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By R. J. Blackwell, A. L. Pozzi

Scaled laboratory-model studies provide a powerful method for evaluation of a proposed oil-recovery process. In recent years, models have been used extensively to evaluate processes in which solvents displace oil, both for general cases and for specific reservoir conditions. Since the performance of a miscible flood in a horizontal reservoir can be significantly affected by transverse mixing between solvent and oil, this displacement mechanism must be accurately simulated in the scaled model studies. Unfortunately, precise scaling of transverse dispersion coupled with the requirement of geometric similarity requires impractically large laboratory models and long times for experiments. If scaling requirements for miscible displacements could be relaxed while accurate simulation of essential displacement mechanisms is maintained, the utility of model studies would be greatly enhanced. The purpose of the work reported herein was to evaluate the relative importance of various mechanisms affecting miscible displacement and to ascer tain whether the essential features of the displacement process can be simulated even though some scaling groups are not satisfied. These studies were performed with completely miscible systems in linear, horizontal models packed with unconsolidated media. From the experimental results, a set of relaxed scaling criteria was formulated which allows the requirements of geometric similarity and equality of the ratio of viscous to gravity forces to be omitted for specified conditions. The relaxed criteria are valid whether transverse mixing is by molecular diffusion or by convective dispersion. Correlations which permit prediction of vertical sweep efficiencies in linear, horizontal reservoirs were developed from the experimental data when transverse mixing is by molecular diffusion. These same correlations may be used when transverse mixing is by convective dispersion if an empirically defined, effective, transverse dispersion coefficient is used in the description of the mixing process. The effective transverse dispersion coefficient correlation essentially duplicates the dispersion coefficient correlation for equal-viscosity, equal-density fluid systems. Experimental values for the effective transverse dispersion coefficient can be measured readily. INTRODUCTION One of the most effective methods for evaluation of miscible-displacement oil-recovery processes is that of displacements in laboratory models scaled to simulate reservoir conditions. For these laboratory studies to be meaningful, however, the essential displacement mechanisms affecting reservoir performance must be accurately simulated. Since the performance of a miscible flood in horizontal reservoirs, or in dipping reservoirs at high rates, can be significantly affected by transverse mixing of solvent and oil, this mechanism must be considered in the design of laboratory experiments. Unfortunately, precise scaling of transverse dispersion coupled with the requirement of geometric similarity requires impractically large laboratory models and long experiment times. This difficulty seriously limits the utility of laboratory model studies. Craig,et al,1 demonstrated that geometric similarity is not required when mixing is unimportant. Their experimental data indicate, for the cases studied, that the displacement is sufficiently characterized by scaling the ratio of viscous-to-gravitational forces. This work suggests that relaxation of the requirement of geometric similarity and, possibly, other criteria might also be permissible when mixing is important, provided suitable groups describing the mixing process are scaled. The purpose of the work reported here was to evaluate the relative importance of various mechanisms affecting miscible displacement and to ascertain whether the essential features of the displacement process can be simulated even though some scaling groups are not satisfied. Consequently, laboratory investigations were made of the dependence of recovery on dispersion and other variables,

By James J. Bean

HE task of measuring the specific gravity of the -*- operating medium in a heavy-media separation system has never presented a particularly difficult problem because the medium is fairly stable and the overflow of the separatory vessel, as well as its underflow, can be sampled easily and accurately and the specific gravity of the suspension determined easily by weighing a known volume. However, while this method is simple and accurate it does require the operator to take the sample by hand and to weigh it and there is considerable temptation to avoid the periodic sampling if everything seems to be going well, or if something is occupying the attention of the operator. Furthermore all operators do not sample in exactly the same manner and considerable practice is required for two operators to be able to "check" each other to the last few hundredths, particularly if the sample is cut underneath the drainage screen where location of the point of sampling and load on the screens tends to influence the determination. While none of the above presents much of a problem, we have all recognized that some mechanical method of continuous measurement and recording would be advantageous since the operator would merely have to glance at the meter to check the gravity and to have an indication of the trend of any changes. Also if the instrument were of the recording type, a permanent record would be available for the guidance of the superintendent. The Eagle-Picher Mining and Smelting Co. was the first heavy-media user to actually install such a recording meter. In 1946 they installed in their Central Mill at Cardin, Okla., a specific gravity recorder manufactured by the Bristol Co. of Water-bury, Conn. R. A. Barnes, of the Bristol Co., working with E. H. Crabtree, Jr. and Elmer Isern, of Eagle-Picher, made the application and worked out the problems of sampling and measuring. Their attempts to measure the specific gravity of the medium in the cone itself were not entirely successful and they resorted to an outside sample tube for actually making the determination. Because of the particular flowsheet used, it was possible to tap off from the medium return pipeline a stream of medium and divert it into the sampling tube, which was provided with a constant level overflow and a spigot underflow, and into which the bubbler tubes dipped. The Eagle-Picher installation was successful and its possibilities were recognized by the Mineral Dressing Laboratory of the American Cyanamid Co. It was decided to install a similar unit in the heavy-media pilot plant to investigate further its possibilities. Chief among these was the continuous record which it was felt would be proof of the steadiness of the gravity in a heavy-media cone, something which is not always appreciated by POtential users. Because the heavy-media pilot plant is required to operate at a wide range of specific gravities, it was realized that the unit would have to record all gravities from 1.25 to 3.50, and do it to the nearest 0.01. It would not be necessary to record all of this wide range on a single chart and the method selected was to have 4 bands, each band range overlapping the other a small amount and calibrated so that with standard charts one division would represent 0.01 sp gr. A shift from one band to another could be arranged without alteration of the instrument itself, being accomplished by a simple change in the bubble-tube lengths, as described later. Accordingly, a recording type instrument was purchased and installed. Because there were some advantages in doing so, the first installation attempted to measure the gravity of the cone proper by placing the bubble tubes in the cone. This was not at all satisfactory and the second scheme utilized a fixed vertical screen at the surface of the cone, and an external sample-tube arrangement. We were particularly anxious to make this work as we felt it would be advantageous to measure the top level of medium where the separation was actually being made, but we were doomed to disappointment because it was impossible to keep the screen clean of float. Since the top gravity of the cone is the most convenient place to sample for control, a launder about 2 in. wide was installed longitudinally beneath the

Jan 1, 1951

By W. H. Emmons

Although gold is one of the rarer metals, it is widely distributed; it is found on all of the continents and in each of the grand metallogenic provinces of the earth. It is prominent particularly in the shield areas of the earth; these areas have produced a large part of the world's lode gold and in most of them gold lodes are more important than the lodes of other metals. The Scandinavian shield is the only one that has not produced much gold. Nearly all of the world's gold has been derived from lodes and from sands and gravels where gold placers formed by the destruction of lodes. The gold derived from magmatic segregations, from pegmatites and from contact metamorphic deposits is quite subordinate to that derived from auriferous lodes. The lodes include all veins and related deposits that are formed by hot waters that move along fissures or other openings and that deposit vein 'matter :in the fissures and by replacement of the country rocks along the fissures. All of the shield areas of the earth are characterized by large areas of granitic rocks including granitic gneisses, granodiorites and other acid intrusives which here are included in the general term "granite." The granites are intruded into schists, ancient lavas and other rocks which here are designated as the "invaded" rocks. The granites are parts of what once were great batholiths: that is, they are the remaining portions of great deep-seated bodies that slope outward, have very irregular roofs and so far as known have no floors but extend downward to great though unknown depths. Some of them are scores or hundreds of miles across and contain islands or "roof pendants" of the invaded rocks at places where the roofs of the batholiths were low—that is, where erosion has not yet completely unroofed the batholiths. It is in these islands of older rocks and in the narrow marginal belts and cupolas of the batholiths that practically all of the gold lode deposits of the shields are found. Valuable lodes are lacking generally in the granites themselves except in grahite within a mile or less from .the contacts with rocks of the islands (Fig. 1). It is probable that the great areas of granites and gneisses that surround the islands are not all of the same age, and that at places unmapped granite intrudes gneiss or older

Jan 1, 1932

By L. R. Duncan, O. M. Wicken

Magnesium, the eighth most abundant element in the earth's crust, is found widely distributed in a variety of minerals. Among the more commercially important ones are magnesite (MgCO,), brucite (Mg[OH],) , dolomite (CaMg[CO,],), and the salts magnesium sulfate and chloride often found in natural brines. Among other commercially important magnesium-containing minerals are olivine ([MgFe],- SiO,) , talc (H,Mg,[SiO,],) , and serpentine (H,Mg,Si,O,) . These are valuable because of desirable characteristics given them by the magnesium content and its placement in the particular crystal structure. These minerals are the raw materials for a host of products including magnesium metal and several grades of magnesia or magnesia- containing materials for refractories, fluxes, fillers, insulation, cements, decolorants, fertilizers, and chemicals. Considering only those minerals valued for their magnesia or magnesium content, over 85% of the material tonnages are processed to be used as refractories. Dolomite, which is used in enormous tonnages for its physical properties in construction, has an important use as a refractory raw material in its own right and, after calcination, as a precipitant for magnesium hydroxide, which is an intermediate for the production of magnesia or magnesium metal. Magnesia from the reaction of calcined dolomite (or limestone) with sea-water or magnesium-containing brines has supplanted much of the production of magnesia from mined magnesite, particularly in the United States. The best known of the minerals directly and widely exploited for magnesia content is magnesite, one of the calcite group of rhombo- hedral carbonates which includes calcite (Ca- CO,) , siderite (FeCO,) , and rhodocrosite (MnCO,) among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence, magnesite and siderite form a complete series of which breunnerite (ferroan magnesite) is a well-known end member. However, the radius of calcium ion is 36% larger than that of magnesium ion, and only limited substitution exists at each end of the MgC0,-Cam, series. Dolomite is not a member of the calcite group, but results when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of these relationships is that calcite and dolomite, often found intermixed with magnesite, occur commonly as identifiable crystal entities which can often be separated to a varying degree from the magnesite by various beneficiation techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO,. The pure mineral is sometimes, but rarely, found as transparent crystals resembling calcite, but, preponderantly, magnesite contains variable amounts of the carbonates, oxides, and silicates of iron, calcium, manganese, and aluminum. Magnesite may be either crystalline or "amorphous" (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black with shades of yellqw, blue, red, or gray. The color is not a fundamentally significant indicator of purity, but in a given deposit, an experienced person can often roughly grade magnesite by assessing color and crystallinity. The crystalline form of magnesite occurs in

Jan 1, 1975

By R. D. Vaughn

The analysis of laminar flow of power-law non-Newtonian fluids in narrow, eccentric annuli is employed in this paper to discuss the problems of lubricant flow in journa! bearings and of errors introduced by eccentricity in experimental studies with concentric annuli on extruders and wellbore annuli. The velocity profile and pressure loss-flow rate equations are developed for the laminar flow region. In addition, the expected error in flow rate and pressure-loss measurements for concentric annuli as a result of eccentricity is determined. For example, a 10 per cent displacement of the core of an almost concentric annul us would cause a 1.8 per cent decrease in the observed pressure loss for a fluid with a power-law exponent n of 0.25. The corresponding increase in the observed volumetric flow rate would be 7. 5 per cent. INTRODUCTION Non-Newtonianism and eccentricity occur simultaneously in two engineering problems: (1) flow of lubricants in journal-bearings and pressure-reducing bushings, and (2) flow of non-Newtonian fluids in plastic extruders and wellbore annuli. The lubricants used for moving parts are often non-Newtonian in character — often they are plastic in behavior. A solution to the problem of flow of non-Newtonian fluids in narrow eccentric annuli is particularly pertinent to this problem. In all experimental studies of laminar flow of fluids in concentric annuli, such as in extruders and well casings, the error due to eccentricity must be estimated or studied. A number of publicationsl-4,6,7 have dealt with this problem for Newtonian fluids; however, I am not aware of work for non-Newtonian fluids. This work is directed to the non-Newtonian problem. Before the solution to the problem is given, the pertinent conclusions from the work on Newtonian fluids will be reviewed. Heyda 1 and Redberger and Charles 2 have published general solutions to the problem of the laminar flow of Newtonian fluids in eccentric annuli, apparently without knowing of the earlier work of Ca ld well 3 and Bairstow and Berry,4 which is reported by Dryden, et al. 5 Although several mathematical routes are encompassed by the work of these authors, the results appear to be equivalent. Redberger and Charles2 show that the error caused by eccentricity in concentric annuli is negligible for small diameter ratios (k < 0.5); however, for large diameter ratios (k + l), the error in the predicted flow rate can be as great as 100 per cent or more. Partial solutions to the problem are available from the work of Dryden,5 Tao and Donovan6 and Piercy, et a1.7 Tao and Donovan examined the case of flow in narrow, eccentric annuli (k + 1) with and without rotation of the annular core. These authors also reviewed previous work on this subject and verified their approach with experimental data. Dryden gives the solution for the limiting case of complete eccentricity or tangency. Piercy, et a l. published an early solution to the problem of narrow eccentric annular flow. The conclusions of Redberger and Charles2 and the experimental proof of Tao and Donovan6 both suggest that the region of large diameter ratios (k + 1) is of main interest and that the parallel planes approximation to the solution in this region is satisfactory. This method will now be extended to the laminar flow of non-Newtonian fluids in narrow eccentric annuli. THEORETICAL SOLUTION The geometrical aspects of the problem are illustrated in Fig. 1. To represent the non-Newtonian fluid the power-law model was selected. This model has many disadvantages which have been pointed out; nevertheless, its simplicity, its frequent and wide applicability justify its use in this work. Fredrickson and Bird8 and Savins9 have used it as a basis for a theoretical study of laminar flow of non-Newtonian fluids in concentric annuli.

Jan 1, 1966

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell&apos; It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully&apos;s theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955

By N. H. Fisher

Geographical Distribution &apos;he most important known deposits in Australia of what are commonly referred to as the beach-sand minerals are along the most easterly part of the Australian coast, between Southport, 17 miles north of the Queensland-New South Wales border, and Ballina, 50 miles south of the border, and most of the production has come from this area (Fig I). Smaller deposits are known to occur farther to the south at intervals for several hundred miles, and beaches have been worked at Yamba, 96 miles south and Woolgoolga, 150 miles south of the border and at Swansea, 60 miles north of Sydney. Important deposits have been shown to exist on north Stradbroke Island and others have been located farther to the north, as far as Tin Can Bay at the south end of Frazer Island. (Fig 2). Table I gives the list of operators with the location of their deposits and workings, their approximate maximum monthly capacity expressed in tons of heavy mineral produced by their concentrating plants before separation into individual mineral concentrates, their methods of mining and concentrating the minerals, and the products obtained. This table applies as of June 1948, but all the operators are remodeling or improving their plants and plant practices will be modified accordingly. In addition, active boring campaigns have been carried out by Alluvial Gold, Ltd., of Sydney, in the Cudgen-Cudgera area, and by Zinc Corporation Ltd., of Melbourne, on Stradbroke Island, and in other places. Physiography Submergence of the order of 100 to 200 ft at the close of the Pleistocene period left the pre-existing hills as promontories and the valleys as deep inlets. Wave action has built bay-bars and sandspits in a northerly direction from the headlands, and lakes and marshes have formed between these bars and the initial post-submergence coast line. These lakes and swamps have been or are being filled in by river-borne sediments or wind-blown sand. Beasley1 has presented evidence that suggests a recent emergence of the coast line of about 10 ft. The evidence for this belief is the presence of a black sand seam 1/3 mile inland and 17 ft above sea level (Fig 3), and although it is not entirely certain that this seam is of beach formation and owes nothing to windblown concentration, other evidence supports the suggestion of recent emergence. Such emergence would undoubtedly aid the formation of bars and sandspits and the easterly progress of the beach front, leaving a series of parallel dunes (Fig 4). This belt of north-south coastal dunes ranges up to 56 mile in width and as many as 15 lines of dune have been counted (Fig 3). The foredune is generally the highest, upto 25 ft high, and there is in many places a flat platform in front of the dune known as the berm. The dunes behind the foredune are lower and less well defined

Jan 1, 1949

By J. Hunter

DuXing 1942, Louisiana attained the rank of fourth among the great oil-producing states of this country. Its present prominent position is the result of an orderly and systematic program of exploitation with emphasis on conservation. Even before the functioning of M-68, the Federal spacing order, development and production in Louisiana were regulated by various acts of legislation, the most recent of which and by far the most effective is Act 157 of 1940. Under the authority of this act, it has been possible for the Department of Conservation to hold many public hearings and thereby to secure data and evidence regarding the feasibility of issuing rules and regulations for development of various oil and gas fields in the state. As a result of information compiled at such public hearings, many orders have been issued by the Commissioner of Conservation that have in most cases provided reasonable solutions to the problems that arise in the exploitation and development of fields in this state. Probably one of the most effective powers granted the Commissioner of Conservation in the state of Louisiana has been the authority to provide for fieldwide unitiza-tion and pooling of condensate fields. This has led to the erection of huge cycling plants in Louisiana, which permit the most efficient recovery of the liquid content of the reservoirs, and further conserve most of the gas reserve that undoubtedly will be of considerable future value. Many months have passed since various orders of the Department of Conservation were put into effect, and all are accomplishing their purpose; namely, the elimination of waste. Although the effectiveness of these orders provides considerable satisfaction to the members of the Department of Conservation, it is also a tribute to the members of the oil and gas industry in Louisiana, who, in addition to providing carefully prepared technical data, have also given unstinting cooperation and have thereby enabled the Department to cope intelligently with the many problems. Production On Dec. 31, 1942, oil and/or gas was being produced in 50 parishes, or 78 per cent of all the parishes in the state. Thirty-three of the parishes produced oil and gas, 12 produced oil, and 5 produced solely gas. This is indeed an enviable record for any state. However, it is reasonable to assume that eventually all parishes in the state of Louisiana will be productive. From a geological viewpoint, there is no apparent reason to assume otherwise—a point that a11 operators seeking oil and gas production in this state may well bear in mind. Twenty new fields were found during 1942—a rate of discovery that does not compare favorably with the 30 new fields found during 1941. The record of discoveries in Louisiana during 1942 is further disappointing when it is realized that 8 of the 20 new fields discovered were gas fields. During this period of war emergency, there are, of course, many

Jan 1, 1943

By Martin Weinstein

A technique is described for preparing finegrained lead telluride by ultrasonic agitation of a solidifying melt. Material prepared by this technique is dense and chemically homogeneous. N-type PbTe, containing 0.03 mole pct PbIz, has been made and its thermoelecCric Properties have been measured as a function of temperature. For comparison, the properties of similarly doped PbTe made by cold pressing and sintering, and by extrusion, have also been measured. The ultrasonically prepared material compares favorably with the others in its thermoelectric-efficiency factor. Comparison of compressive-flow curves for the three kinds of PbTe show that the ulhasonically prepared material has much superior ductility. The cleavage strength of the ultrasonic material is related to the grain size, D, by the Petch relation:Extrapolation to infinite grain diameter yields a fracture strength of 5000 psi for single-crystal PbTe. WHEN metals and semiconductors solidify in a mold they normally assume one of three cast structures illustrated in Fig. 1.&apos; Solidification in a casting starts at the mold walls where a large number of fine crystals of random orientation can be nucleated to form the chill zone. Because of the anisot-ropy of the growth rate, those crystals whose direction of maximum linear growth is parallel to that of the heat flow grow faster and crowd out the crystals of less favorable orientation. A second zone, having a preferred orientation, called the columnar zone, thus forms adjacent to the chill zone. The speed of growth of the columnar grains will depend, in the case of limited undercooling of the melt, on the rate at which heat can be abstracted. The columnar zone can extend to the center of the casting, Fig. l(a), but it is frequently followed, in solid-solution alloys, by another zone of equiaxed randomly oriented grains in the central portion of the casting, Fig. l(b). The equiaxed structure in Fig. l(c) represents the completely grain-refined case where the equiaxed grain size is small. The third type of structure is the most desirable because it imparts a somewhat higher strength for all except high-temperature applications, it reduces segregation of the doping constituent, and it reduces the possibility of hot tearing (the separation of grains due to the melting of a low-melting point constituent in the grain boundaries). In order to obtain fine-grained castings, the nu-cleation frequency must be increased and grain growth must be restricted. Various techniques have been employed for obtaining this end, namely: rapid cooling, vibration, and inoculation of the melt. The success of these techniques depends upon the characteristics of the metal species and on factors controlled by heat transfer through the crucible walls. Recent studies2" have shown that the application of ultrasonic energy to the solidifying ingot is an extremely powerful tool in the improvement of the crystalline structure of metallic castings. Both the mechanical properties and homogeneity of the ingots are improved. Ultrasonic oscillations may affect the crystallization process by 1) permitting subcritical nuclei to agglomerate and thus form nuclei of sufficient size to cause crystallization, 2) changing the state of surface adsorption of various catalysts found in the liquid melt, 3) breaking pieces of solid from the solidified surface near the supercooled region thereby increasing the number of possible nuclei, 4) causing temperature fluctuations to occur in certain parts of the melt thereby increasing the supercooling at specific points in the liquid, and 5) decreasing the critical nucleus size by increasing the pressure at specific points in the melt.&apos; Various investigators have concluded that the effectiveness of the ultrasonic oscillations results from cavitation which disrupts the growing solid-liquid interface The present paper describes the application of ultrasonic oscillations to the crystallization of the semiconductor N-type PbTe. The purpose of this study is to prepare crystalline

Jan 1, 1964

By T. B. Massalski, C. S. Barett

THAT metals and alloys of the body-centered-cubic structure tend to become unstable at low temperatures is so nearly universal that any exceptions are worthy of special attention. Studies of the exceptions may disclose unrecognized examples of metastability or may shed light on the nature of some of the factors that stabilize the body-centered-cubic phase. Among the structurally analogous body-centered-cubic 3/2 electron compounds, the ß-phase in the Cu-Zn system deserves further attention for, although this phase is known to undergo partial mar-tensitic transformation on cooling below room temperature to the temperature of liquid nitrogen when the composition is less than about 42 wt pct Zn, it does not transform on cooling .when there is more than this amount of zinc present.1-4 The present authors recently found that an alloy containing 48.35 wt pct Zn could be transformed, however, if deformed severely at room temperature or lower temperatures.V his discovery led to the suggestion that the jerky flow of ß-brass single crystals6 and some of the unusual temperature variations of the yield strength and hardness are due to strain-induced transformation during the tensile tests. The present investigation is an extension of that work to cover the entire available range of compositions of Cu-Zn ß-phase alloys and certain interesting compositions of the ß-phase in the Cu-Zn-Ga system. Particular attention is given to the structure of the transformation product resulting from cold work, which is found to vary with alloy composition, and to the temperature range in which transformation can be induced in the various alloys. The composition limits of the body-centered-cubic phase in the Cu-Zn system, based on a recent review by Raynor7 and the precision determinations of Beck and Smith: are shown in Fig. la; in the ß region the alloys are disordered and in the ß region they are ordered. The rate of ordering is so rapid that a high degree of order is found in any of these alloys immediately after quenching. Experimental The nine binary and four ternary alloys of this investigation were prepared from cathode copper (99.99 pct purity), electrolytic zinc (99.99+ pct), and gallium (99.98+ pct). All alloys were cast in transparent Vycor tubing, homogenized at temperatures between 800° and 890°C, and quenched in water. Ternary alloys were cast in small amounts (-5 g) to predetermined compositions to fall along a line of constant electron concentration in the ternary system. Changes of weight during the casting operation of the ternary alloys were not greater than 1 part in 2500 from the intended nominal weights and therefore their compositions were accepted without chemical analyses. All binary alloys were cast in larger amounts (100 to 150 g), homogenized, and hot rolled after preheating to 800°C. The central portion of the rolled strip of each alloy was annealed for eight days and quenched in brine. All binary alloys were analyzed chemically. The compositions, heat treatments, and metallographic appearances of all alloys are tabulated in Table I. Various samples were subjected to heat treatment or cold work at several temperatures and were then examined metallographically or by means of X-rays. Specimens about 6x6x3 mm in size were examined metallographic ally to confirm the presence of the ß-phase after quenching. Cold work was introduced by fastening each sample between two pieces of steel, cooling the assembly to the desired temperature, and transfering it rapidly to a vise where moderate or severe compression was immediately applied. Cold working at liquid helium temperature was done by a chisel-shaped tool mounted on an X-ray spectrometer, described elsewhere.% A!! metal-

Jan 1, 1958

By H. A. Wriedt

A method of calculating activities in binary systems having miscibility gaps is described. The method, which applies only to the phase in which the gap occurs, is exact when the function defined by the equation varies linearly with composition. Analytical and numerical solutions (as a function of the conjugate phase compositions) are presented for two coefficients A and B from which the thermodynamic activities can be calculated. Deviations from Henry&apos;s law, calculable by the method presented, are shown graphically for the particula~ case of the component i at the edge of the miscibility gap more remote .from pure component i. For symmetrical gaps, the deviation from Henry&apos;s law at this gap edge becomes smaller as the gap becomes wider, The interrelation of gap location, the direction of departures from Henry&apos;s law and the occurrence of maxima and minzma in these departures is discussed in some detail. Values for a and for activity calculated from phase diagrams show fair to excellent agreement with corresponding experimental values in the Al-Zn and CaO-SiO2 systems. WHEN structurally similar phases, B and 6, lie at the sides of a two-phase region in a constitution diagram, it can be assumed that, stably or metast-ably, they will become completely miscible at a higher temperature. The B and 6 phases are particular composition ranges of a single B6 phase region with a miscibility gap. Below, as above, the critical solution temperature, the free energy of formation of the 06 phase is a continuous function of composition through the range of the miscibility gap. It is the purpose of this paper to use this continuous free-energy function in order to develop a simple method for computing the thermodynamic activities in the B6 solution of a binary system. To make these calculations it is assumed that the function ai, familiar from Gibbs-Duhem integrations and defined by the equation

Jan 1, 1962

By R. L. Slobod, B. H. Caudle, E. R. Brownscombe

An earlier publication has discussed three methods lor obtaining relative permeability data on small core sample-: and the apparatus and technique for the capillary pressure displacement method. This paper describes the apparatus and technique for the solution gas and the dynamic displacement methods and presents a routine procedure for obtaining oil-gas and water-oil relative permeability data. Theoretical and experimental considerations are presented to show that the end effect commonly associated with the dynamic flow mechanism is extremely small where constant rates are employed in the flowing phase. An effect of flow rate on relative permeabilities obtained by the dynamic system is found only when gas is one of the flowing phases and this effect is ascribed to a form of channeling in the capillary system. The apparatus and procedure* used to obtain relative permeability data with three phases flowing are described and some preliminary results of the use of this method are shown. INTRODUCTION In a previous publication from this laboratory there appeared a brief discussion of the concepts behind three basic methods for obtaining relative permeability data.&apos; These three methods were called the capillary pressure displacement method. the solution gas displacement method, and the dy. namic displacement method — the names being suggestive of the type of process used for obtaining the desired saturation prior to making the permeability measurements. In the same publication, the apparatus and technique for the capillary pressure displacement method were described and some typical results obtained by this method were presented. This paper will present: 1. The routine procedure used to obtain complete relative permeabilitv data (In small core samples with two phasec flowing; 2. The experimental techniques for the solution gas and dynamic displacement methods for obtaining relative permeability data; 3. The results of some studies on the mechanism of fluid flow through consolidated porous media; and, 4. The preliminary results on the determination of relative permeability for a system in which three phases are flowing. TECHNIQUE AND APPARATUS FOR THE DETERMINATION OF RELATIVE PERMEABILITY WITH TWO PHASES FLOWING In order to obtain relative permeability data on a small core sample which will describe the various phases of reservoir depletion. it is necessary that the methods used duplicate, as closely as possible, the various mechanisms involved in rescbrvoir depletion. It is important that. in any type of relative permedbility determination. the core be originally at virgin reservoir conditions with respect to the fluids within the pore *paces. (for example. oil used to displace water from core until connate water saturation estahlished). and that the subsequent saturation changes in the core be analagous to tile reservoir depletion mechanism for which the data are to he used. PROCEDURE OF DETERMINING RELATIVE PERMEABILITY DATA WITH TWO PHASES FLOWING A standardized procedure has been set up for obtaining relative permeability data and other information on small core samples. This procedure essentially consists of 11 steps as shown below: 1. Determination of tile capillary pressure curve.&apos;! This information is used to help select samples for relative permeability determinations and to charactrrize. in general. the pore size distribution of the sample. 2. Determination of the specific permeabilities to air, oil. and water. These values are those on which the relative pern~eahility calculations are based. 3. Reduction of the core to connate water by an oil drive using the high speed centrifuge. 1. Determination of the critical gas saturation value and the associated relative permeability to oil by the solution gas drive method. 5. Determination of the relative permeabilities to oil and gab in the region where both phases are flowing by the capillary presqure method. 6. Reduction of the sample to residual oil in the centrifuge by an air drive. and the determination of the relative permeability to gas at this point.

Jan 1, 1951

By R. A. Morse, C. R. Stewart, F. F. Craig

This paper preFents the results of a series of model flow test on a number of large limestone cores, having different pore configurations. For limestone cores having substantially sandstone type porosity, the production characteristics for solution and external gas drives are similar. For cores whose pore spaces were microscopically heterogeneous (i.e., consisted of combinations of solution cavities, matrix. and fissures), the production characteristics lor solution and external gas drives vary widely. The degree of divergence between gas-oil relative permeability relationships calculated from solution or external gas drive tests is an indication of heterogeneity of rock pore structure. The results of water floods on cores depleted by solution gas drive for each of these two general types of limestone porosity are also shown. Generalizations are made on the water flood recovery that could be expected from each of these two types of limestone porosity. The similarity between solution drive field performance and model solution drive performance on cores from the same formation is shown for several cases. This indicate? the feasibility of predetermining limestone field performance from such large core tests. Photomicrographs of plastic-impregnated rock thin sections of the samples tested are presented as an aid in understanding the flow test performances. INTRODUCTION During the past 15 years. reservoir engineers and research workers have developed methods of testing rock and fluid samples and applying the results, through calculation, to allow reasonably satisfactory predictions of oil recoveries and performances to be expected in sandstone oil recervoirs. It has been determined that representative fluid flow data can be obtained on rock samples as small as three-fourths in. in diameter by one in. long in most sandstones. However, little has been accomplished toward the laboratory determination of fluid flow characteristics in limestones. There has been a great deal of speculation as to the influence of variations in pore size, shape, and degree of interconnection upon oil recovery processes, and a great deal of thought has been given to the interpretation of limestone field perfomance. It has been generally recognized that predictions of reservoir performance based on oil displacement tests on small limestone core samples the size of those used for sandstone tests can often be misleading because of the improbability of obtaining a representative sample in such a small core. Obviously, if there are present in the rock, pore openings of the magnitude of 1/16 in., or fractures or solution channels up to one in. or more in length, it will be impossible to cut any sample less than one in. in any dimension which would represent the flow geometry of the gross rock system. In some formations, the individual openings in the rock are of such size that it would be impossible to obtain a good sample of the flow system even in the total core available from conventional-sized well cores. However, by increasing to the maximum the size of the sample used, it should be possible to obtain representative flow data from the majority of limestone reservoir materials which can be used for prediction of future primary production performance or response to be expected from secondary recovery measures. The only alternatives to obtaining good laboratory test data to serve these purposes are extrapolation of primary performance data obtained by partial depletion of a field, or obtaining information from pilot tests. It has been shown previously, and will be demonstrated further by the work reported in this paper, that extrapolation of solution gas drive performance for an estimate of gas injection response can be very misleading in reservoirs of heterogeneous type porosity. Although it cannot be expected that laboratory information can ever eliminate the necessity of small-scale pilot operations, it is expected, as is now the situation with sandstone reservoirs, that laboratory tests should provide reliable information for screening of

Jan 1, 1953

By Tomek Ulatowski

This presentation discusses the necessary ingredients for the creation of an acceptable credit structure, i.e., the structure that enables the borrower to attract the funding from different groups of lenders. As the amount of debt in the capitalization of new projects increases, it becomes quite critical that the mining venture sponsors obtain funding in a manner which maximizes the project economics. Attention normally is focused on the inherent operating cost characteristics of a venture such as the cost of mining, milling, transportation, smelting, and refining. The projected costs are derived from lengthy feasibility studies often taking millions of dollars and years to prepare. For a variety of reasons as the amount of equity directly provided by the sponsors declines, the balance must be made up from external credit sources. As a result, once the project becomes operational, debt service requirements assume crucial importance. For most new ventures, in the early years of production, the total amount of periodic debt amortization charges together with the projected interest expenses equals or exceeds the total operating cost. Utmost care must be taken, therefore, to reducing these costs which will then increase the chances for the implementation of the project. Project sponsors must carefully evaluate different funding sources in terms of their potential economic impact and, concurrently, evaluate alternative credit structures in order to be able to attract the selected funding vehicles. In this presentation I will discuss credit sources in the order of their relative appeal; i.e., from the standpoint of maximizing rates of return to the project owners. The tenor of the credit, that is the period from signing a loan agreement to the time of last repayment under the loan agreement, is undoubtedly the most important variable in evaluating the attractiveness of debt sources. Therefore, I will begin by discussing debt sources with the longest maturities and will end with a description of credits with relatively shorter tenors. The availability of different funding possibilities will naturally depend on the geographic location of the proposed venture, the creditworthiness of the borrower and the sponsors, the project economics, and finally the actual liquidity conditions in the capital markets at the time that the funds are committed. U.S. LONG-TERM DEBT MARKET - PUBLIC OFFERINGS AND PRIVATE PLACEMENTS The long-lived nature of most mining projects dictates that the majority of the mine financing be raised from long-term sources. In today&apos;s world capital markets U.S. debt issues probably carry the longest maturities available. The maturities can range from 5 to 40 years. Various types of long-term corporate debt instruments can be differentiated from one another by their terms, seniority as to claims against the assets of the issuer, legal form, and whether issued privately or through a public offering. The terms of these debt issues vary widely. For example, the interest rate which is typically fixed at the time of issuance, is determined by the credit quality of the issuer, the maturity, the average life, the seniority of the debt, the quality of control covenants or type of assets pledged as security, and other exogenous factors such as: economic policy, general level of interest rates and cur-rent level of financing activity. The entire principal amount of the debt may be due and payable at maturity (known as a "bullet" maturity) or, more typically, through periodic repayments in equal or staggered amounts. Almost all such debt issues allow for prepayment at the option of the issuer, but require varying amounts of repayment penalties. Disbursements are made over a relatively short period after signing of the debt documentation which may not coincide with the actual funding needs of the project. Financial covenants can be quite stringent, covering areas such as the issuer&apos;s financial leverage, working capital, payment of dividends and other distributions, merger and acquisition activities, and limitations on the disposition of property. Long-term debt issues may also be distinguished by the seniority of their claims against

Jan 1, 1985

By R. D. Satterley

The Sherwood mine is an iron-ore mine owned and operated by the Inland Steel CO. in the Iron River district of the Menominee Range in Michigan. The property consists of an 80-acre tract in the village of Mineral Hills, about a mile north of the city of Iron River. The Ore mined is a reddish brown, nonbessemer hematite and limonite. The ore bodies lie in a large syncline having an east-west strike and are associated with a rock structure that is folded in a complex manner. The two 40-acre tracts run north and south and the shaft is at about the center of the north forty. The shaft is 1286 ft. deep, with the principal operating level at a depth of 1000 ft. from surface. A new level at a depth of 1200 ft. is in process of development. The ore body at the 1000 ft. level is east and west at approximately the line between the north and south forties and at this elevation is from 50 to 250 ft. wide and extends above the level at varying heights of from 50 to 250 feet. The 1000-ft. haulage drift extends south from the shaft, through the east-west ore body to the slates on the south side of the body. The ore body was intercepted in the drifting at about goo ft. from the shaft and was about 200 ft. wide at that point. A crosscut was extended to the east and west property lines along the south boundary of the ore body. This east-west ore body is laid out in areas go ft. wide for stoping with pillars 40 ft. wide. With this plan a stope is approximately 80 by 200 ft. and has a pillar on both sides that is approximately 40 by 200 ft. The ore has a height of from 50 to 250 ft. above the elevation of the level, therefore the height of the stopes varies in accordance with the height of the ore body at each location. From the crosscut, two main raises, each 6 by 7 ft., are put up into each 80 ft. stope area (Fig. 1). One of the main raises serves as a manway and the other as an ore raise, through which the ore is transferred from the stope to the tramming equipment. The original layout as for scraping of the ore from under the stopes into the ore raises. The ore raise is put halfway (east and west) along the 80-ft. stope area and usually is in iron formation. The manway and ore raise are on approximately 15-ft. centers. These main raises are Put up to a height of from 22 to 30 ft. above the level floor, then from the toll of the ore raise a scraper drift (8 X 8 ft.) is driven across the width of the ore body, which is in the neighborhood of 200 ft. From the scraper drift, mill raises are put up at 12½-ft. centers, staggered on opposite sides of the drift, and these are extended 23 ft. above the elevation of the scraper-drift floor. The sublevel connecting the top of these mill raises is called a mill "sub." Other sublevels are developed parallel to the scraper and mill subs at 25-ft. vertical intervals above the mill sub. The mill sub and the other subs above the mill sub are known as sublevels or dog drifts, and are 4 ft. wide and 6 ft. high. These dog drifts

Jan 1, 1946

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure&apos; which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies&apos; have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969

By J. H. Scaff, W. G. Pfann

The effects of impurities on the electrical properties of silicon are discussed in a companion paper by Messrs. Scaff, Theuerer, and Schumacher.&apos; It was shown that an ingot of silicon which contained boron and phosphorus in certain concentrations consisted partly of p-silicon and partly of n-silicon2 and that the common boundary between these regions was the source of a photo-voltage. These features were ascribed to the segregation of boron and phosphorus during solidification of the ingot. Because of different rates of segregation the first portion of the ingot to freeze contained a molar excess of boron over phosphorus and hence was p-silicon. The last-solidified region contained a molar excess of phosphorus and was n-silicon. This paper is concerned with the microscopic examination of such ingots. The microstructures are rather unusual in certain respects and their study has helped to show how the segregation of minor elements modifies the electrical properties of silicon. The microstructures of ingots prepared from two lots of silicon, designated 1 and 2, will be described. These lots were obtained from the Electro Metallurgical Co. Both contain 99.8+ pct silicon, but they differ in impurity analysis. For each lot will be shown the microstruc-ture of a slowly cooled ingot, for which the time of solidification is 6 min., and that of a rapidly cooled ingot, for which the time of solidification is 2 min. The ingots were prepared from 45 g charges of silicon. When an alloy freezes a cored structure is generally produced because of insufficient diffusion to remove concentration differences established during freezing. As a result of coring the first portion of a crystal to freeze is usually poorer in solute than equilibrium requires, while the last material to solidify is richer. In a columnar grain, growth is principally unidirectional and coring can produce a concentration gradient along the entire grain. By carrying the picture of the coring process from a single grain to an entire ingot in which columnar grains are aligned more or less radially, one can easily see that a composition gradient could be established between the outside and center of the ingot. This, to a considerable extent, occurs during the solidification of a slowly cooled ingot of silicon. Slowly Cooled Ingot In slowly cooled ingots of both lots of silicon, columnar grains which are approximately radial in direction and longest at the top of the ingot enclose a region in which the shapes and align- ment of the grains are considerably less regular. The central region is last to solidify and contains cavities and inclusions. The sketch of Fig 1 illustrates some of these features, as well as others which will be described below. If a polished section of an ingot is etched in a mixture of 2 parts of 20 pct HF and 98 parts of HNO3 the p-n barrier becomes visible. The overall shape of the barrier in a slowly-cooled ingot is roughly oval, as may be seen in Fig 1. The proportion of n-silicon, that is, the region enclosed by the barrier, is considerably greater in ingots of lot 1 than in those of lot 2. A sample about 34 x 1/8 X 1/8 in. was cut from a slowly cooled ingot of lot 1 with its long direction extending from the top of the ingot to the porous region. Thus its upper half was psilicon, its lower half n-silicon. A longitudinal face was polished and etched in the acid mixture. The areas of interest are identified in Fig 2. A band of parallel markings extends across the sample in the columnar region. These striae are roughly parallel to the upper surface of the ingot and cross grain boundaries with only slight deviations. They are quite distinct in the n-silicon,

Jan 1, 1950

By W. O. Philbrook, K. M. Goldman, G. Derge

THIS is the third in a series of papers from the Metals Research Laboratory dealing with the transfer of sulphur across the iron-slag interface in a carbon-saturated system. The first paper&apos; showed that the transfer obeyed first-order kinetics. The second&apos; presented detailed evidence in support of the three-stage mechanism: FeS(Fe) FeS(slag) FeS(slag) + CaO(sing) ? CaS(slag) + FeO(slag) FeO(slag) + C ? Fe + CO. This emphasized the role of an iron-sulphur complex as the transfer agent across the interface and as an essential intermediate in the overall process. The present paper shows the influence on the process of the individual elements, carbon, silicon, manganese, and phosphorus, the alloying elements normally present and of interest in commercial blast furnace operations, aluminum, which has a pronounced accelerating influence, and nickel and copper, which are common minor impurities in the raw materials. The experimental methods and procedures for interpretation of data are the same as described earlier.1,2 Induction heated, graphite crucibles were used, and sulphur-free slag was added to the molten iron containing sulphur and the selected alloy. Slag samples were taken at regular time intervals and analyzed for sulphur and other components of interest. The authors wish to state specifically that these experiments were not intended to simulate industrial blast furnace operations. However, they do represent a study of the kinetics and mechanism of sulphur transfer at the slag-metal interface under specified laboratory control of the major variables in the system. It is believed that the results can be usefully applied to the blast furnace if consideration is given to the differences which are known to exist between the two conditions. A rigorous evaluation of the accuracy of rate studies is difficult. Recognized sources of error include sampling and analysis of both slag and metal, temperature measurement and control, selection of zero time, composition of the gaseous atmosphere over the reaction system, and extraneous sources of sulphur from the graphite crucible and reagent materials. In this study carefully standardized procedures were followed consistently in order to minimize the errors. It is believed that the reproducibil-ity of duplicate runs indicates that errors have been rendered negligible relative to the observed effects from intentional variables. For example, original experimental points for duplicate runs are shown in Figs. 1, 2, 7, etc. In most cases in this paper the drawn curves represent an average of at least two heats. The spread in sulphur values at a given time ranges from 0.02 to 0.08 pct, which is a small frac-tioi of the total values ranging up to 2 pct S in slag. In the systematic study of the influence of alloy additions, each element was added over a range of concentrations. The two slags used in this study were designated as "acid" or 1530 and "basic" or 1545. They had the nominal compositions given in Table I. Rates were measured in the temperature range 1500" to 1650°C. Data will now be presented to illustrate the various features of the study. Silicon The first alloying element examined was silicon, because its presence is unavoidable in any silicate slag system through the reaction y/2SiO2(slag) + xM?y/2Si(liq.Fe) + MxOy where M is any reducing agent such as iron or carbon. It is known that the attainment of equilibrium by this reaction is extremely slow and probably not reached in the blast furnace." The influence of silicon on the final stages of the sulphur reaction has also been studied.&apos; It has been shown5 hat silicon increases the activity of sulphur in iron. For such reasons silicon may also be expected to influence the kinetics of the reaction. The observed effects will now be described. The general procedure was to melt 530 grams of ingot iron in a graphite crucible, 3 in. OD, 2 1/4 in.

Jan 1, 1955

By R. Stickler, A. Vinckier

An optical and electron microscope study was made on a commercial 302 stainless steel heat treated for massive carbide precipitation. Convincirg evidence was obtained that the grain boundary precipitate does not grow away from the grain boundary into the matrix, but grows as a network of large thin dendrites in between the grains. IN austenitic stainless steels the carbon in supersaturated solution precipitates when the steel is heated in the temperature range 450" to 1000°C. During such heat treatments the chromium-rich carbide occurs primarily at the grain boundaries and has adverse effects on the corrosion resistance and low-temperature ductility of the material. It has been shown that the morphology of the precipitated particles differs widely depending on the time and temperature of the heat treatment, the nature of the boundary, the misfit between the grains, and so forth.1"5 It was assumed by Mahla et al.,&apos; Streicher,&apos; and Mc Nutt&apos; that the carbide particles which nucleate in the grain boundary grow in various geometric or dendritic forms away from the boundary into the matrix. However, Kinzel,&apos; Hatwell et a, and Plateau et aL4 found that the particles nucleate in the grain boundary and grow as a network of thin dendrites in the grain boundary interface. We have made a comprehensive studyg of the precipitation occurring in a commercial 302 austenitic stainless steel heat treated for times ranging from 0.15 to 1500 hr at various temperatures from 480" to 1065"~. This study was made to elucidate the influence of heat treatments on both the mechanical and the corrosion properties of this steel. Part of this investigation which is pertinent to the morphology of the grain boundary carbides referred to above is separately reported here. We found that the particles which nucleated in the boundaries grew in the interface of these boundaries, thus supporting the viewpoints of Kinzel,&apos; Hatwell et al.,3 and Plateau et al.4 Furthermore, when carbide particles nucleated in the matrix very close to the boundaries, they possessed a morphology distinctively different from the particles growing in the grain boundaries. MATERIAL A study of metallographic samples and of fracture surfaces of a 302 stainless steel is reported in this paper. The composition and heat treatments are listed in Table I. Polished and etched samples were examined und813r the optical microscope, and carbon extraction replicas of etched micrographic samples and various fracture surfaces3&apos;8&apos;9 were examined under the electron microscope. RESULTS AND DISCUSSION A representative optical micrograph of the 302 steel, condition A, is shown in Fig. l(a). Particles can be seen on the grain boundaries but no traces can be found of particles which grow from the grain boundaries into the matrix. A carbon extraction replica of this sample shows numerous large thin dendrites, Fig. l(b). The lateral dimension of such carbide particles vary up to 100 p, and their thickness estimated from the amoun! of electron penetration i:; between 500 and 1000A. Such large dendrites are extracted from almost all grain boundaries and, if they had grown into the grains, they would definitely be revealed by etching traces in the matrix, Fig. l(a). The reason why these large dendrites on the extraction replica appear to be grown into the grain is due to the mechanism of the extraction replica process. Thus, these dendrites are supported by the carbon replica film only at the edges originally along the grain boundary trace A-A, Fig. l(b), in the polished metal section and have subsequently fallen over onto the carbon replica film during handling. Although such dendrites generally fall only to one particular side of the grain boundary trace, one finds occasionally that parts of a dendrite have fallen to both sides, as shown in Fig. l(b). Further evidence for the growth of carbide in the grain boundary can be obtained from the appearance of fracture surfaces. A small impact specimen of the 302 steel, condition A, was broken at liquid nitrogen temperature. The fracture path follows the

Jan 1, 1962

By L. C. Chang, T. A. Read

Diffusionless transformation in Au-Cd single crystals containing about 50 atomic pet Cd was investigated by means of X-ray analysis of the orientation relationships, electrical resistivity measurements, and motion picture studies of the movement of boundaries between the new and old phases during transformation. The nucleation of diffusionless transformation by imperfections and the generation of imperfections by diffusionless transformation were discussed. THAT connections exist between plastic deformation and diffusionless phase changes has long been recognized. Thus it is often possible to produce a diffusionless phase change in a temperature range, above that in which the change occurs spontaneously, by cold-working the initial phase. Certain aspects of the dislocation theory of the plastic deformation of crystalline solids also provide for a rather direct connection between the processes involved in plastic deformation and in diffusionless phase changes. Heidenreich and Shockleyl have pointed out that simple edge dislocations in f.c.c. metals are probably unstable, and that the more probable lattice imperfections, called extended edge dislocations, consist of two half dislocations separated by a distance of the order of magnitude of 100A. The region about two atomic planes thick between the half dislocations because of this stacking fault may be described as having the hexagonal close-packed structure. Presumably the stacking faults observed by Barrett" fter cold-working f.c.c. Cu-Si alloys resulted from the passage of such half dislocations through the lattice of the initial phase. It is now becoming clear that the development of a detailed theory of the atomic movements involved in diffusionless phase changes will require a consideration of the role played by lattice imperfections, just as such considerations are necessary to the understanding of plastic deformation mechanisms. This point of view has been recently set forth, for example, by Cohen, Machlin, and Paranjpe3 who pointed out the role which might be played by screw dislocations in nucleating diffusionless phase changes. The present paper reports on some aspects of the diffusionless phase change in single crystals of the beta phase alloy Au-Cd which serve to emphasize further the importance of lattice imperfections in diffusionless phase changes. The diffusionless phase change of Au-Cd possesses several remarkable features. One of these is that the interface between the high-temperature beta phase and the low-temperature orthorhombic phase typically moves with a low velocity, in contrast to the behavior observed in the transformation of austenite to martensite. Motion pictures of this slow interface motion have been prepared in the course of the work reported here. Another important feature of the Au-Cd transformation is the small amount of undercooling observed. The reverse transformation occurs on reheating to a temperature only 20" higher than the transformation temperature observed on cooling, and under some circumstances the hysteresis observed is substantially less than this. This narrow temperature range between transformation on heating and cooling is presumably in part a consequence of the fact that the transformation requires a lattice shear of only about 3". Finally, the orthorhombic product phase possesses unusual mechanical properties, as was first pointed out by olander&apos; and Benedicks." After completion of the transformation on cooling the specimen can be severely deformed, yet on the release of load it springs back to its original shape in a rubber-like manner. Explanation of this phenomenon will require an understanding of the lattice imperfections in the orthorhombic structure and, correspondingly, of those in the initial body-centered cubic structure. Single crystals of Au-Cd alloy containing 47.5 and 49.0 atomic pct Cd were prepared from fine gold (99.95 pct purity) and chemically pure cadmium (99.99 pct purity) by melting the alloy in an evacuated and sealed fused quartz tubing and growing into single-crystal form by the Bridgman method. The Au-Cd alloy containing 47.5 atomic pct Cd undergoes a diffusionless transformation from an ordered body-centered cubic structure to an orthorhombic structure when it is cooled to about 60°C, while the reverse transformation takes place when the alloy is heated to about 80°C, according to electrical resistivity studies. The structures of these two phases have been studied by Blander,4 reinvestigated by Bystrom and Almin.e he lines of Debye photo-gram of powdered samples of Au-Cd alloy containing 47.5 atomic pct Cd prepared in this laboratory were identified and agreed fairly well with those of

Jan 1, 1952