in short cores since it is a scattering method. Russell, Morgan and Muskat' employed radiovanadium in a study of the mobility of interstitial water. Coomber and Tiratsook used radioiodine as an oil-phase tracer and measured profiles in unconsolidated sand packs. ADVANTAGES OF RADIOACTIVITY METHOD A thorough discussion of the theory of radioactive tracers and the technique of using them to study the movement of fluids in sands is given by Coomber and Tiratsoos and need not be detailed here. The method requires less equipment than the X-ray method; the counting problem is similar, but the generation and regulation of the radiation, which is a major problem in the X-ray method, is not required in the radioactivity method. In the X-ray method it is customary to add up to 20 per cent of absorber, usually an iodine compound, to the phase to be labeled. while in the radioactivity method a mere trace is sufficient. A possible disadvantage of the radioactivity method is that a disproportionate amount of the activity comes from the portion of the core nearest the counter, whereas the X-ray gives a true average saturation in the region traversed by the beam. 011 the other hand, this characteristic of the radioactivity method renders it peculiarly adaptable to study of certain types of radial variations in saturation. As with the X-ray method, a tracer may be added to either the oil or water-phase. An oil-phase tracer is more generally useful. however. since it permits work on oil and gas in the

Jan 1, 1952

By P. Hazebroek, C. S. Mathews, E. E. Allen, H. C. Lefkovits

A rigorous study was made of the behavior of reservoirs composed of horizontal layers, unconnected except at the well and filled with a compressible fluid. The report is presented in two parts. Part I deals with the practical implications of the results obtained; Part 11 contains the mathematical derivation of the solution. The main portion of Part I is concerned with application of the results to reservoirs composed of two layers. Relative rates of depletion of the layers are studied, and it is shown that differential depletion between layers exists in the transient stage of the reservoir, which generally is of an order of magnitude longer than the transient stage in a single-layer reservoir. In the transient stage, the more permeable layer is depleted faster than the less permeable. However, the reservoir approaches a steady-state situation where both layers contribute equally to production. Theoretical build-up curves from such reservoirs are presented, and the influence of a skin effect and flow into casing and tubing are also evaluated. The build-up curves are predicted to have, first, the familiar logarithmic straight-line section and, subsequently, a rising and flattened section. The results found are compared with an extension of an approximate theory, and it is found that this simplified theory is applicable over most of the life of the reservoir. Extensions to reservoirs containing more than two layers are indicated, and examples of the performance and build-up curves for three-layered reservoirs are presented. The theoretical results on build-up curves were applied to field examples of such reservoirs, and satisfactory results were obtained. From the build-up curve, the pemeability-thickness product, the wellbore damage and the static pressure are obtained. However, it apparently is not possible to determine the properties of the individual layers from the combined build-up curve. A large number of reservoirs have been found where the producing formation is composed of two or more layers of differing physical characteristics, such as permeability and porosity, and where also the thicknesses of the layers differ. Since in general a differential depletion should exist between the layers of such reservoirs, it would be advantageous to know the amount of the differential depletion under a given production history. It also would be valuable to know the pressure behavior, because it could be undesirable to produce a reservoir in such a manner that the pressure in one of the layers would have fallen below the bubble point of the oil at a time when another layer might still be virtually undepleted. The determination of static pressures in shut-in wells with slow build-up is another feature of importance in layered reservoirs. If the behavior of the reservoir differs appreciably from the predicted behavior of a single-layer reservoir, the type of analysis for build-up curves suggested for single-layer reservoirs is not applicable. Several authors have treated the problem of finding the pressure and production characteristics of multilayer reservoirs. Horner treated the problem of n layers in an infinite field, the layers being connected only at the well. Tempelaar-Lietz2 has presented an approximate treatment of the characteristics of a bounded reservoir composed of two layers of different permeabilities and equal thicknesses. Homer gave no information on differential depletion between layers, and the treatment of Tempelaar-Lietz was not applicable for prediction of pressure build-up behavior. In addition, it was thought that a more rigorous treatment than the one by Tempelaar-Lietz would be valuable in determining the range of validity of this solution. The present study, therefore, was made of a bounded reservoir composed of two or more layers,

By A. D. Marriott, J. V. N. Dorr

This paper reviews recent developments in the application of classification practice to the origination of fine-grinding flow sheets and traces the history of the mechanical classifier from its initial application for separating cyanide process sands and slimes down to its present six or more distinctly different applications at copper concentrators; it undertakes to show also, by reference to diagrammatic fine-grinding flow sheets and accompanying operating data from nine copper concentrators in western North America, the advantages gained from improved classi-ficiation flow sheets at these properties in terms of reduced grinding costs, improved flexibility of operation or increased recovery. Comparison is only made between different fine-grinding flow sheets at a given plant and no attempt is made to compare different concentrators, on account of ore variations and differences in metallurgical objectives sought,. The adoption of the flotation process in recent years, and especially the development of selective flotation, has brought a demand for much finer grinding than formerly. This has caused much thought to be given to grinding efficiency, and today there is hardly a mill where the grinding flow sheet is not under close study and subject to frequent changes. When closed-circuit grinding was introduced into metallurgy some years ago, its value was recognized at once, and since then the combination of mills and classifiers has been regarded and operated as a grinding unit. Apart from variations in both the grinding and classifying elements of this unit, there have been many variations in grouping tried by different mills to suit varying conditions of ore and plant limitations. Although operators feel that in most cases their present flow sheets are on trial, and the data on present work are often incomplete, we have felt that a discussion of the progress that has been made and an endeavor to show present trends and their results should be of use to the profession. We have therefore prepared flow sheets of some of the larger mills with which we have been in contact and present them with available data as to their results, in the hope that they may be of service now rather than later when practice may have become more standardized and more complete records and analyses have been made. We believe that the data given,

Jan 1, 1930

By W. T. Turrall, M. J. Cook

A discussion of modern developments in beneficiation of fine sizes of anthracite, this paper includes a description of the plant flowsheet, an analysis of operating results, and a summary of fundamentals of mineral separation relative to plant operation.

Jan 9, 1953

By A. H. Daane, J. J. Hanak, F. H. Spedding

IN the study of the rare earths at the authors' laboratory, methods have been devised for preparing pure rare earths and many of their properties'- have been determined. Very little information is found in the literature on the properties of europium metal, which is the scarcest of the naturally occurring rare earths. Since we have recently prepared europium in appreciable quantities, we are in a position to describe the method of preparation and some of the properties of this metal. Metallic europium was first prepared by Klemm and Bommera who heated a mixture of potassium and EuC1, in vacuo, and obtained a mixture of europium metal and KC1. Trombe4 electrolyzed a molten salt bath containing NaC1, KC1 and EuC1, and collected the europium in a molten cadmium electrode as a cadmium alloy. The cadmium was subsequently removed by distillation but the properties of the residue indicate that pure europium was not obtained. McCoy attempted to prepare europium by distilling mercury from europium amalgam, but the stability of the Eu-Hg intermetallic compounds prevented a complete separation of the two elements. The preparation of very pure europium was suggested by previous work in this laboratory1,4 in which ytterbium and samarium were prepared by heating the respective sesquioxides with lanthanum metal turnings to 1450°C in vacuo and distilling ytterbium and samarium from the mixtures. Subsequently, small test experiments showed that europium also could be prepared by this method. A more detailed version of this method was used in the work described in this paper. Klemm and Bommer3 found by X-ray analysis that the metal had a body-centered cubic (bcc) structure with a lattice constant a, = 4.582 ± 0.00A (converted from kX units), with a bulk density of 5.30 g per cu cm. They found europium to be weakly ferromagnetic. Spedding, et al,7 found a,, to be 4.606 ± 0.001A. Barrett' showed that the bcc structure persists throughout the temperature range 5 to 3000K with a, at 5, 78, and 300°K being 4.551 ± 0.003, 4.551 ± 0.004 and 4.577 ± 0.001A, respectively. Trombe1 described europium as being iron gray, malleable, about as hard as neodymium and not attacked by cold water. He estimated the melting point to be between 1100 and 1200°C. Previous work in this laboratory indicated that the pure metal corrodes rapidly in air and reacts with cold

Jan 1, 1959

By D. Beregekoff

In the routine examination of a wide variety of metal specimens it is sometimes necessary to have special methods of polishing in order to retain and reveal certain details in each specimen. Among such special cases is the retention of graphite in malleable and gray cast irons, the preservation of all types of nonmetallic inclusions in both hard and soft steels, obtaining a scratch-free surface with soft metals, and avoiding the usual relief effects with very hard specimens such as tool metals con-taining various carbide and nitride phases. It is the purpose of this paper to give an account of some of these special polishing methods in use at the Union Carbide and Carbon Research Laboratories. The polishing procedures outlined have been found to give uniform results. It is obvious that only general rules and the most important working details can be given here. Following these rules, the polisher can obtain satisfactory results if he possesses the necessary patience and has a sincere desire to give as nearly perfect a finish as possible to his work.

Jan 1, 1939

By C. K. Dumbauld, B. E. Morgan

The need for a low-strength cementing composition for use in well cementing is reviewed and results are presented of laboratory and experimental field tests of a modified cement having a controlled ultimate tensile strength of approximately 200 psi. The modified cementing composition may he prepared from either high early strength or normal portland cements by the addition of bentonite clay and a suitable agent for dispersing and controlling the set of the slurry. Substitution of the modified cement for conventional slow-set cements may give better completion results in many wells because the modified cementing composition has lower set strength, lower slurry density, and greater slurry stability than conventional cement slurrieh. The lower ultimate strength allows greater penetration with less shattering of the set cement when perforating casing and cement. The lower elurry density allows the placement of longer columns of cement slurry, and the greater slurry stability reduces the possibility of having an uncemented section caused by the settling of cement particles before the cement set.. INTRODUCTION High strength lias always been one of the accepted criteria of a good cement. During the early use of portland cement in well cementing. emphasis was placed upon securing cements with higher strengths. In 1931, Barkis' reported that, "Normal oil well cements have been improved to develop greater strengths and uniformity of product, which has aided in producing successful jobs in cementing the deeper strings." As long as most wells were completed by the open-hole method. the use of cements having high strengths seemed desirable, and there was no objection raised against high-strength cementing compositions. For a number of years. how-ever, the industry has been completing a large numher of wells by setting and cementing casing through productive horizons and then obtaining production by gun-perforating the section of casing opposite the desired interval. Although this method has been generally successful, difficulties have been experienced in some cases in completing or recompleting wells because of apparent lack of adequate penetration by the bullets through the casing and surrounding sheath of cement and into producing formation. In addition to the penetration trouble: there have been indications that fracturing and shattering of the set cement by perforating might he a contributing factor in causing the failure of some jobs to exclude water or gas from oil producing zones. The possibility that cements having high set strengths were contributing to til difficully ill obtaining satihfartory perforating results has re. ceived attention during recent years. Gun perforating tests conducted in 1944 showed that the depth of bullet penetration into set cement varied with the hardness of the cement, the greater the strength of the cement the less being the penetration. In 1946, Farris2 pointed out that high strength cements were not needed in well cementing, and in 1947, data published by Oliphant and Farris3 showed that set cement was perforated without shattering at approximately 150 psi tensile strength. whereas at approximately 300 psi tensile strength severe cracking and shattering occurred. Oliphant and Farris suggested that wells be perforated at the proper time interval after placement of the cement so that the set cement would have the desired strength. Several difficulties may he encountered in trying to perforate a cement job at the correct time to catch the tensile strength near 150 psi. The rate of strength development of different cements varies considerably. This fact is illustrated by results of tensile strength measurements presented in Fig. 1. These data show that at 175°F the tensile strengths of three conventional slow-set cements varied from 75 to 235 psi at the end of 12 hours. After 24 hours, the tensile strengths varied from 200 to 455 psi. The rate of strength development is affected. also. by the temperature of the forniation, and this adds to the uncertainty of perforating at the rorrect time, since accurate well cementing temperatures may not he known in many cases. Furthermore, in the recomple-tion of wells it is sometimes necessary to perforate cement which has set for a long period and has developed maximum or final strength. In view of the apparent need for a cementing composition having a controlled ultimate strength, an investigation was

Jan 1, 1951

By C. S. Barrett, O. R. Trautz

Previous investigations have shown that lithium is body-centered cubic from near its melting point to the temperature of liquid air.1,2,3 Nevertheless there was an incentive to search again for a transformation at low temperatures: C. Zener4.5 has remarked that the low value of the elastic modulus (C11 — Cl2)/z of body-centered cubic metals and alloys implies a rapid increase in free energy with decreasing temperature, which would favor the occurrence of a transformation; also the shear movement to which this modulus applies is one that can transform a body-centered cubic structure into a slightly distorted face-centered cubic structure. It was confirmed that lithium does not transform spontaneously at liquid nitrogen temperature, but it was found that a transformation can be induced at this temperature by cold working the metal,6 and at slightly lower temperatures a different transformation occurs spontaneously. Transformations were also found in solid solutions of magnesium in lithium. The Nature of the Transformations Before presenting a detailed treatment of the technique used and the specific data obtained, it would be well to give a brief survey of the general characteristics of the transformations. A new crystal structure begins to form spontaneously in a specimen when it is cooled below a critical temperature. In lithium the structure appears to be close-packed hexagonal; in theLi-Mg alloys most of the diffraction lines (but not all) are near those for hexagonal lithium. The transformation proceeds as the temperature is lowered and soon stops if the temperature is held constant or raised. The course of the transformation on cooling is indicated by the curve at the lower left of Fig -I. This curve is drawn in stepped fashion because the transformation goes by discrete steps with audible clicks. Because of the similarity to the decomposition of austenite into martensite in steels, it seems appropriate to designate the beginning of the spontaneous transformation on cooling as the Ms point. On heating to room temperature after the low temperature treatment only the usual BCC structure is found. On heating, the low temperature modification begins to disappear at a temperature which will be designated as Ac. The transformation on heating is halted when the rise in temperature is halted. The temperature must be raised 40 to 50°C above Ac before the reversion is complete—an interval which is sensitive to the rate of heating and to the time of holding at temperatures above Ac. This behavior on heating thus has similarities also to the formation of martensite in the cooling of steels.

Jan 1, 1949

By A. S. Hewitt

After an interval of fourteen years, saddened for all of us by the death of David Thomas, the father of the anthracite iron-trade, first president of the Institute, and by the untimely loss of his successor, Alexander L. Holley, whose memory we are about to honor by loving services, the members of the American Institute of Mining Engineers have conferred upon me for the second time the office of president, under circumstances similar to those which led to the choice in 1876. Then the whole world was represented at the great exposition of industry which was held in Philadelphia to celebrate the one hundredth anniversary of our declaration of political independence. In 1890 it is our privilege to receive as guests the members of the British Iron and Steel Institute, who, with singular and graceful felicity, have appointed a meeting in the United States in the year when we pass from the second to the first place in the international column of the production of iron, and thus celebrate our industrial independence. For the honor of being chosen to extend to our distinguished guests the right hand of fellowship and a hearty welcome I return to my associates the grateful acknowledgment of one whose chief claim to your favor is to be found in his love for the professional occupation in which we are all engaged, and in his efforts, public and private, to promote its advancement into new fields of usefulness. In order to indicate the full significance of the visit of our foreign guests at this time, it will be proper to explain briefly the origin, aims and work of the Iron and Steel Institute. It unquestionably owes its birth to the International Expositions held in London in 1851 and 1862, and in Paris in 1867. These expositions served to break down the jealousies of nationality and to diffuse a better knowledge of industrial processes. Trade-secrets, which had been carefully guarded, became common property; manufacturers who had previously regarded themselves as rivals formed bonds of union and ties of friendship, as the results of an intercourse which

Jan 1, 1891

By C. G. Dunn, E. F. Koch, K. T. Aust

Strain-induced grain boundary migration was studied in a series of silicon-iron (3% pct Si) bicrystals of controlled orientations. Each bicrystal was given a 7 pct cold-rolling strain rind annealed at 1100°C. The direction of boundary migration was found to depend on orientation; results for several orientations related by a common [110] axis are given. Analysis of the micrographic and X-ray data is made in terms of the residual strain-energy densities within the crystals (energy per unit volurne) and a driving force on the boundary due to an energy density difference across the boundary. Relative strain energies were obtained for the various orientations investigated. A CHROME-acetic acid electroetching method for revealing dislocation sites in silicon iron was previously applied to clarify the structural features and the energetics involved in strain-induced grain boundary migration.',' The present paper is a continuation of this study, but is primarily concerned with the influence of crystal orientation. Sperry, as reported by Beck,3 attempted to determine the factors that influence the preferred growth of one grain over another in aluminum due to strain-induced boundary migration. He found that the particular grain of a pair which work hardened more was invaded, although exceptions to this correlation were noted. The index of work hardening was determined from microhardness measurements of each grain before and after cold-rolling. In the present study, orientation itself was taken as a useful variable for studying the behavior of individual grains in a bicrystal and the direction of boundary migration, since the extent of work hardening is orientation dePendent." The effect of strain on boundary migration is evident from a consideration of driving forces. Thus, in the absence of inclusions, the driving force (per unit area of boundary) for growth of grain A into grain B when a bicrystal is strained and annealed may be expressed as follows:2

Jan 1, 1960

By L. S. Castleman, L. L. Seigle

THE formation and growth of intermetallic phase layers is of considerable practical importance to metallurgists interested in diffusion bonding and cementation processes and has been the subject of extensive qualitative investigation. In contrast, it is somewhat surprising that so little quantitative data have been amassed. The need for additional fundamental work was pointed out by Mehl in 1936,' and persists to a large extent to the present day. The early studies have been reviewed by Rhines,2 and his conclusions have been summarized by Lustman and Mehl3 substantially as follows: 1) All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two metals; however, in some cases, certain of the phases may be too thin to be observed and identified easily. 2) The isothermal growth of intermetallic phases generally obeys a simple parabolic equation of the form X2 = Kt, where x is the thickness of the alloy layer, K the temperature dependent reaction rate constant, and t the time. 3) The rate of thickening varies with temperature according to the Arrhenius equation k = Ae -Q/RT , where k is the parabolic rate constant, A, a temperature independent constant, Q the heat of activation for the process, R the gas constant, and T the absolute temperature. Subsequently, Lustman and Mehl made a quantitative study of the laws of growth in intermediate layers in a number of binary systems, in which one of the components was either zinc or cadmium, and the other component was one of the following: nickel, copper, silver, cobalt, gold, iron, or Monel metal; the interdiffusion times used were for the most part less than 24 hr. It was found that the simple parabolic law was not obeyed in general, but that a generalized parabolic law of the form xn = kt was valid, where n was a temperature dependent constant; also,

Jan 1, 1959

By W. H. Bassett, C. Davis

Although brasses and bronzes have been made for ages, a systematic study of their physical properties has been carried out only during the years of the present century. Among these properties may be included those which are to be detected by means of microscopic examination; in other words by the science of metallography. The earlier workers in this field, both in this country and abroad, gave their attention to steel. When the senior author explored the situation in 1902, there was little encouragement to be found in undertaking the study of the non-ferrous alloys. A start was made, and the metallography of the brasses and bronzes, as well as of the copper-nickel-zinc alloys developed materially under his direction. Annealing experiments were begun in 1902, and in the succeeding years the effect of temperature, and the influence of previous working, on the grain size of brass were studied. The conclusions so well known and widely published today were largely reached during those earlier years. In 1905 the first complete annealing series were made. By this it is meant that brass and copper sheet, 5 B & S Nos. hard, was machined into tensile test specimens, then annealed under accurate control for 30 min. at temperatures up to the melting point of the material. Various determinations were made, including tensile strength and elongation in 2 in. There rapidly followed similar series on all of the copper-zinc alloys from 100 to 60 per cent, copper, on the bronzes, cupronickels, and on copper-zinc-nickel alloys. At this point there was published by Grard, in October, 1909,' the very comprehensive and complete work on the tensile properties of cartridge brass, 90-10 copper-zinc, and electrolytic copper. The excellent photomicrographs in that paper illustrated the changes in structure produced by cold rolling as well as by annealing at different temperatures, but where Grard's work was confined to copper and to two alloys, the investigations in this laboratory have been over the entire fields of the commercial copper-zinc alloys, copper-tin alloys, representative copper-nickel and copper-nickel-zinc alloys as well as aluminum bronzes and others of a more special nature.

By R. H. Edsal, G. Horvay

The transient one-dimensional heat-conduction equation is solved for two semi-infinite media, at different initial temperatures, brought into (poor) thermal contact. It is shown that the two interface temperatures gradually approach the well-known, instantaneously assumed, common interface temperature of the case of zero contact resistance. The present analysis, with slight modifications, may be used in fair approximation also for the class of problems involving a change of phase. One particular application of the boundary value problem solved in this paper concerns the determination of the temerature distribution in metal castings and molds.P This problem has been treated extensively by analytical methods (see e.g., the literature listed in Refs. 1 to 4) by electrical analogs (see e.g., Refs. 11 to 14) and also by experimental methods (see the literature listed in Refs. 4, 5), but prior to the work of Pellini and Ruddle the experimental results were rather unreliable. Immediate motivation for the work described in this paper was to better understand the results of Pellini,' which are typified by the curves of Fig. 1. Pellini cast 20-in. high, 7-in. sq steel ingots into cast-iron molds of various thicknesses. He measured the temperatures at mid-height, at a number of stations in the casting and the mold, and obtained the cooling curves shown in Fig. 1. The most conspicuous thing about Fig. 1 is the large temperature discontinuity at the interface between casting and mold, due presumably to the shrinking away of the casting from the wall and the attendant creation of an airgap, as the casting cools. Such a contact resistance slows down the anticipated freezing rate; an analytical prediction of this is of much interest in foundry practice. The determination of the effect of contact resistance in the presence of a change of phase will be dealt with, by an approximate method, in a separate paper.' In the present paper the much simpler problem is considered in which there is contact resistance but no change of phase. This problem frequently arises in the analysis of aircraft structures.+ It can initial temperature, and may be regarded as semi-infinite. We suppose the thermal properties in the two media to be time, temperature, and space independent; there are no sources or sinks within the media. In Fig. 2(a) we illustrate, schematically, the case of no contact resistance. The semi-infinite media "0" and "2:' initially at temperatures 8 (- m) and 8(+ -), respectively, are brought into contact at time t =0. A common interface temperature 8,i = is instantaneously established, and thereafter remains constant. Temperature curves are drawn for three instants of time. When there is contact resistance between the two media, the temperature equalization occurs as sketched in Fig. 2(b). Fig. 2(c) illustrates a temperature curve, using the dimension-less notation Barber-Weiner-Boley6 have stated the equations [23a, b] given below, which govern the heat transfer in the two media, and solved them for a rather complicated special case. In their example both media "O" and "2" are finite, are insulated at their far ends, and there is steady heat input into medium 2. In Eq. [27] we give the general solution of the most important special case, where the two media are semi-infinite and there are no sources or sinks. In this case the results may be stated in simple closed form. In Fig. 3, to be discussed in the next section, we illustrate the variation of the interface temperature when steel at 2760" is brought into contact with iron at 100". This example, if we disregard the effect of the heat of fusion, is comparable to Pellini's experimental results, Fig. 1. (Unfortunately, however, experimental determination of the interface temperatures was difficult to carry out, and hence Fig. 1 is not very accurate near the interface.) In Figs. 4 and 5 of the following section, we similarly compare Pellini's sandcasting tests with analytical results for the case where steel at 2760" is brought into contact with sand at 100". It will be pointed out that, insofar as the interface temperatures are concerned, heat of fusion has a minor effect, and so the present approximation, with small modifications, may be

Jan 1, 1961

By S. Andrew Kulin, L. Kaufman

A general treatment of the broadening of X-ray double-crystal spectrometer rocking curves due to distributions of tilts and strains has been carried out. The results of this treatment have been applied to the case where dislocations in a crystal give rise to both tilts and strains. On this basis it is found that the rocking-curve halfwidth due to imperfections in the crystal, ßC , increases with increasing Bragg angle, 8. These considerations predict linear relationships between & and tan2 , and ßCand tan 8, for Gaussian and Cauchy distributions of dislocations, respectively. The zero intercept of the ßC us 8 curve, which is a measure of the degree of imperfection of the crystal, is found to depend directly on the distribution rather than the number of dislocations. In addition, the slope-intercept ratio for the ßc - ? curve has been calculated for both the Gaussian and Cauchy distributions. Experimental determination of the - 8 curves for a series of copper single crystals prepared by the Bridgeman and Czochralski methods yields results in agreement with the calculated slope-intercept ratio for a Cauchy distribution of dislocations. CERTAIN X-ray techniques have been used to study the perfection of single crystals. Gay, Hirsch, and Kelly have considered the spreading of spots into arcs on Debye-Sherrer rings due to imperfections. The Double-Crystal Spectrometer has also been applied to this problem.2 The characteristics of Double-Crystal Spectrometer Rocking Curves have been described in the literature by various workers.2-4 By assuming a random spacing of dislocations which give rise to a Gaussian distribution of misorientations relative to some mean orientation in a crystal Gay, et al.,1 arrive at the conclu- sion that the most probable misorientation is given by where h is the spacing between dislocations, and 8 and are the relative misorientations of neighboring regions. If ßC is the halfwidth of the rocking curve (the width at one-half the peak intensity) due to dislocations in the crystal then5

Jan 1, 1960