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By F. W. Jessen, C. A. Johnson

The effect of treatment with ferrochrome lignosul-fonate on both sodium and calcium bentonites has been examined. In the early stages of treatment it appears that some base exchange of iron and chromium for sodium may occur with the sodium bentonite. Such exchange appears specific for exchange of sodium ions when the calcium ion concentration represents 40-5.5 per cent of the total exchangeable cations, and when additions of lignosulfonate are less than 1 lb per bbl. Adsorption appears entirely physical above 1 lb per bbl treatment level for all concentrations of calcium studied. Gel strength and plastic viscosity of both calcium and sodium bentonite systems were reduced with treatments of ferrochrome lignosulfonate up to 2 Ib per bbl, the greatest reduction occurring within a range of calcium concentration of 40-5.5 per cent of the total exchange capacity of the clay. INTRODUCTION The problem of control of viscosity and gel strength of drilling fluids by the action of thinners or dispersants has been studied by many investigators.1-7 In addition, much work has been done on formation of gel structure in clay suspensions. However, gel formation and structure still are incompletely understood, and the use of the various dispersing chemicals is based, to a large extent, on data almost entirely empirical in nature. In recent years the lignosulfonates have become increasingly important in the treatment and control of drilling fluids. More specifically, ferrochrome lignosulfonate has found rather wide acceptance, particularly in calcium systems.5-7 Lignosulfonates are refined lignin products made from spent sulfite liquor from which the fermentable sugars have been removed.15 The exact structure of lignin is not known; however, it is believed to be a phenolic propane type polymer which may exist as a branched chain or cross linked structure. The molecular weights of lignosulfonates probably range from 300 to 100,000 or more.15 A better understanding of the mechanism of adsorption of dispersants is essential before improvement and development of characteristics of drilling fluids and drilling fluid control is possible. This investigation was undertaken to determine the action of ferrochrome lignosulfonate on sodium and calcium montmOrillonite' LABORATORY INVESTIGATION A Stormer viscosimeter and Fann V-G meter were used to measure viscosity and gel strength. A Zeiss spectrophotometer was used for analysis of Fe and Cr and the flame attachment was employed in the analysis of Na, Ca and Mg. A General Electric X-ray diffraction unit utilizing Copper Ka radiation and a Ni-filter was utilized in the X-ray studies. PROCEDURE Two systems were studied. Predominately sodium clay, obtained from Wyoming, and a predominately calcium clay from Texas were used. These particular samples were chosen because of the extensive work of characterization completed by Mungan. Ionic base exchange capacity determined by flame photometry and total exchange capacity by the Kjehldahl method were obtained experimentally. A 7-per cent suspension of the sodium clay and a 20-per cent suspension of the calcium clay in distilled water were prepared by mixing with a high-speed mixer. The suspensions were allowed to stand for two weeks for complete hydration. Calcium chloride was added to portions of the sodium and calcium cla suspensions to obtain suspensions varying in Ca++ concentration as shown in Table I. A series of treatments was run with 500-ml portions of the original suspensions using a ferrochrome lignosulfonate. Treatment was carried out in the same way with each of the suspensions of varying Ca concentration. Viscosity and gel strength were measured and a filtrate obtained at each treatment level. Ten ml of filtrate were diluted to 50 ml, and aliquot portions of the 50 ml were taken for the Na, Ca, and Mg analysis by the flame photometer. The pH of these filtrates ranged from 7 to 7.3. Standard

By R. S. Rickard, H. D. Peterson, J. D. Miller, M. C. Fuerstenan

Pure chrysocolla is floated with chelating agents that form insoluble complexes with copper at ambient temperature. Complete flotation is obtained with potassium octyl hydroxamate as collector at pH 6. Flotation response is enhanced with increased temperature when low additions of hydroxamate are involved. A natural ore was floated with 0.4 1b per ton octyl hydroxamate at pH 6.5 and 58°C, and a flotation recovery of 76% was obtained with a concentrate grade of 31.6% copper. The flotation characteristics of the oxide copper minerals, malachite, azurite, and cuprite, have not presented the difficulty for concentration as have those of the copper silicate, chrysocolla. The copper carbonates and oxides respond reasonably well to flotation with conventional collectors, whereas chrysocolla will not respond to flotation with fatty acids or xanthates under normal flotation conditions. In this view then, other reagents will have to be devised to function as collectors for chrysocolla. The most obvious general class of reagents for this purpose would seem to be the organic copper chelating compounds. The utility of chelating agents as collectors in flotation systems has already been demonstrated. For example Vivian1 has floated cassiterite using ammonium nitrosophenylhydroxylamine. Holman2 studied the flotation of nickel oxide ores with dimethylglyoxime and also suggested the use of taurine on oxidized lead ores. A rather detailed study on the application of certain chelating agents to some flotation systems was presented by Gutzeit.3 This work indicated that the formation of surface insoluble chelates is probably responsible for flotation in many cases. The role that soluble chelating agents assume was also presented, that is with effective removal of polyvalent cations by complex formation, effective depression of quartz can be obtained. DeWitt and Batchelder4,5 have shown that oximes function well as collectors for chalcocite, malachite, azurite, and cuprite. Ludt and DeWitt6 have presented the possibility of using dyes, such as octyl malachite green, as a collector for chrysocolla. These works presented by DeWitt et al suggest that organic copper chelating compounds offer considerable promise for concentrating chrysocolla, but that the most suitable chelating reagent from the standpoint of cost and flotation response has yet to be determined. The present investigation was undertaken to study the flotation response of chrysocolla to selected copper chelating compounds, that is ethylenediamine, hexamethylenetetramine, potassium octyl hydroxamate, dimethylglyoxime, and benzoin a-oxime. EXPERIMENTAL MATERIALS Chrysocolla: The chrysocolla used in the microflo-tation studies was from New Mexico and analyzed 20.8% copper. X-ray diffraction showed this material to be amorphous in character, but some faint lines of quartz were noted. A natural oxide copper ore from Utah was also used in the investigation. This ore contains malachite principally but also contains chrysocolla and tenorite together with some sulfide copper. The sulfide copper comprises from 15 to 20% of the total copper content of the ore. Water: Conductivity water was used in the microflo-tation experiments, while Golden tap water was used in the experiments with the natural ore. Reagents: Reagent grade n-amyl alcohol was used as frother in the experiments with pure mineral, while MIBC was used in the work with the ore. Ethylenediamine, hexamethylenetetramine, dimethylglyoxime and benzoin a-oxime were reagent grade in quality. Pure potassium octyl hydroxamate was prepared as follows: 1) 1.0 mole of KOH in 140 cc of methanol was combined with 0.6 mole of hydroxyl-amine hydrochloride in 240 cc of methanol at 40°C (KC1 precipitates under these conditions and to effect complete removal of KCl, the system was cooled to 10°C and filtered), 2) a light methanol wash was then given the KC1 cake, 3) the filtrate was agitated at room temperature and 0.33 mole of the methyl ester of the organic acid (i.e. methyl octanoate) was

Jan 1, 1965

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By Orville R. Lyons

CENTRIFUGAL force has been utilized for the dewatering of fine coal for over 50 years by means of machines commonly called centrifugal dryers. In any centrifuge the coal and water are subjected to a spinning action which usually inctedtocreases in intensity as the coal progresses through the machine. This spinning action, or the centrifugal force that it induces, tears water away from coal particles and produces a dewatered coal. The effectiveness of the dewatering action for any particular machine is governed by the size-consist of the coal and the centrifugal force imparted to the water on the coal. Four makes of centrifuge are currently being used to dewater fine bituminous coal in the United States. These include the vertical, basket-screen C.M.I. (Centrifugal and Mechanical Industries) Carpenter, Reineveld, and the horizontal solid-bowl Bird. The C.M.I. and Reineveld centrifuges are similar in construction and are variations of the Elmore centrifuge, varying principally in the slope of the basket, operating speed, size of perforations in the basket, and diameter of the basket. The same operating description suffices for both. These centrifuges are made up of two rotating elements, an outside conical screen frame and an inside solid cone which carries spiral pusher blades. The screen frame is supported by a hollow shaft, and the solid cone by a spindle shaft passing through the hollow shaft. Both the screen frame and the solid cone rotate at high speeds; the solid cone, with its scraping flights, rotating somewhat more slowly than the screen. The wet coal enters the machine at the top, falls on the cone, and is thrown against the screen by centrifugal force. The coal slides down the screen until it meets the upper end of the flights, where it is moved slowly along the flights until discharged at the bottom. The elfluent passes through the sieve basket or screen and discharges into a launder. The Carpenter centrifuge consists of a conical rotating element with a vertical axis, built up of three rows of perforated stainless-steel plates or stainless-steel wedge-wire or round-wire sections cut and rolled to conform to the surface of the cone. Wet material is delivered to a conical hopper inside the centrifuge casing and is distributed in a thin, even layer over the inner surface of the cone by a disk mounted on the rotor shaft. Impacting of the coal against the screen and the centrifugal force exerted as the material moves downwards creates a dewatering effect. The moisture is forced through the coal bed and then through the perforated plates of the basket, collecting in a circular trough built into the centrifuge. The effluent is conducted from the trough through the centrifuge casing by outlet pipes. The dewatered coal is discharged over the inside bottom edge of the rotor. The Bird centrifuge consists of a tank or truncated conical shell, which is revolved at the desired speed by means of a drive sheave. A screw conveyor rotates inside the cone or bowl at a slightly lower speed in the same direction of rotation. The feed entrance, in the center of the large end of the truncated cone, is high enough to allow formation of a pool of slurry. Adjustable effluent-discharge ports are located in the large end of the bowl so the level of the liquid can be regulated. The solids are moved forward by the screw conveyor as fast as deposited and carried above the level of the pool for an interval before leaving the bowl. In the past these four makes of centrifuge could be compared only by indirect means. The author published a rough comparison method in 1949' but

Jan 1, 1952

By R. F. Blakely, P. E. Potter

Any stratigraphic section or bedding sequence can be synthesized if there is a transition procedure from one lithology or bedding type to another, and if thickness distributions of the different lithologies are known. Stratigraphic sections of a fluvial sandstone body were synthesized with five bedding types: cross-bedding, massive beds, parting lineation, ripple mark and mudstone. The transition procedure from one bedding type to another used dependent, Markovian random processes which have a memory that extends one step backward in the depositional process. As observed in nature, median grain size and sand wave thickness (cross-bedding and ripple mark) decline upward in the synthesized sections as proportions of the different bedding types change. Grain size and permeability were also incorporated into the sections. By changing the transition procedures, bed thickness distributions, rate of upward decline or sand wave height and length, different types of sections can be synthesized, thus making it possible to model many different sedimentation problems. INTRODUCTION This paper describes a general method for synthesizing stratigraphic sections and bedding sequences of sedimentary, metamorphic or igneous origin. Synthetic generation is of interest for several reasons. Close correspondence between real and synthetic sections suggests that the factors used in the synthesizing model may indeed be the correct ones, thus giving the investigator a check on his assumptions. Rapid, inexpensive simulation of many stratigraphic sections permits one to synthesize a rock body (sandstone or carbonate reservoir) or, on a larger scale, the fill of a sedimentary basin. Harbaughl gives an example of mathematical simulation of a carbonate basin. He simulated the basin in the hope that improved prediction would follow better understanding of the depositional processes. From the petroleum engineer's viewpoint it seems reasonable to believe that the synthetic generation of rock properties and their distribution in a reservoir should be relevant in the study of reservoirs. Any stratigraphic section or bedding sequence can be generated provided there is a transition procedure from one lithology or bedding type to another, and provided the thickness distributions of the different units are known. The transition procedure involves random processes that are either independent or dependent. If the depositional process is independent, previous deposition will have no influence on present deposition. However, if it is dependent, past deposition will influence either present or future deposition. Such a dependent depositional process can be thought of as having a memory that extends backward in time through one or more pulses of deposition. A process with a memory can be described by a Markov process. Because the concept of memory or dependence appears to be in accord with our understanding of many depositional processes, Markov processes were used to synthesize the bedding sequences of this study (see Appendix). The above methods are perfectly general and are appropriate for any stratigraphic section or bedding sequence: bedding types in a beach deposit, an evolving carbonate bank or the changing lithologic fill of a thick geosyncline sequence. We chose to synthesize a vertical profile of a fluvial sandstone body because its characteristics were well documented, much was known about fluvial processes and fluvial-deltaic sandstone bodies constitute an important class of petroleum reservoirs. CHARACTERISTICS AND ORIGIN OF FLUVIAL CYCLE The fluvial cycle has been well documented in recent years by Bersier,2 Allen3-5and Visher.6,7 Deposits from fluvial cycles range from 10 to 150 ft or more in thickness and are characterized by a "fining upwards": coarse sandstones with occasional conglomerates grade upward into medium- to fine-grained sandstone, and hence into siltstone and mudstone. The dominant sedimentary structure is inclined bedding: thick cross-beds in the lower half

By H. Bernstein

Grain coarsening tests were carried out on AI-4.5 pct Cu and AI-4.5 pct Si alloys. The effects of three variables, melt composition, pour temperature, and mold temperature, were determined. It was found that the macrostructure generally coarsened with increased pour and mold temperatures. Coarsening was extreme in the unrefined alloys but was retarded by the active grain refiners like titanium and columbium. The effect of boron was spectacular in suppressing coarsening tendencies. The results of the investigation support the carbide theory of nucleation as opposed to the peritectic theory. A REVIEW of prior work on the subject of grain refinement in the light metals indicated that, for the most part, it had been concerned with the positive effects of addition agents upon structure. This work produced various theories of refinement. Prominent among them were the peritectic theory and the transition element carbide theory. Certain inadequacies in the former theory appeared to be explained satisfactorily by the transition element carbide theory. In order to appraise these theories further, a study was undertaken of the permanence of grain refinement effects when subjected to thermal or chemical variations. It was considered that a study of this kind would be of practical value, since the light metals are exposed to thermal and chemical variations in the normal course of foundry operations. Accordingly, two alloys of commercial importance were selected for this investigation, the A1-Cu and A1-Si alloys. Experimental Procedure and Results Raw Materials: The base alloys, A1-Cu and A1-Si, were prepared from virgin aluminum and hardeners, induction melted, and pigged for remelting. The grain refiners, including titanium, columbium, zirconium, and boron, were added as master alloys. Analyses of the raw materials and base alloys are listed in Table I. Melting and Casting Practice: The metals were melted in clay-graphite crucibles in a Hevi-Duty pit-type resistance furnace, equipped with a Leeds and Northrup Micromax Recorder and Controller. After melt down of the base alloys, the additions were made. For each casting, approximately 80 grams of metal were poured into a preheated graphite mold held in a transite flask. The mold (Fig. 1) weighed 320 grams. To determine the effect of superheat upon structure, a set of melts was heated successively to four temperature levels, 705°, 775°, 845°, and 915°C, and test specimens were cast at each level. Prior to each pour, the furnace temperature was held constant for 20 min. Next, a set of melts was put through a superheat cycle and test specimens were cast at melt temperatures of 705" and 915°C successively. The crucibles then were cooled in air to 705°C as deter-mined by immersion thermocouple and additional test specimens were poured. The cooling interval was approximately 1 min. Another set of melts was furnace cooled with the cover slightly ajar and test specimens cast as before. The interval in this case was 15 to 20 min, varying with the superheat temperature. The mold temperature for all these tests was 400°C. To determine the effect of cooling rate without superheat upon structure, a set of melts was heated to 705°C, and castings were poured at mold temperatures of 205", 400°, and 540°C. An interval of 15 min elapsed between each pour. Mold temperatures were measured by a direct reading millivolt-meter, using a chromel-alumel thermocouple located at midwall thickness of the mold. To demonstrate the phenomenon of chemical coarsening, agents such as chromium and beryllium, which had acted as coarseners in a previous investigation,' were added to the A1-Cu alloy. Test speci-

Jan 1, 1955

By Goldye Leeds, Marian Balicki

A SURVEY of literature reveals the scarcity of experimental evidence relating to work hardening and reannealing of silver.'-'" With the exception of the well-known X-ray investigation of silver and other metals by W. A. Wood? the effect of progressive cold working has not been studied. The determination of thermal stability of silver in the work-hardened state by means of isochronal or isothermal annealing has been confined apparently to very high reductions only. In the survey made, no study was encountered which endeavored to produce a complete picture of the changes in various properties due to cold working and subsequent reannealing. To fill these gaps and to assemble data that could be used for the determination of activation energies and of frequency coefficients of primary recrystallization, a systematic experimental approach, which was developed by one of the authors, has been applied to pure silver. Material and Processing The silver used was Handy and Harman fine silver, with a spectroscopic analysis at the testing stage of Cu, 0.0001 to 0.001 pct; Te, 0.0001; Pb, Si, Ca, Mg, and Mn, traces. The material was supplied in the form of a rod 0.406 in. diam and was converted into test samples according to the procedure condensed in Table I. It should be mentioned that air annealing was adopted to simulate industrial practice, though it was realized that annealing in a neutral gas or in a vacuum would be preferred. The usual precautions have been taken to eliminate any structural changes and property changes resulting from the storage of the samples prior to annealing or testing. Thus the wires were kept at the fully annealed stage, and the final wire drawing, which produced the desired degree of work hardening, was done just prior to the final annealing or testing. During the short waiting period, the samples were kept in a thermosflask filled with ice. Even with these precautions some strain-age-hardening or self-annealing could occur. To test such a possibility, wires of different reductions were prepared in the manner adopted and portions of them were immediately tested. The remaining portions were similiarly tested after different periods of storage, both at room and melting-ice temperature. Within experimental error, all samples obtained from a wire of a given percentage of reduction yielded identical values. This result qualified the material for further tests and interpretations, because it showed that either strain-age-hardening and self-annealing were absent, or that these effects fully balanced each other. The final annealing was carried out in an electric resistance furnace automatically controlled to within a 10°F. It was realized that the temperature fluctuations were greater than desired for this type of work. TO diminish the errors due to fluctuations of temperature, the hot junction of the thermocouple was placed as close to the samples as possible; the time of soaking was reduced to 15 min; and the number of samples annealed at different temperatures was increased. It will be seen from Table I that some tests were performed on the same material at rising temperature. These will be discussed elsewhere. Room temperature testing was limited to the determination of some of the mechanical properties that are known to be additive in a degree sufficient to be used for indirect study of the kinetics of the reannealing process, Tensile tests, carried out on a manually operated J. Camillon machine, accurate to within permitted the determination of the ultimate stress (U.S.1 and of the 2 in. elongation, (A,). The proof stress (d,e) has been determined from a series of bend tests carried out on a Tinius Olsen Stiffness Tester by using the offset method. This involved accurate determination for each sample of load-angular deflection curves, finding a

Jan 1, 1952

By James H. Boettcher, W. Durand Eppler

INTRODUCTION In the second quarter of 1979, Rapid Mining Co., Inc. ("Rapid") inquired whether Crocker National Bank ("CNB") would provide $4 million in term loan financing to help ("Dry Creek") acquire the outstanding shares of the Dry Creek Coal Company ("Dry Creek") in West Virginia. Prior to approaching CNB, Rapid had sought financing with the assistance of a financial advisor from a number of commercial banks without success. A summary of the initial terms requested by Rapid is shown in Table 1 compared with the actual terms on which the transaction closed. It is not difficult to note that the two sets of terms differ significantly. This is often the case when financing requests based on the expectations and vision of a mine developer are juxtaposed with more pragmatic requirements of a commercial bank. The "art" and fund of structuring financing plans for mining ventures (highly leveraged acquisitions or grass roots) comes in working with mine developers to arrive at a final financial structure that meets their objectives and constraints as well as those of the bank or other financial institutions providing much of the financing. Beginning with the terms requested by Rapid and ending with the terms that closed the transaction, this article briefly describes the process we went through with Rapid Mining. The Seller and Buyer The Dry Creek Coal Company was established in 1961, after its owner acquired the coal leases from Republic Steel. Republic has mined the primary coal seam from 1948-1961. Dry Creek was owned as a subchapter S corporation (i.e., for federal income tax purposes, income is taxed at the shareholder level) and had been run on a low key basis. Since the company had virtually no debt and limited cash needs, the owner produced primarily when rail cars were available and income was required. Output was therefore erratic as is shown in the top of Table II, but the result was a profitable little company with an attractive free cash position. Because the owner wished to retire and enjoy his wealth in a more readily spendable form, he had put the mine, with stated recoverable reserves of approximately 13 million tons, up for sale. In contrast, Rapid Coal's investors consisted of a number of investors of disparate financial situations. They had agreed upon a primary objective of income maximization and planned an annual production rate of 120,000 TPA which they and the current owner believed realizable. The Formulation of a Financing Structure Figure 1 presents a simplified overview of the sequence of steps taken in the financing process which lasted approximately three months from start to finish. Since banks see many requests for funding and considerble time is required to follow up on each, an important step was determining, after a brief review of the materials provided to us, whether the basic "eonomic entity" was viable. In this case, the size and quality of the reserves, the inherent operating cost characteristics, the sales arrangements, the management/labor situation and Rapid's principles all appeared to be sound enough to warrant investing the time necessary to do a thorough analysis of the project. Once this decision was made, the evaluation and analytic process shown in Figure 2 was initiated. The first and most fundamental concern of any banker is whether the loan will be paid back as scheduled from the cash flow generated by the project. The amount of debt relative to the owner's equity is of course crucial in such a determination. Before the debt/equity issue was addressed, however, a number of more qualitative factors had to be studied and if

Jan 1, 1985

By R. V. Smith

The theory for unsteady radial flow of gas, as simplified by Aronofsky and Jenkins, has been reviewed and compared with actual well performance. This study indicated that the theory should be modified by the introduction of an empirical "rate of flow" function "Y(q)". The expansion of the theory on the flow of gas to include a Y(q) term bridges the gap between the theory of unsteady-state flow of gas and actual gas-well behavior. Apparently, the Y(q) term is a function only of the rate of flow for a given well. The completion factor or skin effect is associated with the Y(q) function in such a manner that at least two or more sets of drawdown or pressure build-up tests are needed to separate the Y(q) function and the completion factor. Since the Y(q) function used in this report represents an energy loss dependent on rate of flow near the well-bore of a gas well which is in addition to the loss required by Darcy's law, the Y(q) function is related to the exponent of the back-pressure curve for a gas well. Techniques and equations are presented which permit the estimation of stabilized and "short-time" deliver-abilities. INTRODUCTION The published theory of radial unsteady-state flow of gas through porous media may be divided into papers1-" which use Darcy's law as a premise and other papers4-7,16-10 which recognize that Darcy's law may not hold for flow into gas wells. Miller8 compared theory based on Darcy's law with actual gas-well behavior and concluded that flow into gas wells deviates from Darcy's law. Houpeurt4,5 in a thorough investigation of flow into gas wells concluded that the flow rate into a gas well is proportional to the difference between the squares of upstream and downstream pressures elevated to a power between 1.0 and 0.5. Houpeurt also concluded that the deviation from Darcy's law is caused by irreversible, kinetic energy exchange between the flowing gas and the porous media. Tek9 presented a complete evaluation of the flow problem in gas wells. Several investigators state that the inclusion of gas compressibility into flow equations based on Darcy's law does not begin to explain the flow problems suggested by gas-well behavior. For many years, natural-gas engineers have realized that gas wells by actual test exhibit behavior which cannot be explained entirely by Darcy's law. Many tests on gas wells have indicated that a value of 0.85 for the exponent in the back-pressure equation is a fair average for many wells. However, Darcy's law either for steady or unsteady-state conditions indicates that the exponent should be 1.0. The purpose of this paper has been to examine this deviation from Darcy's law and to present a reasonable mathematical means of evaluating the deviation. The method presented in this paper combines previous theory with an empirical function to provide a description of gas-well behavior. All equations in this report are for constant terminal-rate-of-flow conditions. While present methods of testing wells usually are not based on this concept, they are believed to approach the constant terminal-rate conditions closely in many tests. However, several gas wells were tested by holding the rates of flow constant in order to approach more closely the constant terminal rate of flow; the results confirm the concepts presented in this paper. REVIEW OF THEORY FOR UNSTEADY-STATE FLOW OF GAS The basic partial differential equation for the flow of natural gas has been given in technical literature; the equation for a cylindrical reservoir with the well in the center is

By A. Schild

The effect of heating a producing well on the rate of oil recovery has been analyzed in the simple case of a well producing oil by a radial drive and in the steady state. Differences of production rates with and without borehole heating have been calculated and plotted; these measure some of the benefits of the thermal recovery process. A striking feature is that the production increase tends rapidly to a constant value for large production rates. Some concrete examples, including a rough comparison with field data. are discussed. Heating requirements have been calculated and plotted on the assumption that the heaters used are 100 per cent efficient. Heating has been thought of as applying only to low volume wells producing heavy oils. However, the calculations suggest that the thermal process considered might be profitable even for some wells producing large quantities of light oil, especially in unconsolidated formations where fracturing is not possible. In the case of wells producing other fluids with the oil or of wells producing partly or wholly by gravity drainage, the theory developed does not apply in detail. It can be expected, however, that any general qualitative be-havior will remain valid. Under normal temperature conditions, high viscosity emulsions sometimes form around the wellbore, lowering the permeability in the vicinity of the well and impeding the production of oil. Borehole heating often prevents such emulsification. This important effect is not easily amenable to mathematical analysis and has not been included in the theory presented here. It should therefore be kept in mind that the benefits due to borehole heating may in fact exceed the values given by the following calculations. INTRODUCTION The recovery of viscous, low gravity oils can often be stimulated by applying heat to the production zone. The higher temperature lowers the viscosity of the oil, increasing its mobility, and therefore its rate of production. One thermal method of recovery 1,2,3,4. consists in operating a heater inside a producing well and, at the same time, producing oil from the well. In this paper a simple theoretical model is analyzed to study the effect of such heating on the recovery of oil. The reservoir mechanics of the process is the only aspect of the problem which is considered here. The details of the heating system are ignored, and it is simply assumed that the heater raises the temperature in the immediate vicinity of the producing well to a pre-assigned temperature T w. Although heating requirements are calculated, these refer only to the heat supplied to the formation and to the oil being produced; they do not include heat losses due to the inefficiency of the heater. A short outline of the theory follows: The heat supplied to the producing well flows out into the formation by means of thermal conduction. At the same time, the flow of oil carries heat by convection from the formation towards the producing well. After sufficient time has elapsed, a steady-state is reached where the temperature, the velocity of the oil, etc., no longer vary with time but are functions of position only. In the steady state the temperature decays like an inverse power from the high value Tw at the wellbore to the original reservoir temperature T. at some distance away from the well. The effect of the high temperature and low oil viscosity near the producing well is the same as if the oil were produced at reservoir temperature To but through a producing well of a larger radius. From this point of view, the energy and money being expended to provide heat

Jan 1, 1958

By G. Sachs, E. J. Riping

All ferrous alloys can be made brittle by straining at sufficiently low temperatures. However, the changes in mechanical properties for different ferrous materials with decreasing testing temperature do not appear to follow any universal law. In particular, complex effects of testing temperature have been observed if cold worked steels were subjected to tensile tests at low temperatures. EFFECTS OF PRESTRAINING AT A TEMPERATURE ABOVE THE TESTING TEMPERATURE ON THE FRACTURE CHARACTERISTICS‡ A considerable amount of data has been presented by a number of investigators on the fracture characteristics of various cold worked steels.' These data usually relate to a two-step procedure first used by Davidenkov,² consisting of stretching by tension to a certain strain or " prestraining" at room temperature and then completing the tensile test, or "testing" at the temperature of liquid air. On the basis of data of this type made available to date, ferrous alloys can be classified into two groups with respect to their fracture characteristics observed on testing at a low temperature after prestraining at room temperature. Very complex phenomena have been observed for all annealed steels. On the other hand, some observations indicate that steels in certain other conditions represent a fundamentally simpler relation. In considering the effect of prestraining at one temperature on the properties obtained at some lower temperature, it should be expected that any cold work reduces the ductility retained in proportion to the magnitude of the cold work. However, the test data presented to date indicate that only heat treated (quenched and tempered) steels appear to conform to this expectation, according to the very limited test data in Fig 1, presented by McAdam, Geil and Mebs. This series of tests, Fig 1, shows that the retained ductility became smaller the larger the prestrain. However, this decrease is less than the amount of prestrain or, in other words, less than the decrease in ductility at the prestraining temperature. These effects of prestraining are fundamentally identical with those observed by Bridgman3 when a steel was prestrained (in tension) under hydrostatic pressure and then subjected to a regular tension test. It appears, therefore, that the basic effect of prestraining under conditions which yield a higher ductility than the (subsequent) testing procedure, consists of gradually increasing the total ductility of the metal from the initial low value of testing to the higher value of prestraining. On the other hand, all annealed steels, if cold worked by tension at room temperature and then tested at a lower temperature, provided that some ductility is retained, showed a far more complex behavior than that discussed above. This relationship is exemplified by Fig 2, for three pearlitic steels.4,5 These particular steels were selected because of the various shapes of their ductility-prestrain curves. All three steels, and any other investigated so far, suffered a rapid decrease in retained (and consequently also in total) ductility when subjected to small pre-strains. Then, after exceeding a certain prestrain it was generally observed that the ductility recovered.* This rather complex behavior of annealed steels may be tentatively correlated with the presence of stretcher strains at small restrains. Heat treated steels do not exhibit stretcher strains. This fact might possibly explain their simpler prestrain-retained ductility relationship. The destructive effect of these stretcher strains may possibly be associated with the presence of triaxiality, which may occur in any highly non-uniform stress and strain state (and which is retained as residual stress after unloading). Even a small degree of triaxiality may then cause a reduction in ductility, or even embrittlement at a sufficiently low testing temperature. The discussion presented above deals with the effects of cold working at a high temperature on the fracturing

Jan 1, 1950

By A. E. Powers, J. F. Libsch

THE simultaneous influence of time and temperature upon the tempering process in steel is well known. Hollomon and Jaffe¹ have expressed the effect of time and temperature upon the progress of tempering by a single parameter, T (c + log t); where T is the absolute temperature; t, the tempering time; and c, a constant characteristic of the steel and treatment. It was found that when hardness data for plain carbon and low alloy steels were plotted vs. this parameter, a master tempering curve was obtained which satisfied all the data for a given steel and a given hardening treatment. Roberts, Grobe, and Moersch² successfully applied the tempering parameter to various tool steels, including high speed steel for tempering times ranging from 6 min to 100 hr. The influence of tempering time and temperature upon the physical properties of high speed steel has also been extensively investigated.'" Recently, the use of induction heating for very rapid tempering treatments has received attention. The authors% have shown that tempering treatments of only a few seconds duration may be successfully applied to plain carbon and low alloy steel. However, the influence of such short tempering treatments in high speed steel has not been explored. Since high speed steel is a highly alloyed steel exhibiting physical reactions during tempering that are often relatively slow and large in magnitude, it is an interesting steel for the study of tempering reactions. It was the purpose of the present investigation, therefore, to study the early progress of reactions leading to secondary hardness in high speed steel, type 6-5-4-2, and to determine if induction-tempering treatments of a few seconds duration are able to produce results equal to those of more conventional long-time tempering cycles. Experimental Details The chemical compositions for two different heats of W-Mo high speed steel used in this study are given in Table I. Table II summarizes the heat treatment given various groups of specimens cut 21/2 in. long and centerless ground to ¼ in. diam. Hardening treatments consisted of preheating to 1600°F (870°C) for V2 hr and then oil quenching from 2250°F (1230°C). Heat I was subjected to the high temperature in a salt bath for 3 min, while specimens of heat II were austenitized in a carbon-block muffle furnace for 10 min. Specimens of series E were immediately refrigerated to — 318°F (— 195°C) in liquid nitrogen following the hardening treatment to transform the major portion of the retained aus-tenite. Specimens of series F and G were subzero cooled to — 100°F (-75°C) in a dry ice-alcohol mixture. Induction tempering was performed with a Lepel high frequency converter operating at a frequency of approximately 300,000 cycles per sec. Heating cycles were controlled and recorded for each specimen using a chromel-alumel thermocouple, percussion welded to the surface of the specimen, and a modified high speed instrument with a timer previously used and described.' Temperature oscillation of the specimens, while being held at the tempering temperature, was ± 15°F (8°C). Tempering Treatments: After hardening, specimens were tempered between 900" and 1500°F (480" and 815°C) to study the progress of retained austenite decomposition and secondary hardening. The specimens tempered in salt for 1 hr (series C, G, and I) were considered to represent conventional treatment and are used for comparison with rapid tempering treatments. Several induction-tempering cycles were employed: 1—flash tempering, i.e., induction heating to the tempering temperature and immediately cooling (series A, E, and F); 2—induction heating for 60 sec at temperature (series B); and 3—double-induction tempering by two successive heating and cooling cycles (series D). All specimens tempered by induction were heated at an initial rate of 450°F (250°C) per sec except those of series E, which were heated at an initial rate of 1300 °F

Jan 1, 1952

By R. L. Pober, L. Kaufman, E. V. Clougherty

Composite structure of hafnium, zirconium, and titanium diboride with additions of metals and/or compound phases were prepared by reactive high-pressure hot pvessing and evaluated in air and in mixtures of oxygen and helium at temperatures up to 2400°K and at linear flow rates of 0.1 to 0.2 ft per sec stp. Oxidation characteristics, principally depth of conversion of diboride to dioxide, were determined by a gas analysis method and by postoxidation metallo-graphic analyses. The best oxidation resistance was observed for hafnium diboride-silicon carbide composite which exhibited a 6-mil conversion to dioxide for a 1-hv oxidation in air at 2200°K compared to a 20-mil recession for hafnium diboride with no additive. Analogous improvements in oxidation resistance were observed for the addition of silicon carbide to zirconium. EARLIER investigationof the oxidation behavior of the diborides of the transition elements of Groups IVA and VA in flowing gas mixtures have produced a ranking of these compounds according to which HfB2 is the most oxidation-resistant followed in turn by ZrB2 > TiB2 > TaBz > NbB2. Other ~tudies~-~ have examined the physical, thermal, and thermodynamic properties of these diborides to provide a sound basis for the more detailed and specialized investigations which are required to generate the information needed to assess the usefulness of such materials in high-temperature oxidizing environments. Recent oxidation studies7 have examined the effect of variations of metal and boron content on the oxidation characteristics of zirconium and hafnium diboride in flowing gas mixtures including air and helium plus oxygen. Results obtained in the latter investigation confirmed the superior oxidation resistance of HfB2 over ZrB2. Moreover, metal-rich compositions of hafnium diboride showed improved oxidation resistance over boron-rich compositions at temperatures up to 2000°K; at higher temperatures the differences are not distinguishable. In particular HfBI.7 exhibited a diboride to dioxide conversion depth of 4 mils in 1 hr at 2000°K; HfB2. 2 exhibited a conversion depth of 16 mils for the same exposure.~ Specimens for the study of metal and boron stoichiometry on the oxidation characteristics of HfB2 and ZrB2 were prepared by high-pressure hot pressing, a specialized type of fabrication which produced dense crack-free bodies of the desired compositions with no significant impurity introductions. The purpose of the present investigation was to explore the possibility of further improving the oxidation resistance of the metal-rich ZrB, and HfB2. The plan to accomplish this objective was based in the formulation of several diboride compositions containing other compounds and phases which are generally known to have good oxidation resistance in one or more types of test environment. Ideally, such additives would also enhance or at least not diminish other boride property values principally mechanical strength and those parameters related to thermal stress resistance. The additions selected for HfBz included zirconium, aluminum, and (Ta + TaB2) designed to produce ternary metal diborides, hafnium to form a discrete HfB phase, chromium to provide a metal skeletal phase, (Hf + Si) to form a discrete hafnium silicide phase, and Sic to provide a discrete second phase. Additions to ZrB2 included A1 + B designed to produce a ternary metal diboride, Zr + Si to form a discrete zirconium silicide phase, and Sic to provide a discrete second phase. All the specimens were prepared by high-pressure hot pressing which was used to advantage to fabricate billets of the variety of compositions desired and suitable for oxidation testing. The present investigation also included the evaluation of high-pressure hot-pressed TiB2and TiB2-20 vol pct Sic, conventionally hot-pressed Boride 2,' and KT silicon carbide. Boride

Jan 1, 1969

By P. R. Sahm, T. V. Pruss, D. A. Gandolfo

Cb 3 Sn powders were hot-pressed to estahlish densi-fication conditions and assess the possible use of such compacts in multiphase structures with ceramic or magnetic inclusions. Superconducting transition temperatures, Tc, were measured as a function of powder particle size, pressing temperature, and second-phase admixtures. The highest transition temperatures were found in coarse powder (5 to 500 u) compacts and were only weakly depended on pressing temperatures up to 1200°C. Fine powders (below 5 p), however, both single-phase CbsSn and Cb3 Sn-composites, showed a stronger dependence on hot-pressing temperatures. While Al2 O3 phase admixtures did not affect T, much more, a Pronounced T, degradation was observed upon the addition of ferrimagnetic Fe2 Mno. 5 Zno.5 O4 powders. Likewise, critical current densities, Jc, at 4.2° K were lowered appreciably in the ferrite doped samples, whereas the neutral A1203 inclusiow gave slightly improved Jc values. MULTIPHASE structures in electronically active materials have recently gained in interest as pointed out by Galasso in a review article.' In superconductors the most widely reported group are eutectic alloys which have been mostly investigated with respect to the proximity effect.2"4 In addition, "artificial eu-tectics", for example in the form of mercury-vycor glass sponge5 or fine niobium wires imbedded in a copper matrix,= have been prepared to attain higher critical fields and critical current densities. The idea was to enhance flux pinning phenomena by second-phase inclusions or ho1es. 7 Flux pinning should also be possible by the introduction of insulator inclusions into a superconducting matrix. Ceramic-metal combinations are most easily produced by hot pressing (= pressure sintering), as it permits an almost unlimited selection of material combinations. Cb 3 Sn has been prepared by vapor phase growths or in the form of thin films. Large compacts must be sintered,1° however, and normally present difficulties. At temperatures below 1350°C insufficient densities are obtained and at higher temperatures the loss of tin due to dissociation upsets the stoichiometry. Hot pressing is a natural approach to circumvent the problems, since one can obtain satisfactory densities despite low sintering temperatures. This work was mostly concerned with establishing conditions to hot press Cb3 Sn and Cb3 Sn multiphase structures (= composites), because no data are presently available, and to evaluate these with respect to their transition temperatures. However, a few measurements on critical current densities were also carried out, in particular to assess the value of ferrimagnetic inclusions. I) EXPERIMENTAL PROCEDURE The experimental procedure involved the preparation of feed material and powders, hot pressing, and evaluation of the resulting ingots. As no attempts were made to synthesize Cb3Sn from the elements during hot pressing, feed material had to be produced. For this purpose, a stoichiometric Cb-Sn powder mixture was compacted into a 3-cm-diam ingot (80,000 psi) and then inserted into a quartz tube and evacuated. Rf heating was employed. Above the tin melting point (230°C) liquid tin was forced out of the ingot, but was pulled back by capillary action after approximately 0.5 hr of continuous pumping at 700°C. Thus, it appears that evacuation at this temperature caused desorption of impurity gas creating wetting surfaces which, later on, favored alloying at relatively low temperatures. After a presintering period of 17 hr at 800°C, the quartz tube was tipped off and sealed into another such larger-diameter tube which, in turn, was connected to a pump system. This configuration permitted a temperature treatment at 1400°C, carried out for 65 hr, without collapsing of the glass walls or unfavorable chemical interaction of Cb3Sn with the quartz. The resulting material was

Jan 1, 1969

By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson' measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans' and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner's data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970

By S. C. Sun, John A. L. Campbell

Objective of the ittvestigation was to determine the electrokinetic differences, if ally, of anthracite lithotypes and thus establish the feasibility of making a coqlstituent separation by froth flotation or other surface-dependent processes. The elec-trokinetic properties were determined by streaming potential methods. In addition, chemical and physical analyses of the lithotypes were made to establish nonsubjec-tive parameters for their diflerentiation. Electrokinetic results indicate a difference in the characteristics of the lithotypes. The isoelectric points of 4 anthracites and 12 lithotypes were obtained. It was suggested that the relative flotation rates of the lithotypes were pH dependent and that the maximum flotation rate of anthracite occurs in an acidic circuit. Although there has been an increased interest in the electrokinetic properties of coal,' research on the subject is still in an early stage of development."' To the authors' knowledge, no electrokinetic studies have been made on coal lithotypes, particularly anthracite litho-types. This paper presents the results of an investigation of the double layer properties displayed at the anthracite/water interface (whole coal and lithotypes) as determined by streaming potential methods. It is hoped that this investigation and related future investigations will provide correlations from which the surface properties of any coal can be predicted and then related to surface-dependent processes such as froth flotation and flocculation. Another aspect of this research, undertaken to determine the physical and chemical parameters necessary for anthracite lithotype differentiation, was previously published.? The number of parameters involved, lithologic, organic and inorganic, and the wide divergence of these parameters within an individual coal limits the practical utilization of the results; however, the result? are of value and of interest in guiding theoretical developments. Keeping the limitations in mind, the results are analyzed in terms of their application to froth flotation processes and are used to indicate the feasibility of making a lithotype separation by flotation. Experimental Procedure Prior to discussing the experimental work per se, it would be of value to establish an understanding of anthracite lithology. Anthracite Lithology: Coal seams display two different modes of variation, rank and type. A coal's position in the continuous series ranging from peats through anthracites determines its rank. The rank of the material under consideration is anthracite. The different bands of coal which constitute a coal seam are distinctly contrasted in regard to physical properties and chemical composition. These megascopic bands are the coal types and are termed lithotypes., A megascopic examination of 11 anthracites revealed three distinct, homogeneous, lithotypes. The classic description of bituminous coal lithotypes as proposed by Stope" was found to be quite adequate for recognizing the three lithotypes in anthracite, namely vitrain, durain, and fusain. The term vitrain describes the brilliant constituent of coal; durain describes dull coal; and fusain is the term applied to fossil charcoal. The anthracites studied were generally found to contain 60-80% vitrain, 10-30% durain, and 1-10% fusain. A complete description of the physical characteristics and chemical composition of the studied lithotypes can be found in a previous publication.' Sample Preparation: Nine of the anthracites used in the investigation were from Pennsylvania, one was from Russia, and one from Wales. Table 1 shows the various designations and sources of the employed anthracites. The letter V, D, or F added to the whole coal designation indicates respectively the vitrain, durain or fusain lithotype of that coal. The samples were carefully collected to avoid contamination. To insure against oxidation, the samples were obtained as fresh as possible and stored under nitrogen or water. Generally a representative sample of the seam and samples containing high concentrations of one or another of the petrographic constituents were secured for each coal. Pure lithotypes were prepared by manual separation and selection. The pure lithotypes and representative samples were ground to —35 mesh and screened to 35 x 48 mesh. The 35 x 48-mesh fraction was then passed over a magnet to remove iron contamination, washed with doubly

Jan 1, 1971

By T. G. R. Rawlins, L. E. Brosselard

Direct platinum carbon replicas have been used to study substrates prior to growth and after initial nu-cleation of the layer. Replicas have been directly stripped and correlations have been made with other replica techniques. Mechanically polished substrates are very flat with occasional areas of "dirt", which is apparently silicon. When such substrates are etched in hydrochloric acid gas, scratches and hexagonal defects (thought to be polishing compound) are revealed, together with areas of apparent redeposition. Chemically polished substrates are much less flat although much more homogeneous in appearance. Heat treat)nents have no effect. Nuclei deposited on these surfaces, using a normal silicon tetrachloride system, have been examined. Nuclei on mechanically polished subsrates occur in random areas only, whereas on chemically polished surfaces they are more uniformly distributed. THE interest in the study of thin films and now their rapidly expanding use in many fields has increased over a period of years. Much of this current interest, particularly in the field of single-crystal or epitaxial thin films, has derived its stimulus not only from possibilities for application but also from fundamental electron-microscope studies which have indicated the manner of growth of such layers from the initial nuclei.1-5 Previous work involving study of growth processes may be divided into three categories. First, vacuum deposition, primarily of metals, on a variety of substrates has been studied by electron microscopy and electron-diffraction techniques. These have shown the three-dimensional aspect of nucleation and the remarkable liquidlike behavior of the growing nuclei which coalesce to form a complete layer. More recently this work has been expanded in two ways: by growth inside the electron microscope this has obvious advantages for kinetic studies; and by growth in ultrahigh vacuum—much of this work has been done on semiconductors.8-11 It is of interest to note that metals, specifically gold deposited on rock salt, will form only polycrystalline layers in ultrahigh vacuum unless the substrate surface is contaminated.12 In general the mode of growth for vacuum-deposited semiconductor films is the same as that for metal films. The second method of growth that has been studied is that of electrodeposition.13,14 The little that has been published suggests that the mode of growth is similar to the vacuum case, except that irregularities may perturb the electric field and disturb the growth process. The third and last primary method of growing epitaxial layers is by use of chemical methods. These techniques have generated much interest and much has been published on them. Considerable electron-microscope work has been done on the defects in the layers; however comparatively little work has been undertaken on the initial nucleation and early stages of growth. Confining ourselves now exclusively to the case of silicon, Charig et a1.15 have considered the growth of silicon on silicon substrates by hydrogen reduction of trichlorosilane, and studied the films by means of replica and transmission techniques. Subsequently they have studied the same system for growth on quartz,16 and with the addition of pyrolysis of silane on quartz and alumina.17 Also Manasevit el al. have studied deposits using silane and silicon tetrachloride on sapphire.18-14 Finally, in this volume studies of deposition on beryllia and sapphire are reported. Although Revesz and Evans20 have examined complete layers, grown by means of the widely used silicon tetrachloride reaction, no detailed examination similar to that published by Charig and Joyce21 for the trichlorosilane system has been given. Therefore this investigation has examined substrate surfaces prior to growth and then nucleation on these surfaces for the silicon tetrachloride system. EXPERIMENTAL In this work the surfaces have been studied by means of standard replica techniques. Because of the very real problems associated with artifacts introduced,22 different replicas and different cleaning

Jan 1, 1967

By L. H. Robinson

A proposed method of drilling utilizes sequential detonation of two types of explosive charges delivered to the hole by a conventional drilling fluid through pipe. A shaped charge first produces a long thin hole. A second charge, called a gauging charge, is pumped into the thin hole, explodes, and enlarges it to full gauge. In one suggested configuration, the explosives are contained in cylindrical capsules 4- to 5-ft long. A drilling head is positioned 2- to 3-ft off bottom. When a capsule is pumped to the bottom of the hole and stops, pressure inside the drill pipe increases and differential pressure detonates the explosive. Primacord along the length of the capsule disintegrates the capsule. The debris circulates out of the hole with the drilling fluid. The gauging-charge action was examined using 2-ft cubes of Berea sandstone. The sandstone (18 per cent porosity) was vacuum-saturated with water and surrounded by concrete. To prevent reflected tensile pulses, the acoustical impedance of the concrete matched that of the sandstone. A 750-psig pressure was applied to a drilling fluid within a shaped-charge-formed hole before detonating the gauging charge. In these tests, 190 gm of rock were removed for each gram of explosive detonated. A similar series of experiments on low-porosity (0.40 per cent) metamorphic limestone provided a more rigorous test. Extensive fracturing from the gauging-charge action prevented an estimate of the volume of the expanded hole. The diameter of the hole was irregular, ranging from about 2 to 4 in, or about fivefold larger than the hole created by the shaped charge. INTRODUCTION In the past, explosives have found a varied but somewhat limited use in the oil field. An early well stimulation technique, still in use today, in vo lves shooting ni troglycerin to en large the borehole and to increase matrix permeability near the wellbore. Bullets and jets are now the conventional method of perforating casing and tubing. Detonations are frequently used to "back off" or "shoot off" stuck pipe and, of course, seismo-graphic work has long depended on explosive-generated pulses to find attractive earth structures. Efforts to use explosives in drilling operations have received limited examinations1-3 which, in one respect, is surprising because explosives offer one way to transmit large amounts of energy directly to the bottom of the hole. Recently, Ostrovskii l described a Russian method of drilling with explosives that utilizes small capsules containing explosives which are pumped into the mud stream to the bottom of a borehole. As the capsules leave the end of the drill pipe, a detonation mechanism is armed. Impact detonates the explosive. In another configuration, two liquids (an oxidizing agent and fuel) in the capsule are separated by a frangible membrane. Separately, the liquids are nonexplosive. Near the bottom of the drill pipe, the capsule passes through a narrow constriction which ruptures the membrane. The mixing of the liquids produces an explosive. Impact is again used to detonate the explosive. About the time Ostrovskii was developing his method, Humble Oil & Refining Co. was independently doing research on another explosive drilling concept based on the sequential detonation of two types -of explosive charges. The proposed technique consisted of alternately pumping a shaped charge and then a "gauging charge" down a well. The shaped charge should drill a long, tapered hole, and the gauging charge should expand it to full gauge. This paper presents the visualized drilling concept and gives results of laboratory work which showed that sequential firing of charges can form hole at an attractive charge-to-rock removal ratio. An important finding was that increased environmental pressure, which is to be expected in wells, increases rock removal efficiency of the gauging charge.

Jan 1, 1966

By M. R. J. Wyllie, Walter D. Rose

The use of electrical well logs for the quantitative determination of such reservoir parameters as connate water saturation, formation permeability and connate water salinity has recently been attracting the attention of a number of workers1,2,3,4,5. While the theory of the determination of connate water salinity from the self potential S.P. log has received rather detailed treatment, relatively little attention has been paid to the theoretical aspects involved in the quantitative interpretation of resistivity data. It is clear that if electrical well logs can be used for the quantitative evaluation of physical characteristics of reservoir rock, they will provide a valuable tool to supplement cheaply information obtained by more laborious core analysis. In certain cases it is conceivable that the coring program could be considerably curtailed if the electric log could be relied upon to give reasonably accurate quantitative information. It is our object in this paper to examine the theoretical basis of quantitative log interpretation as expressed in such well-established logging concepts as formation factor and cementation factor. It is also our object to investigate the physical aspects of the rela- tionship which is presumed to exist between resistivity index and brine saturation in reservoir rock. In particular, we will endeavor to draw attention to the fact that it is possible to express these logging concepts in terms of capillary pressure-saturation relationships, permeability and tortuosity, parameters which we will consider in this paper to be fundamentally indicative of rock texture. The probability of being able to obtain from log recordings alone the data theoretically essential to permit quantitative log interpretatiou will be examined, and consideration will also be given to the problem of formulating simple semi-empirical relationships for use in the field. THEORETICAL CONSIDERATIONS The concept of formation resistivity factor, or as it is now commonly called, formation factor, appears to have been introduced by G. E. Archie",". Formation resistivity factor as defined by Archie is the resistivity of a rock 100 per cent brine-saturated divided by the resistivity of the brine. This relationship had previously been used by physical chemists and the concept is, for example, implicit in an early treatment by Fricke7 of the conductivity of aqueous slurries. Archie was able to establish the fact that although the relationship between formation factor and porosity did not change too greatly for different rock textures, the relationship between formation factor and permeability was markedly dependent on rock texture. The relationship found by Archie between formation factor and porosity was expanded by H. Guyod8. Archie had suggested that the formation factor, F, could be expressed in terms of the porosity, F, as follows: F =F-m .... (11 where, F = effective porosity fraction of the sand, and, m = an exponent greater than about 1.3. Guyod introduced the term cementation factor for the exponent, m, since it may be qualitatively shown that formation factor for any given porosity tends to increase as the sand becomes more cemented. It would appear that the concept of m as an exponent representing the cementation in a sand is strictly only of qualitative value, since the quantitative estimation of m by means other than the determination of F and F has not been possible. Guyod suggests that m can be estimated from a visual examination of a sample of rock, but this method appears to be both arbitrary and unreliable. It can be said, however, that in intergranular reservoirs of practical interest, the range of m is from about 1.4 to 3.0. A possible explanation for the fact that m is found to lie between these limits will be offered below. The determination of formation factor is an essential preliminary to the

Jan 1, 1950

By Douglas J. Harvey

The surface tension of lead-tellurium alloys (in the range 0 to 6.70 at. pct Te) ad lead-arsenic alloys (in the range 0 to 10.53 at. pct As) has been examined by the maximum bubble pressure method. The surface tension of high purity lead can be expressed over a range of temperatures (M.P. to 750°C) by the relationship = 512 — 0.133t. Arsenic and lellurium were both found to be surface active in lead. The surface excess concentration at 700°C was .found to be constant at 0.74 x 10-10 moles per sq cm for tellurium. The surface excess of arsenic at 700°C varied between 0.26 x 10-10 moles per sq cm at 0.16 at. pct to 1.5 x 10-10 moles per sq cm at 8.3 at. pet. The surface tension of lead has been investigated sporadically over the last 90 years. The first recorded study was made by Quincke1 who used a rather crude application of the drop-weight method. Hogness2 obtained the first reliable value for the surface tension of lead by measuring the pressure necessary to force the liquid metal from the end of a small capillary of known radius. Hogness gives the empirical formula: ?(surface tension)= 444 - 0.077 (l-327) which describes the relationship between surface tension and temperature ("C); This work was followed by that of Bircumshaw3 who applied the two-capillar maximum bubble pressure method of Sugden.4 The values published by Bircumshaw are in good agreement with those found by Hogness. Matuyama5 examined the surface tension of lead by the drop weight method. However, the values found are somewhat higher than those previously reported. More recent investigations by Greenaway6 and by Melford and oar' have resulted in data which are not in close agreement, but which are well within the expected range at most temperature levels. The study of the surface tension of lead alloys began with Drath and sauerwald8 who examined the lead-bismuth system. They found that the surface tension values of the alloys in this system deviated only slightly from the ideal mixture rule. Matuyarna5 examined the lead-antimony system. Bircumshaw the lead-tin, and the lead-indium system was studied by Hoar and Me1ford.10 The results of these investi- gations are summarized in Fig. 1. It may be seen that the data vary only slightly from the ideal mixture rule. As none of the metals studied and reported in the literature has a very interesting effect on the surface tension of lead,*the next logical step might be to examine the effect of metals of low solubility or nonmetals having some liquid solubility. Baes, and Kellogg11 have pointed out that the elements most likely to be surface active in liquid metals are ones of limited solubility in the liquid state and possessing weak intermolecular bonding forces in the solid state. Therefore, Group V, VI and VII nonmetals are most likely to be surface active. It was decided to examine the effect of a borderline metal, arsenic, and a nonmetal tellurium. Arsenic forms a eutectic with lead having a melting point of 290°C and a composition of 6.9 at. pct As.13 Pure arsenic sublimes when heated above 610°C. Even though alloying with lead lowers the vapor pressure, fumes containing arsenic are evolved at a very noticeable rate when lead-arsenic alloys are heated above 650°C. Tellurium raises the liquidus temperature of lead sharply to 904°C,14 the melting point of PbTe (lead-telluride). The solid solubility of tellurium in lead was determined by Greenwood and worner15 to be 0.0007 at. pct at room temperature. EXPERIMENTAL METHOD Surface Tension Measurement—The two capillary maximum bubble pressure method for measuring surface tension developed by Sugden,4 and used later

Jan 1, 1962