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By L. F. Mondolfo, W. T. Collins

A study of the relationship between undercooling for nucleation and structure in Sn-Cu alloys with 0.1 to 5 pct Cu has shown that in hypereutectic allojls the halo of tin that surrounds the primary crystals of Cu3Sn5 is larger, the larger the undercooling for nucleation o,f the tin. This increase of halo size results in a decrease of coupled eutectic, and, in alloys far from the eulectic composition, may produce its complete disappeavance, with the formation of a divorced eutectic structure. This was confirnred by the excrrnination of other alloys in which divorced eutectic slructuves are formed, and leads to the conclusion that they ave only an extrenle case of halo forrtzalion , which results when the two phases freeze one at a time and solidification of the first is completed Defove the second starts. It was also found that under proper conditions of nucleation all types of eutectic structures can be formed in the sartte system , and therefore divorced eutectics, like normal and anomalous, are not characteristic of the syslett~, but are mainly controlled by nucleatiorz. Dizlovced eutectics are formed when the phase that tutcleates the eulectic vequires a large undevcooling for ils nucleation and when the cotnpositiorz of the alloy is far from the eutectic., on the side of the primary phase that does not nucleate the other phase. It is recommended that the tevm "divorced" be used in preference to degenerate because it is more desct-iptice of the morphology and mode of forinalion of the structures. ThE variety of structures found in eutectic alloys has been extensively investigated and classified. The most accepted classification is the one by ~cheil,' in which three different types of eutectic were distinguished: 1) normal, 2) anomalous, 3) degenerate (divorced). ATornlal eutectics are typified by the simultaneous growth of the two phases ("coupling") by which the two phases appear as interpenetrating crystals. The presence of a crystallization front, in which the two phases grow side by side, creates the eutectic grains, with the boundaries where the fronts meet. The presence of eutectic grains is the .distinguishing feature of a normal eutectic, according to Scheil. Straumanis and Brakss2 examined the Cd-Zn system and showed that there was a crystallographic relationship between the phases. Later, others4 also investigated additional systems and found definite crystallographic relationships in the coupled eutectics. The anornalous eutectic shows much less coupling than the normal; the two phases are intimately mixed but 'grow without a uniform crystallization front—a consistent crystallographic relationship— and the eutectic grain is conspicuously absent. As in the normal eutectics faster rates of growth result in a finer structure, but there is not the typical uniform spacing of normal eutectics. The degenerate eutectic shows no coupling; in fact the two phases attempt to minimize their area of contact and to form separate crystals. It has been suggested5" that slow cooling may favor this type of structure. Scheil believes that normal eutectics are formed when the two solid phases are present in more or less equal proportions, whereas both anomalous and degenerate eutectics form when one of the phases is present only in small amounts. spengler7 extended much farther this qualitative relationship between the eutectic type and the ratio of the two phases, and added a relationship to the melting point of the constituents. On this basis he proposed two equations for determining into which of Scheil's classifications an alloy belongs. The first equation is: where TI is the melting temperature of the lower-melting component, Tp of the higher-melting component, and Te the eutectic temperature. The second equations is: where is the volume percent of the lower-melting phase and $2 of the higher-melting phase at the eutectic composition. If 0 and/or 4 are in the range 0.1 to 1, a normal eutectic is formed; if in the range 0.01 to 0.1, anomalous; if less than 0.01, degenerate. Although the examples given by Spengler show a good agreement with the formulas, chadwick found that the Zn-Sn eutectic is normal to all growth rates, even though the volume ratio is 12/1, and Davies9 reports that the A1-AlgCo2 eutectic is normal, with a volume ratio of more than 30/1. Many more discrepancies of this type can also be found. Neither Scheil nor most of the other investigators have considered nucleation as a factor in the formation of divorced eutectics. Daviesg states that divorced eutectics form when neither phase acts as

Jan 1, 1965

By R. L. Manegold

IN RECENT years there has been a decided trend toward bringing ores and coal out of open-pit and underground mines by long, sloping single-stage belt conveyors. Because the high investment cost of haulage conveyors dictates maximum speed and full loading for economy, conveyor belts are running faster than ever before, with a greater burden on the belts. In addition, larger blocks of ore are being mined and conveyed. Rougher use of large mining equipment generates more tramp iron; mechanical loading rejects nothing. Therefore the extraction of tramp iron and other deleterious materials for the protection of haulage conveyors at transfer points, chutes, and idlers is becoming an increasingly difficult job. In our experience, the best method of protecting long haulage conveyor belts is to extract the tramp iron, at least the large tramp iron, ahead of the main haulage conveyor or series of conveyors. It is most practical to collect the tramp iron at the earliest source -possible, usually directly after the primary car unloading dump or after the primary crushers, which are ordinarily not affected by tramp iron, see Fig. 1. The coal or ore from its primary source is fed by chutes or feeders onto a buffer or shock belt conveyor, a short, ruggedly built conveyor system that can be considered somewhat expendable. Its primary function is to bring the ore up to speed for transmission to the haulage conveyor. There is no assured method of protecting this conveyor from tramp iron damage at its feed end. Likewise, there is a possibility, although remote if the magnet applied to this belt is installed correctly, that the tramp iron extraction process will damage the shock belt, which is, however, short and comparatively inexpensive. Magnetic head pulleys with their maximum effective range of about 8 or 10. in. cannot be considered for large installations, even though they are desirable because of the continuous and, automatic tramp, iron removal feature. Further, the most dangerous form of tramp iron with respect to potential damage to a haulage conveyor is the long rod, roof bolt, or rail segment, which is not extracted satisfactorily because of the limited tangential contact of such an iron shape with the magnet. Magnetic head pulleys are also undesirable because the dribble or fines from the head pulley discharge at the same point as the tramp iron. Screens must be used to separate the fines from the magnetics, resulting in additional expense and loss of head room. Magnetic detectors have been used with success, but they only indicate the, presence of iron, and the conveyor belt must be stopped for its manual removal. The, stoppage of any conveyor means that all preceding equipment must be stopped or a cascade of material on the idle conveyor will result. Occasionally combinations of detectors and magnetic, head pulleys are used. The detector precedes the magnetic head pulley and detects only large pieces of tramp iron, while the magnetic pulley subsequently takes out the smaller ferrous metals. Suspended magnets overcome the disadvantages of magnetic head pulleys, detectors or a combination of both. There are several magnetic extraction problems involved in applying a suspended magnet at this

Jan 1, 1952

By Edmund C. Pechin

THE iron trade of America seems on the point of a new departure. After years of struggling against heavy odds, patient endurance in periods of depression and loss, fears and hopes alternating as failure or success seemed to be the penalty or reward ; wanting in sufficient capital, embarrassed by reason of imperfect knowledge and lack of skilled labor, confronted by a powerful foe-every doubt has at last vanished, physical and mechanical difficulties have been largely overcome, capital has become more abundant and remunerative, the excellence of our product has been everywhere established, - and the peculiarities of American character-pluck, energy, and perseverance -have at last placed the trade upon a foundation so broad and stable that upon it we begin to erect the structure of a world-wide business. Concerning the future of the iron trade in the United States there can be but little doubt. The growing scarcity and constantly increasing cost of raw material in Great Britain, their loss of labor by emigration, the social disturbances among the working-classes, assuming a more threatening attitude on each new outbreak ; the rapidly decreasing value of money, in consequence of the enormous production of gold and silver, combine to forbid any return to former prices, and indicate that a point has been reached beyond which any marked increase of production is improbable. The same causes are operating to a greater or lesser extent upon the Continent. . In the meanwhile the growing wants of humanity are rapidly outstripping these sources of supply. In addition to the steadily increasing foreign and home demand, we find, the world over, the most intense activity everywhere displayed in enterprises requiring

By Edmund C. Pechin

THE iron trade of America seems on the point of a new departure. After years of struggling against heavy odds, patient endurance in periods of depression and loss, fears and hopes alternating as failure or success seemed to be the penalty or reward ; wanting in sufficient capital, embarrassed by reason of imperfect knowledge and lack of skilled labor, confronted by a powerful foe-every doubt has at last vanished, physical and mechanical difficulties have been largely over-come, capital has become more abundant and remunerative, the excellence of our product has been everywhere established, and the peculiarities of American character-pluck, energy, and perseverance -have at last placed the trade upon a foundation so broad and stable that upon it we begin to erect the structure of a world-wide business. Concerning the future of the iron trade in the United States there can be but little doubt. The growing scarcity and constantly increasing cost of raw material in Great Britain, their loss of labor by emigration, the social disturbances among the working-classes, assuming a more threatening attitude on each new outbreak ; the rapidly decreasing value of money, in consequence of the enormous production of gold and silver, combine to forbid any return to former prices, and indicate that a point has been reached beyond which any marked increase of production is improbable. The same causes are operating to a greater or lesser extent upon the Continent. In the meanwhile the growing wants of humanity are rapidly outstripping these sources of supply. In addition to the steadily increasing foreign and home demand, we find, the world over, the most intense activity everywhere displayed in enterprises requiring

Jan 1, 1873

By F. C. Newton

REFINERS of lead by the Parkes process have always been solicitous of recovering the zinc used in the desilverization, and justly so, as the loss in zinc constitutes one of the heavy costs in this method of refining. Part of this loss is due to the absorption of zinc by lead, and in the present state of knowledge is not recoverable as metallic zinc. The remainder of the zinc, which finds its way into the precious-metal-bearing crust, is recoverable and naturally engages the operators' most exacting attention. Careful elimination of the impurities in base bullion has enabled the refiner to produce a zinc crust better adapted to retorting, which reflects favorably in the zinc recovery; and to produce a richer crust, thereby lowering the zincking cost, as the increased efficiency of the zinc results in less of it being in circulation. It is obvious that if the ratio of concentration be increased, a lessening of the amount of crust formed will ensue, throwing less work on the retorts and diminishing the amount of retort metal sent to the cupels, thus making an actual money saving in all these operations. In the effort to obtain a rich crust, the metallurgist has increased the heat to a considerable degree, upon the assumption that at the higher temperature the zinc-silver alloy could be squeezed free from the adhering lead. A further possibility for improvement suggested itself in the freezing-point curve of Prof. H. C. Carpenter, upon zinc and silver. Study of this curve disclosed the existence of a definite chemical compound, . Zn3Ag2, with a freezing point of 665° C., a promising compound for practical application.

Jan 2, 1915

By Duane H. Haley

Dr. F. Well, the first thing that you have to realize is what is the Bureau of Mines? The Bureau of Mines basically has two functions. First it does the research and development relating to mining, processing, conversion, refining, recycling and substitution for minerals and materials. We work hand in hand with the U. S. Geological Survey on the geological end, although the exploration part of the game is theirs, and there is a very good relationship between the Survey and the Bureau of Mines. There are some overlaps with the Office of Coal Research, and we expect to be able to straighten out the areas of overlap, because it's important than OCR and the Bureau work together. Both the Office of Coal Research and the Bureau of Mines will have increased budgets next year, assuming that they are appropriated by the Congress. The other general area is in the whole area of mineral policy. The Bureau of Mines again is the key agency for developing data and analyses and making recommendations on all types of mineral policy in the Federal Government. It's a focal point for all types of minerals activities. It's the only real centralized focal point, along with the USGS, in the whole Federal Government. The problem areas, to answer your question specifically, are first of all the Bureau of Mines budget this year is $105 million and the budget for next year is $215 million, so it's more than double. Now, assuming that this budget is appropriated by the Congress, most of that money will be used for research and development in the energy area.

Jan 4, 1974

By Ernest O. Kartinen

This report is the accumulation of eight years of experience on only one small phase in the business of oil production. It is not intended as a final report but rather as a progress report dealing with the internal corrosion of oil field dehydrating tanks. The corrosion of dehydrating tanks continues to be a problem in the production of crude oil. The deterioration hy corrosion of these tanks falls into three general classifications: (1) Atmospheric corrosion of exterior areas, (2) corrosion of the underside of deck and the rafters and top area of the upper row of staves in that part of the tank which is known as the vapor space, and (3) corrosion of the bottom and shell areas, and the steam coils which are normally immersed in water and thus exposed to the corrosive action of the water. Atmospheric corrosion is primarily a paint problem, and has been omitted in this discussion. The corrosion in the vapor space, in this company's experience, which has been of great concern only in one area. has also been omitted in this discussion. The third, and most troublesome type of corrosion, and the one with which this report deals, is that which occurs in the water-exposed areas of dehydrating tanks, and, to a lesser degree. in some stock tanks. The operating temperature of these waters varies from 80°F to 160°F and the salt counts run from a few thousand to as high as 25.000 parts per million. Corrosion in these tanks occurs in three forms: (1) pits, (2) ringworm type of attack along the vertical and horizontal bolt seams, and (3) as a general attack, spread over a wide area. Steam Coils In dehydrating tanks, our experience has been that the steam coils are the first to show signs of corrosion, and then the shell and bottom areas. This action is not uniform throughout this company's operations. Some installations have coil troubles with very little tank trouble, and some show just the opposite. But in the majority of cases the coils are the more seriously corroded areas. This may be partly due to the fact that we have tried by periodic application to keep a protective coating on the interior areas of the tanks, and some protection has been afforded by these coatings. Through the years several types of hot and cold coatings have been tried with many various methods of cleaning the steel, ranging from use of cleaning solvents to hot and cold Oakite washes, as well as sandblasting. Although experience has shown that a longer life expectancy of a coating is possible after a very thorough steel cleaning job, it has still been necessary to recoat these tanks at least every two or three years. Until a few years ago, vertical spiral steam coil bundles were installed when the tanks were originally erected. When these coils needed replacement, in some cases within 18 months, it was necessary to remove a couple of shell staves to accomplish this task. This required a down time period of several days and was often very inconvenient to the production operations of the leases. This problem was considered on the basis that the coils were expendable, and thus. to eliminate any unnecessary down time when changing coils, the vertical spiral coils were discarded in favor of horizontal flat coils which could be taken in and out of the tanks by way of the cleanout openings, and put together with unions. This made a fairly easily replaceable and repairable coil. But it was still very much of a nuisance when repairs were necessary. Efforts to increase the useful life of the dehydrating tanks led to the adoption of galvanized tanks at an increased initial cost. The zinc coating was depended upon for protection and no other protective coatings were applied. In July, 1944. during the development of a new lease, a 3-ring 1,500 bbl, black iron water tank was converted into a dehydrating tank with steam coils to handle the new production. This tank was coated inside with a cold, brushed-on coating, for protection against corrosion. After approximately 18 months of service, holes developed in the tank and the steam coils. The tank was emptied and cleaned for repairs. The coils were so badly pitted that it was felt advisable to replace them. Coating Becomes Loose Inspection of the tank showed the protective coating to be still in place but loose, and numerous blisters were in evidence. A closer inspection showed that the interior of this tank was so badly pitted under the coating that any further attempt to use the tank was inadvisable. This tank was therefore discarded and a new galvanized tank ordered and set up at considerable expense and inconvenience. In April, 1946, another dehydrating tank installation was made on an adjoining lease. This installation consisted of a 1,500 bbl. 3-ring galvanized tank with two sets of flat steam coils 12 in. and 24 in. up from the bottom. In September, 1947. seventeen months after installation. salt showed up in the boiler feed water. When the dehydrating tank was opened and cleaned, the steam coils were found to be badly pitted — several holes having penetrated through the wall of the pipe. New coils were installed.

Jan 1, 1950

By J. C. Wilhoit, E. M. Galle

A three-dimensional photoelastic study was made to determine the stress state around the wall and bottom of a wellbore due to fluid pressure within the wellbore and unequal principal geostatic stresses. Models simulating the wellbore were made from a phthalic anhydride-cured epoxy resin. The frozen stress technique of three-dimensional photoelastic-ity was used to determine the stresses within the model. Two separate problems were solved: (1) hydrostatic pressure on all sides of the model with the exception of the inside of the hole, and (2) uniaxial compression perpendicular to the center line of the hole. The results are presented in the form of contour curves for each stress component. The curves cover a region which extends several hole radii from the bottom and wall of the hole. By proper use of these results, the state of stress may be calculated for any point on the wall or bottom of the hole, as well as for any point within the material that surrounds the hole. A systematic method is given for calculating these stress components for any combination of fluid pressure within the wellbore and system of unequal principal geostatic stresses, provided one of the principal geostatic stresses is parallel with the wellbore. The results show that stresses around the wall and bottom of a wellbore, induced by an uneyual system of principal geostatic stresses, are appreciably different from those induced by geostatic stresses that are hydrostatic. For uneyual principal geostatic stresses, the experimentally determined stresses on the wall of the hole several radii from the bottom are in good agreement with the stresses calculated by elastic theory. INTRODUCTION Interest in the problem of determining the stresses around and near the bottom of a wellbore, due to geostatic loading and fluid pressure within the wellbore, originated in the petroleum industry. The stresses on the wall of the wellbore are of interest due to their relation to lost circulation during drilling, the fracturing of formations during squeeze cementing and hydraulic fracturing of producing formations. The stresses on the bottom of the hole are of interest to the drilling segment of the industry because to produce a hole in the earth it is necessary to remove material from the bottom of the hole. This removal of material is produced by structural failure of the rock, whatever the criterion for failure may be. Cunningham and Eeninkl have shown that for certain conditions the effect on drilling rate of the bottom-hole stresses caused by a hydrostatic overburden pressure is small compared to other effects. This question, however, needs further experimental and analytical investigation. Much information concerning the stresses on the walls of wellbores has been published considering both equal and unequal principal geostatic stresses. The problem of determining the stresses around the bottom of the wellbore is considerably more complicated. However, previous investigators have obtained numerical and experimental solutions to the problem for equal principal geostatic stresses. whitworth2 and woods3 have obtained numerical solutions. word415 obtained a three-dimensional photoelastic solution, Durelli and Deily 6 obtained surface stresses only by photoelastic means, and Cheatham and Wilhoit7 determined the stresses around the bottom of a short cylindrical cavity. While Miles and McGuire, Harrison and Kieschnick and Hubbert and Willis 10 obtained the stresses on the wall of a wellbore for unequal principal geostatic stresses, they did not concern themselves with the stresses near the bottom of the hole. The estimates made by Hubbert and Willis of the differences between the principal geostatic stresses indicate that, to obtain a satisfactory solution for the stresses around the bottom of a wellbore, unequal principal geostatic stresses should be considered. This work is directed toward obtaining such a solution. The materials in the earth's crust are nonhomo-geneous, permeable and anisotropic. Previous

By C. R. McEwen

This paper presents a technique for calculating the original amount of hydrocarbon in place in a petroleum reservoir, and for determining the constants characterizing the aquifer performance, based on pressure-production data. A method for doing this based on a least-squares line-fitting computationwus proposed by vanEverdingen,Timmerman andMcMahon in 1953. We found that their method would not work when there is error in the reservoir pressure data — even moderate error. The technique presented here appears to give reasonable answers when pressure data are uncertain to the degree expected in reservoir pressure determinations. The major change introduced in the present analysis is to limit the least-squares line-fitting to yield only one constant— the amount of hydrocarbon in place. The water-influx constant is then taken as proportional to the oil (or gas) in place. The constant of proportionality can be computed from estimates of effective compressibility and reservoir water saturation. It is also pointed out that the commonly used least-squares analysis assumes all of the uncertainty to be in the dependent variable. The material balance should be arranged so that this condition is fulfilled if correct inferences are to be made from statistical calculations. Examples are shown of the application of the new technique to gas reservoirs—both hypothetical and real—and to the oil-reservoir example of van Ever-dingen, Timmerman and McMahon. INTRODUCTION The amount of hydrocarbon originally in place in a petroleum resenroir can be estimated by means of the material-balance calculation. Simultaneous observations of pressure and amounts of produced fluids are required, together with the PVT data applicable to the reservoir fluids. If water encroachment is occurring, it is desirable to try to infer the behavior of the aquifer, as well as the original hydrocarbon in place, from the pressure-production data. This imposes additional demands on the method of calculation, and uncertainty in the data can result in large uncertainty in the answer. In addition, if the size of a gas cap is to be established, the whole problem becomes indeterminate, as pointed out by Woods and Muskat.1 Brownscombe and Collins2 simulated a gas reservoir and its aquifer on a reservoir analyzer and derived quantitative information on the effect of uncertainty in pressure and aquifer permeability on computed gas in place. Among the various techniques of estimating the performance of an aquifer, the method of van Ever-dingen and Hurst? based on compressible flow theory, seems to have been the most generally successful (see Ref. 4, for example). In this paper we shall confine ourselves to their representation of the aquifer. In 1953,' van Everdingen, Timmerman and McMahon5 introduced a statistical technique for deriving the amount of oil originally in place and the parameters which describe the aquifer. (We shall refer to this technique as the "VTM method'', as suggested by Mueller.6) Their example reservoir had no gas cap. It has been our experience that the VTM method gives a reasonable answer when the data are very accurate, but that inaccuracy (particularly in pressure) can cause the method to break down. The effect was first observed in gas reservoirs, but has since been seen in oil reservoirs also. In this paper we present another statistical method which has been successful in achieving a reasonable answer where the VTM method has failed. In the new method, one less parameter is derived from material-balance computations. It is assumed that values can be established for effective compressibility in the aquifer and reservoir water saturation independently of the material-balance calculation. The water-influx constant can then be obtained from these data and the quantity of hydrocarbon in place.

MINING ENGINEERING presents the annual membership report of the Society of Mining Engineers; see page 147.

Jan 7, 1964

By C. Richard Tinsley

INTRODUCTION Project financing has been defined by various authors in this book. It is founded on reliance upon the project's own future cash flows and secondarily on the collateral value of the asset base developed. It is chiefly provided by the banking community who, after an assessment of the risks involved (See Chapter 9) analyse the company's presentation (See Chapter 10) in order to structure a financing package often at a leverage of up to 80% debt. This paper describes the various support and structuring techniques used to delimit and abate the risk components perceived from the banks' experience on project development especially for the period before cash flow is generated (pre completion). ADVANTAGES The advantages of project financing extend beyond the offloading of risks to banks. Among the advantages are the following: 1. Longer loan maturity than conventional, unsecured financing; 2. Loan disbursement and repayment tailored to specific mine; 3. Ability of a joint venture without a "track record" to raise financing; 4. Obtain financing where further direct borrowing (corporate credit) limited by existing indentures; 5. Possibility of arranging finance off-balance sheets; 6. Leverage return on equity; 7. Obtain tax savings with certain project financing structures; and 8. Obtain flexible loan repayment conditions. It can also be said that from the point of view of the company, project financing has certain disadvantages which can be summarised as follows: 1. Perceived higher cost (risk premium) compared with straight corporate credit; 2. More documentation; and 3. Need to negotiate risk-sharing aspects. The main attraction of project financing is the ability to pass certain risks on to the lenders within a flexibly funded transaction. (For a more detailed description of the specific risks see the author's paper at the beginning of Chapter 9. The same risk system is followed here.) The typical project financing has corporate support prior to completion and will usually carefully control the resultant cashflow after completion to ensure the bank does not unnecessarily assume further risks of an equity nature. WITHIN THE COMPANY'S CONTROL Operating Risk This is broken into three interrelated segments for ease of description. Technical Component: This must be specifically addressed if new technology or unproven adaptations are to be used. The banks will have scrutinized the sampling and bulk testing work, perhaps grilling the geological, mineral processing, metallurgical, and mining engineering staff or consultants directly. A number of supports are available such as: TECHNOLOGY GUARANTEE: Either the company itself or the process developer will guarantee that the technology will work for a period of, say, six months to two years after startup. If not, then financial penalties will apply although these are rarely sufficient to repay the loan. Many process developers are weak financially and may have little substance to back such a guarantee.

Jan 1, 1985

By R. J. Evans, A. G. Revesz

Silicon films have been grown by chemical reaction on (111) silicon substrates. The surfaces were examined by various microscopic and interfero-metric methods. Surface structures are classified into two groups depending on whether the angles between the bounding planes and the (111) surface are small (<3 deg) or large (> I0 deg). A layer-gvowth mechanism is postulated to explain the topography and the influence of growth parameters. Growth proceeds by lateral expansion of the (111) layers in (211) directions, thereby forming steps. The step edges are perpendicular to the direction of expansion and are thus along (110) directions. Step bunching md surface nucleation both play an important role in modifying the flow pattern and in the step regeneration. These are influenced ver?) much by impurities, especially oxygen. Although the growth is a result of a surface-controlled ga: reaction, it is very similar to growth from an impure solution. OVERGROWTH ("epitaxial growth") of silicon is important and widely used. During the past years several investigators have observed various topographical features or so-called faults on the grown films. A study of the surface morphology gives some insight into the growth mechanism. I) EXPERIMENTAL Silicon films have been grown on silicon substrates by a method described by Theuerer.&apos; Silicon is formed by reduction of SiCl, in hydrogen. The rate of incidence of SiC1, was varied between 5 x 10"6 and 2 x 10&apos;4 moles min-&apos; cm-&apos;. The mole fraction of Sic4 in the Hz-SiCL mixture was about 5 x X Both the rate of incidence and the mole fraction were calculated on the assumption that the Hz bubbling through the SiC1, reached equilibrium saturation. Assuming uniform velocity distribution, the linear velocity of the gas in the reactor tube was estimated to be 2 cm sec-l. The temperature of deposition was varied between 1070" and 1260°C. Chemically polished p-type silicon wafers of 20 to 100 ohm cm resistivity were used as substrates. These were within 1/2 deg of a (111) orientation. The thickness of the grown n-type film was determined by two methods: a) measurement of the depth of the p-n junction taking into account the junction shift due to diffusion, b) measurement of the traces of stacking-fault tetrahedra on the (111) plane.&apos; The agreement between the two methods was better than 20 pct. The rate of growth varied between 0.2 and 4.0 pmin-&apos;. The formed films were examined by reflection and light-section microscopy, and by multiple-beam interferometry. Phase-contrast illumination revealed height differences of about 30A. For measuring heights greater than 1 p a light-section microscope3 was used. The resolution by multipke-beam interferometry4 was between 50 and 100A. Crystallographic directions on the surface were determined by X-ray and from the orientation of etch pits and stacking faults as revealed by Dash etch (I part HI?, 3 parts HNOJ, and 12 parts CH3COOH). Some specimens have been investigated by electron microscopy. Platinum-shadowing and carbon-replica techniques were used to show the fine topography and reflection diffraction to determine the structure of the grown layers. 11) RESULTS The topographical features can be classified into three groups. he first group is comprised of fine ridges (striations). The second group consists of structures, which are bounded by planes making angles of less than 3 deg with the (111) surface. They are, therefore, vicinal planes. Structures which closely resemble growth or etch pyramids from the third group would normally be bounded by perfect low-index crystallographic planes. In this case they are deformed. The angles between the bounding planes and the (111) surface are generally larger than 10 deg. The fine ridges are present, even on the smoothest surfaces, as shown in Fig. 1. They are along a (110) direction. The height differences could not be resolved with interferometric techniques. The basic characteristic structures of the second group are depressions and hillocks. These are bounded by three planes, two of them with larger slopes than the third one. The edges between the planes, as projected to the (111) surface, point in (211) directions. Various habits of these structures are shown

Jan 1, 1964

By Margaret V. Doyle, R. W. Powers

INTERNAL friction measurements, carried out as functions of temperature, have been used extensively to obtain data on the mobility of interstitial impurities in the Group V metals, vanadium, colum-bium, and tantalum. For a given frequency of vibration, the internal friction peaks at a temperature which depends principally on the particular metal and interstitial impurity. Relaxation times and corresponding activation energies are determined from a knowledge of such peak temperatures for various vibration frequencies. These experimentally determined relaxation times are related to the average jump frequencies of the interstitial impurity atoms using the model of Snoek1 and can be related to macroscopic diffusion coefficients as shown by Polder.2 In these Group V elements, the impurity whose diffusion rate has been the hardest to pin down by the internal friction technique has been carbon. The experimental difficulties associated with carbon in these metals were not evident in the earliest investigation carried out by Ke on tantalum.3 The carbon peak was thought to occur near 140°C at 1 cps on the basis of the enhancement of the height of this peak measured on specimens which had been coated with colloidal carbon and heated in vacuo at 1200°C. Presumably on the basis of similar evidence, Wert identified a peak also near 140°C at 1 cps in columbium with the diffusion of carbon in that element." Later, the difficulties of admitting carbon into these metals without simultaneously introducing oxygen were pointed out by Ang and Wert- nd by Marx, Baker, and Sivertsen.6 The latter suggested that the peaks attributed to carbon in tantalum and columbium might arise from the presence of traces of oxygen, adventitiously absorbed during the carburization. Such suspicion was confirmed, at least in tantalum, when it was found possible to prepare C-Ta specimens without contamination by oxygen. Specimens sci prepared, aitnough high in carbon content, gave no evidence of a damping peak near 140°C.7 Recently, the authors were able to Show that carbon diffuses in tantalum at a rate only slightly slower than that for nitrogen.8 At 1 cps, the carbon peak lies at 34g °C, only a few degrees above the nitrogen peak at 341 °C. However, the two could be distinguished by a different stability with respect to aging at 400 °C and by a different dependence of peak height on solute concentration. On the basis of this experience with tantalum, it appeared worthwhile to search also for a carbon peak in columbium in the vicinity of the nitrogen peak." In this report, the location of the carbon peak in columbium is made known and its position relative to the nitrogen peak is compared with the authors&apos; previous findings in tantalum. In addition, a second source of internal friction seen only in specimens of very high purity is discussed. Columbium was obtained from the Fansteel Metallurgical Corp. as either 30 or 40 mil diam stock. The manufacturer gives the following analysis as typical of this material: 99.4 pct minimum Cb, 0.10 pct maximum C, 0.5 pct Ta, 0.04 pct Ti, 0.02 pct maximum Si, and 0.01 pct maximum Fe. Wires 13 in. long were degassed near 2200°C for 4 to 16 hr in an ultimate vacuum better than 2.10" mm Hg in an apparatus described previously.8 This treatment reduced the oxygen and nitrogen damping peaks observed in the as-received material to less than 0.0001 in Q-1 above background. The latter value varied somewhat from specimen to specimen in the range 0.0004 to 0.0008, depending chiefly on the wire diameter and the frequency of vibration. The high temperature evacuation left the specimen in a rather soft condition, the Vhn being reduced to 40 from a value near 121 in the as-received conGi~iur~. The gram size was about the diameter of the specimen. After outgassing, specimens were loaded with carbon by absorption of such hydracarbons as methane or ethylene. Carbon was also added to a few speclrnens by heating them at

Jan 1, 1958

By Strathmore R. B. Cooke

On the basis of experiments conducted on quartz using a bubble pick-up method, it was shown in an earlier paper1 that this mineral will preferentially adsorb hydrogen, calcium, or sodium ions, depending on the relative concentrations of those ions in the solution in which the quartz is immersed. For quartz particles ranging in size from 0.2 to 1 mm, it was demonstrated that the concentration of calcium in solution (assumed present as ions) necessary to completely activate quartz for flotation is given by the expression: Ca++ = [H+] X 106 + [Na+] X 10-3 In this expression, ionic concentrations are in mols per liter. It was further shown that the pick-up method is apparently more sensitive to changes in reagent concentration than the standard captive-bubble method, and that induction times are apparently much reduced. Since completing these earlier tests, a new type of cell has been constructed; this is shown in Fig 1 and 2. In Fig 1, A is a ground joint, B is a central tube reaching to within a few millimeters of the bottom of the cell, and C is a stopper which may be removed for reagent addition, and serves the further purpose of excluding carbon dioxide from the air during the test. The entire cell is constructed of Pyrex glass, and does not give the trouble experienced with the earlier cell, in which activating ions were released from the glass at high pH values. The only critical factor in the construction of the cell is the clearance between the central tube and the bottom of the cell. This clearance should be sufficiently small that the bubble can be pressed directly on the mineral grains lying on the bottom of the cell. In the pick-up tests to be described in this paper, the reagents used were all of C. P. grade, except the sodium oleate, which was Merck&apos;s "neutral powder." The quartz employed was water-clear vein quartz, sized on screens, cleaned with both hydrochloric acid and sodium hydroxide, and given a thorough final washing with distilled water. Experimental procedures were the same as described in the earlier paper. EFFECT OF SIZE OF QUARTZ ON PICK-UP To ascertain the effect of particle size on the adsorption of calcium ions, the quartz was sized from minus 14 plus 20 mesh through the intervening screen sizes to minus 270 mesh plus 400 mesh. Each size was thoroughly cleaned, and then tested in the cell at different calcium chloride and sodium hydroxide concentrations, and at a constant sodium oleate concentration of 20 mg per liter. All particles, within the size range given, exhibited complete pick-up within the curve expressed by the equation above. This presumably means, when the conditions imposed by the equation are satisfied, that this maximum is independent of particle size. However, it was found that the range through which partial particle pick-up occurred progressively broadened as particle size decreased. This is shown in Fig 3, in which curves B, C, and D show the limits at which pick-up just commences (as the pH is increased) for particles of minus 14 plus 28 mesh, minus 65 plus 100 mesh, and minus 270 plus 400 mesh size, respectively. These results indicate that for satisfactory activation, at any given pH, a lower calcium ion concentration is required for fine particles than for coarse particles. EFFECT OF HIGH ALKALINITY ON PICK-UP At calcium concentrations of between 1 and 10 mg per liter, and at high alka-linities, it was noticed that pick-up ceased as soon as calcium hydroxide commenced to precipitate. This effect was investigated at other calcium concentrations, with the same results. Solutions of calcium chloride, containing 105, 104, l03, and l02 mg of calcium per liter were made alkaline with sodium hydroxide until calcium hydroxide just started to precipitate, according to the following equation: CaCl² + NaOH -+ Ca(OH)2 + 2NaCl The beginning of precipitation was taken as that point at which either a faint opalescence appeared in the solution, or a Tyndall cone became ap-

Jan 1, 1950

By A. M. Adair

The effect of cathodically charging zone-refined iron with hydrogen and the resultant yield stress-grain size relationship has been investigated by tensile testing at -31°C. The resulting Petch plots (using a least-squares analysis) reveal a significant reduction in the slope and an increase in the intercept for specimens cathodically charged with hydrogen, regardless of whether the hydrogen is present during testing or is removed by evacuation. Other than surface blistering, the major effect of cathodically charging this material is to create occasional grain boundary cracks and thus presumably a large number of free dislocations at grain boundaries. These results are consistent with the hypothesis that the slope of the Petch plot is related to the stress required to activate dislocation sources at or near pain boundaries. While there is no significant effect of the presence of hydrogen on the lower yield stress of this material, the ductility is considerably reduced. After hydrogen removal by evacuation, the ductility recovers substantially and almost complete recovery of ductility is experienced by the smaller grain size specimens. THE influence of hydrogen on the mechanical properties of ferritic materials has received much attention throughout the history of the metallurgy profession. This interest has stemmed from the obvious importance of preventing the catastrophic failure of parts in service, and from the desire to determine what mechanism is responsible for the observed behavior. The various mechanisms proposed for hydrogen em-brittlement have been discussed in detail by Tetel-man,&apos;who concludes that a combination of the applied stress and hydrogen pressure within voids best accounts for the many experimental observations reported. From a quite reasonable correlation of the strain aging and delayed-failure behavior of a variety of materials,2-7 Troiano and coworkers are of the opinion that the delayed-failure mechanism (slow strain rate embrittlement as well) is better explained as a lattice effect; solute elements diffuse to regions of high triaxial stress, form uncondensed atmospheres there, and effect a reduction in the cohesive strength of the lattice. Since hydrogen yield points8,9 have been observed in ferritic materials, and since the hydrogen embrittlement process may be related to strain aging, one further contribution to embrittlement could be hydrogen-dislocation interactions which make crack blunting by plastic deformation a more difficult process. The etch" relationship offers a means of comparing the relative ease of initiating and propagating plastic deformation in metals and alloys. In the present study, this relationship was used to compare the behavior of zone-refined iron in three conditions: uncharged, cathodically charged with hydrogen, and cathodically charged with hydrogen and evacuated. These Petch plots and the observed ductility parameters allowed a separation of the effects of the very presence of hydrogen and the act of cathodically charging hydrogen into this material. MATERIALS AND EXPERIMENTAL PROCEDURE An ingot of zone-refined iron was obtained from Battelle Memorial Institute which contained the following (typical) interstitial impurities in ppm: carbon, 10 * 5; nitrogen, 1; oxygen, 22; hydrogen, 0.9. The ingot was cold-reduced to a 1/2-in.-sq cross section, recrystallized 1 hr at 575°C, and then straight-rolled to a thickness of about 0.105 in. Tensile specimens were milled from the strip having a 1-in. gage length

Jan 1, 1967

By John P. Huger

me phase diagram for the system Ag-Si has been established by thermal analysis. The diagram is a simple eutectic type with a eutectic at 3.0 pct Si and 840°C. From the liquidus curve and with the aid of regular solution theory, the thermodynamic properties of the liquid Ag-Si system at 1420 °C have been determined. Silicon exhibits positive deviations from Raoultain behavior at all compositions, while silver exhibits both positive and negative deviations. MEASUREMENTS of silicon activities in liquid iron alloys by means of distribution studies between the immiscible liquids silver and iron have been reported by Chipman, Fulton, Gokcen, and caskey.&apos; The applicability of this technique is dependent, however, on the accuracy of the silicon activity values in the Ag-Si alloys, particularly in the dilute silicon region. Darken and Gurry2 have shown that log ?si/(1-xSi)2 is approximately linear with composition, but uncertainty exists in the extrapolation to dilute solutions. Their calculations are based on the old Ag-Si phase diagram of Arrivaut3 and any variation in the position of the liquidus curves will strongly influence the extrapolation. The purpose of this study is to redetermine the Ag-Si phase diagram and calculate the associated thermodynamic properties. EXPERIMENTAL The Ag-Si phase diagram was determined by thermal analysis of liquid alloys. The alloys were contained in a 35 mm alumina crucible under a protective stream of purified argon. The crucible was placed inside a 64 mm alumina tube fitted with a gas-tight, water-cooled, copper head. The tube and assembly were heated in a manually controlled globar furnace. The temperature was measured with a Pt, Pt + 10 pct Rh thermocouple in a high-temperature porcelain protection tube. The thermocouple calibration4 was checked against the melting point of pure silver at the start and during the course of the experiments, and against both gold and silver at the completion of the experiments. The alloys were prepared from granular silver analyzing 99.95 pct Ag and powdered silicon analyzing 99.88 pct Si and 0.026 pct Fe. Approximately 150 g of alloy were used for each run. The composition of the alloy was determined by withdrawing samples of the liquid alloy with a vycor tube-aspirator bulb device. Analysis of solidified samples agreed, for alloys containing less than 23 pct Si, within ±0.3 pct Si of the calculated composition. Duplicate samples showed a variance within 50.05 pct Si of the mean analysis. The alloy was heated to 100&apos; to 20pC above the estimated liquidus temperature and then the furnace was adjusted to give an average cooling rate of 2" to 7°C per min. A cooling curve was obtained by taking potentiometer readings at 15-sec intervals. Several analyses were made by recording the thermocouple output on a high-speed, Stip-chart recorder, with the exception of run NO. 11, a minimum of two thermal analyses were made for each alloy and the cooling curves then obtained duplicated the liquidus and eutectic temperatures to about 1°C. RESULTS The results of the thermal analysis are given in Table 1, and are represented as the Ag-Si phase dlagram, Fig. 1. The eutectic composition was found

Jan 1, 1963

By J. P. Martin, A. H. Geisler, J. H. Crede, E. Both

The investigation of a 50 pct Co alloy was undertaken to determine whether there was any direct correlation between the structure and properties of Co-Fe alloys which were given various magnetic heat treatments. The magnetic anisotropy and texture of the 0.002-in. cold-reduced 98 pct material tend to decrease and change in nature with increasing temperature of the recrystallization anneal. Annealing samples in a magnetic field had little effect on either the magnetic properties or texture. However, cooling them in a magnetic field greatly improved their magnetic properties. THE beneficial influence of a magnetic field applied during the heat treatment of certain soft magnetic materials has been known for a long time. Early work showed that the presence of a magnetic field of a few oersteds during the heat treatment of Fe-Ni alloys will cause a large increase in maximum permeability. A pronounced increase in the residual induction which is produced by the magnetic anneal causes the hysteresis loop to approach the shape of a rectangle. Such results are beneficial since the desired properties are high permeability, high induction at maximum permeability, high residual induction, and low coercive force. More recently Libsch and coworkers1 studied the effect of magnetic annealing on the hysteresis properties of a series of Co-Fe alloys prepared from powders. They observed good response for the 35 and 50 pct Co alloys but little response for the 42 pct Co alloy. They pointed out that this was somewhat surprising since the 42 pct alloy has a high linear magnetostriction and zero crystal anisotropy and similar conditions in Fe-Ni alloys give excellent response to magnetic annealing. They found optimum properties to be at the 50 pct composition with residual induction, Br = 19,000 gauss and coercive force, Hc = 0.68 oersteds after the magnetic anneal. Before the magnetic anneal these values were B, = 12,600 gauss and Hc = 1.15 oersteds. The optimum treatment consisted of cooling from above the y-a transformation temperature to 900°C in a field of 20 oersteds, holding 11/2 hr at 900°C, then cooling at a rate of 20° to 25°C per min in the field to below 230°C. Cooling rate mainly affected coercive force with the value decreasing from 1.09 to 0.88 oersteds as the rate was increased from 3° to 48°C per min. Cooling from 1020" to 900°C in a field followed by further cooling to 230°C without the field gave properties decidedly inferior to those for samples annealed with the field applied throughout the cooling. They concluded that to get the best properties the samples must be cooled in a field to a threshold temperature above which the alloy is plastic enough to be affected by magnetostriction. In this respect the holding temperature must be high enough so that the alloy exhibits good plasticity to permit the optimum orienting of magnetic domains by relaxation of magnetostriction. In contrast, the holding time was of less significance for there was little improvement when the time exceeded 1/2 hr. The improvement in properties effected by magnetic annealing has usually been attributed to the establishment of a domain texture caused by the "freezing in" of magnetic strains. On the other hand, Smoluchowski and Turner2,3 apparently found that a magnetic field applied during recrystallization could alter the crystal texture. If this effect is real, improved properties would also be expected when

Jan 1, 1954

By J. B. Dorsey, T. W. Brinkley

Performance of a high-pressure, vaporizing gas-drive project in a volatile oil reservoir is discussed. The project has been in operation for over 8 years. Present recovery from the over-all displaced portion of the reservoir is 40 percent, and an ultimate recovery of 60 percent is indicated. Calculations reflect an over-all displacement volume of 50 percent for the entire reservoir; therefore, ultimate oil recovery will be 30 percent of the entire reservoir oil originally in place. Laboratory vaporization tests conducted prior to project initiation also are presented and discussed, along with an analytical method of determining stock-tank oil production and gar injection requirements related to over-all volumetric displacement efficiency from these data. Introduction The Shoats Creek field is located in Beauregard Parish, La., in the extreme western part of the state (Fig. 1). Discovered in 1956, the field is productive in three Cockfield sand zones, ranging in depth from 8,000 to 9.000 ft. The upper two zones, 1st and 2nd Cockfield, are condensate-bearing gas reservoirs. The lowest zone, the 5th Cockfield, is a volatile-oil reservoir. Laboratory work conducted on crude oil from the 5th Cockfield zone shortly after field discovery demonstrated that, when contacted with dry gas, signidcant volumes of the oil could be vaporized at reservoir temperature and at an appropriately high reservoir pressure. Further study led to the conclusion that early initiation of a crude vaporization project in the 5th Cockfield zone would be superior economically to other methods of reservoir depletion. Consequently, the zone was unitized and gas injection operations started late in 1958. This paper discusses laboratory work performed in conjunction with the project, and project performance to the present. History of Development The 5th Cockfield zone in Shoats Creek is composed of a thin, very shaly, low-permeability sandstone. Oil accumulation is controlled by a structural trap bounded by faults along the north and west and by a water contact on the southern boundary (Fig. 2). The zone covers a productive area of 1,550 acres at an average depth of 9,000 ft. The net sand section is thin, having a maximum thickness of 10 ft and an average thickness of 5.5 ft (Fig. 3). Average reservoir rock properties, as determined from core analysis are presented in Table 1. Shaliness of the zone is illustrated by the typical electric log of the 5th Cockfield section in Fig. 4. Because of the thinness and poor quality of the sand, the 5th Cockfield was developed on a wide spacing. Eleven completions were made in the zone between 1956 and 1961 for an average density of 140 productive acres per completion, with the majority of wells being dually completed in the 2nd and 5th Cockfield. Average initial potential for producers in the 5th Cockfield was 130 BOPD. Oil from the 5th Cockfield has a stock-tank gravity of 50.5" API; with a bubble-point pressure of 3,515 psia, the oil was highly undersaturated at the original reservoir pressure of 4,675 psia. Pertinent properties of the oil as determined in the laboratory are presented in Table 2. Because of the volatile nature of the crude, laboratory studies of its susceptibility to vaporization, as well as a vapor-liquid phase study, were conducted in addition to a standard PVT analysis. The vaporization study was conducted in a visual cell; a stepwise illustration of this work and laboratory measurements are presented in Fig. 5. Field

Jan 1, 1969

By C. P. Parsons

During the past year considerable interest has been shown in cementing operations for shutting off bottom water, whipstocking, etc. A number of plug-back methods have been used, with various adaptations for special conditions, but those described in this paper are representative of the methods now in use. Conditioning the Well Various preliminary operations for improving the results from plug-back operations have been evolved. In one method, a nitroglycerin shot is discharged at the upper portion of the formation to be plugged off, the purpose being to make a wide place in the hole in order to give the cement a more secure anchor against thrust pressure of the water against the bottom of the cement plug after the well is again put on production. Another is intended to attain a similar result by under-reaming a wide place in the hole by means of a rotary wall scraper. In one well in which this device was used there was a water sand at the bottom of the well immediately below the cap rock above which the oil sand occurred. Before the plugging back operation, the water sand was underreamed in an attempt to get a square shoulder on the underside of the cap rock, in order to prevent the water from breaking in over the top of the cement plug after the well should be put on production, and also to get a more secure anchor for the cement plug against the thrust pressure of the water against it. As an aid in calculating the amount of cement required to fill a given amount of hole to be plugged back, a device has been developed for measuring and recording the irregularities and cavities in open holes, called an "open-hole recording caliper." If consists of a steel shell, 5 in. in diameter, which encloses a recording mechanism that receives impressions from four movable arms that make sliding contact with the wall of the hole. The arms operate a ratchet, which raises and lowers a recording stylus against a chart. Each arm registers its own radius. The device is run into a well on a steel measuring line. While the device is being lowered, the arms are folded inside the shell; they are

Jan 1, 1936

By C. P. Parsons

During the past year considerable interest has been shown in cementing operations for shutting off bottom water, whipstocking, etc. A number of plug-back methods have been used, with various adaptations for special conditions, but those described in this paper are representative of the methods now in use. Conditioning the Well Various preliminary operations for improving the results from plug-back operations have been evolved. In one method, a nitroglycerin shot is discharged at the upper portion of the formation to be plugged off, the purpose being to make a wide place in the hole in order to give the cement a more secure anchor against thrust pressure of the water against the bottom of the cement plug after the well is again put on production. Another is intended to attain a similar result by under-reaming a wide place in the hole by means of a rotary wall scraper. In one well in which this device was used there was a water sand at the bottom of the well immediately below the cap rock above which the oil sand occurred. Before the plugging back operation, the water sand was underreamed in an attempt to get a square shoulder on the underside of the cap rock, in order to prevent the water from breaking in over the top of the cement plug after the well should be put on production, and also to get a more secure anchor for the cement plug against the thrust pressure of the water against it. As an aid in calculating the amount of cement required to fill a given amount of hole to be plugged back, a device has been developed for measuring and recording the irregularities and cavities in open holes, called an "open-hole recording caliper." If consists of a steel shell, 5 in. in diameter, which encloses a recording mechanism that receives impressions from four movable arms that make sliding contact with the wall of the hole. The arms operate a ratchet, which raises and lowers a recording stylus against a chart. Each arm registers its own radius. The device is run into a well on a steel measuring line. While the device is being lowered, the arms are folded inside the shell; they are

Jan 1, 1936