Search Documents

By Paul C. Merritt

Chrysotile asbestos producers in Quebec may soon experience a unique situation-i.e., strong competition from American ore sources for the short fiber market west of the Mississippi River. This com- petition will be forthcoming from Copperopolis and Coalinga, two deposits now being developed on opposite flanks of the San Joaquin Valley in central California. The combined output now planned from both deposits is 100,000 tons annually, equivalent to about 50% of the annual market demand in the western, central and Gulf States, and more than twice the tonnage sold in 1960 by all other American asbestos producers combined. The principal companies involved in these new undertakings are Jefferson Lake Asbestos Corp. (subsidiary of Jefferson Lake Sulphur Co.), Hidden Splendor Mining Co., Coalinga Asbestos Co. (Johns- Manville Corp. in conjunction with Kern County Land Co.), Union Carbide Corp., and Asbestos Corp. Ltd. Jefferson Lake's principal interest is at Copperopolis where the company's new 70,000-ton per yr mill recently went on stream. The company also holds some claims at Coalinga, but this latter area is better known as the site where Hidden Splendor, Coalinga Asbestos Co. and Todd Industries (a local company) have established operating mines and mills capable of turning out 30,000 tons of fiber each year. Coalinga is also the site of exploration by Union Carbide Nuclear and Asbestos Corp. Ltd.

Jan 9, 1962

By AIME AIME

THE Petroleum Division will hold its first fall meeting in Tulsa, Okla., Thursday and Friday,' Oct. 2 and 3, preceding the. International Petroleum Exposition that opens there on Oct. 4. Headquarters will be at the Hotel Mayo, and members planning to attend should make reservations promptly because of the large attendance expected at the Exposition. The program for Thursday will feature production engineering problems and that for Friday the unit operation of oil pools. The principal papers planned for the various sessions are as follows:

Jan 1, 1930

By P. Greenfield, C. C. Smith, A. M. Taylor

J. E. Harris (Berkeley Nucclear Laboratories, England)—Greenfield et al.11 attribute abrupt changes in slope of their log o/log i curves for heat-treated Mg/0.5 pet Zr alloy (zA) to &apos;atmosphere&apos; locking. It is proposed here that a more reasonable explanation of the apparent strengthening at low rates of strain can be based on precipitation either during the preanneal or during the creep tests. All the tests were carried out above 0.5 Tm where solute atmospheres are likely to be largely evaporated2 and can migrate sufficiently rapidly so as not to impose any &apos;drag&apos; on the moving dislocations. McLean3 has derived an expression for determining the temperature Tc above which, due to the high-migration rate of the atmospheres, Cottrell or Suzuki locking can play no part in determining creep strength. This expression, which holds for an applied shear stress of not greater than 5 X 107 dynes per sq cm is: Tc/Tm= 7/6.8 - log10? where i = secondary creep rate The values for T, corresponding to the maximum and minimum reported creep rates at each temperature have been calculated from the data of Greenfield et al. These are given in Table VII. All the test temperatures were above T,, the margin being greater for the higher temperatures and for the lower strain rates where the breaks in the log s/log ? curves occurred. Dorn and his collaborators14, 17 have studied systematically the effect of solute hardening on the creep properties of an A1/3.2 at. pet Mg alloy. In the temperature range where strain aging occurred in tensile tests, abnormally high-activation energies for secondary creep were obtained but at temperatures above 0.43 Tm, solute alloying did not have any effect on the creep parameters. Moreover, there have been no reports of any strain aging phenomenon during elevated temperature tensile tests with ZA material.18 Instead of the observed strengthening being due to atmosphere locking, it is now proposed that precipitates play an important role in enhancing the creep strength of the material. There are two possibilities—precipitation of zirconium hydride during the high-temperature preanneal and/or precipitation of the hydride or a-zirconium during creep. On the basis of the former the results can be interpreted in terms of a critical stress being necessary to force the dislocations through or over preexisting precipitates. From the latter, if the strengthening is due to pre- cipitation during the test then hardening should be associated with a critical strain rate. At low rates of strain, time is available during the tests for precipitation to occur either directly onto dislocations (thus pinning them) or generally throughout the matrix (which would impede dislocation movements). Examination of the data of Greenfield et al. suggests that both mechanisms may be operative since they observed precipitation during creep and also found that their alloys exhibited high-creep strength in the early stages of the low-stress tests, i.e., before creep-induced precipitation had time to occur. It is not easy to understand why they considered that precipitation of zirconium hydride is unlikely to occur at 600°C while it can take place in tests in air at as low a temperature as 200°C. Precipitation of the hydride during the preanneal cannot be ruled out merely on the basis of metallographic examination. Hydride precipitates in ZA type alloys are very small and can only be accurately resolved in the electron microscope.9 For example, in this laboratory20 hydride platelets with major dimensions <(1/10) µ have been observed by electron transmission through thin film specimens of hy-drogenated ZA material. Complex interactions between dislocations and such particles are illustrated in Fig. 12. Additional evidence for precipitation during pre-annealing is provided by the data presented in Greenfield&apos;s Fig. 1 and Table IT. These show that the creep strength at 200o and 400°C increases with the time of preanneal at 600°C. Such increases cannot be explained on the basis of increases in grain size alone for further improvements in strength were observed when the material was annealed for longer times than that required to stabilize the grains. Although the main discussion is confined to ZA material, similar arguments can be used against the strain aging hypothesis proposed to explain the binary Mg/Mn alloy data. In this case no precipitation is possible during the preanneal, but precipitation-hardening during creep can occur.

Jan 1, 1962

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.&apos; The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.&apos; The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By Robin P. Gardner

Prior work by the author has established that closedform analytic solutions can be obtained for certain steady-state and transient types of operation of open circuit, continuous ball mills. This is possible when the tanks-in-series concept is used with the segregated flow or lumped parameter milling models. Such models should be useful (whenever they apply) in any calculational application since they are efficient and simple to program for digital computation. For example, they might be used within a computer program such as that developed by Herbst et al. for the calculation of model

Jan 1, 1975

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.&apos;&apos; The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-&apos; "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

By H. T. Hildage

Although Greater New York does not bear any resemblance to a great mining district, the mining operations that are being conducted in and about the city are both extensive and interesting in character. With regard to the extent, it may be mentioned that, at present, there is more dynamite used in New York than in any mining district in the United States; that there are under construction about 38 miles of tunnel, and that 66 miles more are projected, most of which must be constructed .in the near future; that since 1903 at least 2,000,000 tons of earth has been removed in underground work, in addition to about 3,500,000 tons that has been removed in open-cut in connection with tunnel-work, and many times this quantity that has been removed in excavating foundations for buildings not connected with tunnel-work; and that there are to-day probably more than 5,000 men engaged in mining-work in and about New lrork City. These undertakings include almost every operation connected with underground work, from exploration by means of trench and boring, to the sinking of large shafts and the driving of large tunnels through every kind of ground from hard rock to soft, semi-fluid silt and quicksand. It is proposed in this paper to give a general description of some of the methods and appliances used in the opening-up of a " mine " in a large city, and a brief description of some of the &&apos;mines" now being developed in New York, connecting as far as possible the methods described with the particular work for which they were designed, in order to give a general idea of the

Jan 1, 1908

By James W. Baxter

Underground mining of limestone is becoming increasingly practicable in Illinois. Most quarries are near rivers on the western and southern borders where competition for land use is intensive. Increasing demands for stone can be met by expanded mining with access by adits in existing quarries and by inclines and shafts at downdip sites. Geologic, hydrologic, and engineering conditions indicate that deep mines in the Ste. Genevieve, Salem, Ullin, and basal Burlington limestones of Mississippian age and in the Moredock member of the Dunleith formation of Ordovician age are particularly feasible, but development will require prudent exploration and planning to ensure that the product will be of good quality.

Jan 1, 1981

By F. H. Deily, Jean M. Quets, Milton E. Wadsworth, John R. 222-000-000-012 Lewis, D. S. Rowley, R. J. Howe

Samples of synthetic magnetite were reduced in hydrogen-water vapor atmospheres in the temperature range 450o to 900oC. The reaction was always surface controlled, indicating the final products of reaction are nonfirotective. Three separate cases have been identified from the kinetic results: Case I, reduction of magnetite to iron below 570°C; Case II, reduction of magnetite to iron above 570°C; and Case 111, reduction of magnetite to wustite above 570 oC. In Cases I and 111 the kinetics have been explained by the formation of oxygen anion vacancies in the magnetite surface followed by associated diffusional processes. In Case 11 the observed kinetics have been related to the concentration of iron cation vacancies in the wustite layer formed, followed by associated steady-state diffusional processes. The concentration of cation vacancies in the wustite is maintained constant by the magnetite-wustite equilibrium. THE reduction of the oxides of iron has been a subject of study and interest for many years. However, few attempts have been made to interpret the results in terms of the mechanism of reduction of an iron oxide by either hydrogen or carbon monoxide. Stalhane and Malmberg&apos; using CO, H2, and CO-Hz mixtures, developed the rate expression: where m = mass of oxide reduced, t = time, k = a constant, s = surface area, P = partial pressure of of CO or H,, and P, = partial pressure of the reducing gas at equilibrium. The rate of reaction per unit area was proportional to the difference between the partial pressure of the reducing gas and its pressure at equilibrium. Hansen, Bitsianes, and Joseph2 studied the reduction of pellets of hematite to magnetite with mixtures of CO-CO,. They concluded that below 450°C the reaction proceeded according to a model in which CO reacts with the hematite surface producing an oxygen ion vacancy. The rate controlling step was then assumed to be oxygen ion diffusion through vacancies resulting in the formation of magnetite. They derived an expression giving the rate of reduction proportional to the cO/CO, ratio. Recently McKewan3 published results for the reduction of magnetite spheres in atmospheres below 570°C. He explained his results by an equation of the form where K, is the equilibrium constant for wustite-iron equilibrium attributed to the formation of wustite as an intermediate in the reduction of magnetite. According to McKewan, Kp is an equilibrium constant for H, -HO adsorption in which oxygen is deposited on the surface from the H,Oand subsequently acts as a poison for reduction by hydrogen. Sample Preparation and Experiments. In this work the authors used the same apparatus and experimental procedure employed in the hydrogen reduction of magnetite. Sintered disk samples weighing approximately 1.5 g and measuring 1.2 cm in diameter and 0.25 cm in thickness were prepared by a method described previously.4 Partial pressures of hydrogen and water vapor were controlled by bubbling hydrogen through a series of flasks containing distilled and deionized water maintained at constant temperature in an oil bath. The total flow rate of the reacting gases—hydrogen and water vapor—was approximately 0.5 liter per min. The entire external system was maintained at a temperature above the oil bath to prevent condensation of water vapor. This was accomplished by wrapping electrical resistance elements over all surfaces. The glass column containing the weighing system-a McBain balance suspended from a gold chain-was enclosed in an aluminum tube heated by nichrome resistance wire enclosed in an insulating material. The temperature of the glass column was held constant by means of a series of thermocouples connected in parallel to a Leeds and Northrup temperature controller. This was necessary since variations in temperature resulted in expansion and contraction of the glass column and could be readily observed with the cathetometer. The spring extensions were measured through a window with a gaertner cathe-

Jan 1, 1962

By B. F. Oliver, C. W. Haworth

Pure tin and Sn-0.5pct Pb ingots have been frozen unidirectionally from the base. For quiescent melts that were initially undercooled, a transition from lower eqlciaxed structure to an upper columnar structure is found in the alloy ingots. Columnar to equi-axed back to columnar transitions are observed in superheated alloy ingots, but no such equiaxed band is observed impure tin. The reproducible equiaxed band is associated with a thermal undercooling followed by a recalescence. This undercooling is <5"C, whereas the critical (maximum obtainable) under-cooling for both the pure tin and the alloys used is -20°C. A similar undercooling is observed at the same position in the pure tin ingots, although in this case no clear transition in structure can be seen. The structure of the pure tin ingots is either entirely columnar or mixed columnar-equiaxed. A consideration of the detailed thermal history of the ingots indicates that the ingot macrostructures are determined by the occurrence of a local therlnal undercooling in conjunction with nuclei multiplication and transport mechanisrris. GENERALLY it is found that a pure metal ingot solidifies so as to produce an entirely columnar structure. Frequently an alloy ingot is found to have a columnar outer zone and an equiaxed central portion. Early systematic work to examine the factors controlling the formation of the equiaxed structure was reported by Northcott&apos; who showed that, for copper alloys frozen unidirectionally with a given ingot practice, the alloying element influenced the length of columnar crystals and the extent of the equiaxed structure. Northcott showed that alloys with a wider freezing range more readily produced the equiaxed structure. The nucleation process can be important in producing equiaxed structures; frequently an alloy which readily solidifies with an entirely columnar structure will produce an entirely equiaxed structure when a nucleating agent is added to the melt.&apos; The formation of the equiaxed structure was attributed by Winegard and chalmers3 to the presence of constitutional supercooling; that is, a region of liquid in front of the growing solid could have a temperature below its equilibrium liquidus temperature. Thus, with a small enough temperature gradient in the liquid, it was suggested that the presence of constitutional supercooling may be sufficient to bring about the nuclea-tion necessary for the formation of an equiaxed structure. Although this explanation is plausible, and may be relevant in many ingots, Walker has described an experiment&apos; for which constitutional supercooling seems to be an unlikely cause of nucleation. A Ni-20 pct Cu alloy, repeatedly undercooled more than 50"C, was crystallized and found to show the typical colum-nar-equiaxed structure. The separation between the liquidus and the solidus for the alloy is 40°C. Thus, in this experiment the nucleation required for the formation of the equiaxed structure must have come about in some other way than by the nucleation catalysis constitutional supercooling hypothesis. Chalmers has suggested more recently5 that nuclei (in a typical ingot) are present immediately after pouring and are prevented from redissolving by the constitutional supercooling effect. More recently Uhlman, Seward, Jackson, and ~unt&apos; have shown direct evidence using ice and organic materials that freeze dendritically that the "remelt mechanism" may be an extremely effective crystal multiplication process during the freezing of ingots under conditions involving dendritic growth. JSlia" experimentally demonstrated the detachment of dendrite arms. chernov14 has analyzed the dendrite arm detachment process as a coarsening phenomena driven by the minimization of interphase area. Katta-mis and ~lemings" working with undercooled steel melts give evidence supporting this mechanism. Mechanisms of dendrite arm detachment such as those assisted by convection are believed to be the origin of the macrostructures obtained in this study. This study makes no attempt to distinguish the relative contributions of these mechanisms. The object of the present work was to obtain accurate temperature measurements during the solidification of an ingot and to correlate these measurements with the formation of equiaxed grains in the resulting ingot structures. Similar previous work is very limited. The measurements carried out by Northcott are neither sufficiently extensive nor sufficiently accurate for any interpretation. Plaskett and winegard7 carried out experiments on A1-Mg alloys in which they observed values of the temperature gradient, G, in the liquid and rate of freezing, R (for a given alloy solute content Co), at the transition from a columnar to an equiaxed structure. They reported that equiaxed crystals were produced at values of G/G approximately proportional to the solidus composition. Similar experiments using Pb-Sn alloys carried out by £111011" showed a linear relation between G/R and the solidus composition. However, the thermocouples were in the mold wall rather than in the melt and, in one case, ingot surfaces were examined. There is ambiguity in the meaning of the values of G and R measured in all these experiments. APPARATUS AND EXPERIMENTAL PROCEDURE Alloys were prepared by induction melting 99.999 pct Sn and 99.999 pct Pb to form a Sn-0.5 wt pct Pb alloy in air in a graphite crucible and casting into a cylindrical graphite mold 6 in. long, 1 in. in diarn , and with a & in. wall thickness. This mold was mounted on a copper base through which cooling water could be

Jan 1, 1968

By R. H. Swallow, George Hess

C. G. BALL*—These maps are obvi-~,usly quite helpful in many types of mining engineering, but I want to find out if the prints which you obtain in the first step toward making any aerial contour map have already been corrected for tilt. Is that done afterwards only if you are going into the process of making a contour map ? GEORGE HESS (authors&apos; reply)— The tilt correction is the first step in either compiling the mosaic or compiling the total map. They must be corrected. C. G. BALL—But are the contact prints themselves corrected for tilt? GEORGE HESS—They are not corrected. E. R. KAISER†—I enjoyed this paper very much, and am glad to learn that the methods have a high degree of accuracy and are in use in the coal industry. Accuracy in dimensions is understandable from the paper. Would you tell us how accuracy can be obtained in the vertical dimensions by means of the photographs so as to permit drawing contour lines? GEORGE HESS—To explain our process, even in a limited way, is quite a large order. However, the basic principle involved is the measurement of parallax by viewing two overlapping photographs stereoscopically. It would almost be necessary to have the various instruments here on view to adequately explain their operation. E. R. KAISER—Are the elevations for reference obtained at more than four points ? GEORGE HESS—The pattern of control is four points obtained in the corners. Primarily. that is to restitute the picture and horizontalize it. The vertical control points are read ill on the stereometer and a direct comparison is made while draw- ing the contour lines. You do have to have those four points. But one stereoscopic pair of 5 ft contours has some 340 acres on it, consequently for every four points picked up 340 acres are contoured. E. R. KAISER—How does your method compare with that used by the military reconnaissance during World War II? GEORGE HESS—The Army did not get into this refined mapping. Most of their work has been reconnaissance mapping by taking one vertical and two oblique views. Basically, the same principle is used. Our maps are for engineering purposes. The Army was primarily interested in reconnaissance. E. R. KAISER—You could take more than 48 pictures in one flight? GEORGE HESS—Yes, the Brock camera accomodates 48 pictures per magazine. We are limited by the hours of greatest light, though, 2 hr before high noon, and 2 hr after high noon. Shadows do affect the picture. The shadows can-

Jan 1, 1950

By W. M. Rutherford

A knowledge of the limits of miscibility between reservoir oil and possible injection fluids is required for selection of the optimum miscible-injection fluid. Limits of miscibility can be estimated from the results of equilibrium phase-behavior experiments. They can also be determined by means of displacement experiments conducted in a high-pressure sandpack. This paper describes the equipment and procedure which have been developed for determining miscibility conditions by stable displacement. A systematic series of displacements of a West Texas reservoir oil was carried out. The results indicate that, at constant pressure, miscibility is a function only of the pseudocritical temperature of the injection gas. This fact, together with improved experimental methods, makes the displacement technique a rapid, reliable means for determining miscibility conditions. In conjunction with the displacement experiments, phase diagrams were constructed for the oil with dry gas and propane and with dry gas and ethane. Phase behavior of the methane-ethane-propane system was determined at 110°F. The experimental work demonstrates the feasibility of using ethane-rich gases to reduce cost and pressure requirements for miscible displacement. INTRODUCTION In recent years, interest in the miscible displacement of oil by light hydrocarbon mixtures has been high. Many pilot and a few field scale projects have been started.1 These projects have made use of various methods for achieving miscibility: (1) the LPG-slug process, (2) the enriched-gas-drive process and (3) the high-pressure gas-drive process. Some field projects have been successful; the results of others are debatable. In general, projects which have performed best have involved the injection of an appreciable fraction of a pore volume of miscible material. Economical application of miscible displacement depends strongly on the cost of the miscible-injection fluid. If an appreciable fraction of a pore volume of material is required for successful application of these methods, a precise knowledge of the minimum requirements for miscibility in terms of composition of injection fluid is essential. Therefore, reliable experimental methods for determining miscibility conditions are important, and a procedure for estimating these conditions from the composition of the reservoir fluid is highly desirable. The subject of this paper is the problem of determining conditions which result in miscible displacement of oil by light hydrocarbon mixtures. Miscibility conditions can be estimated by means of equilibrium experiments conducted in a PVT cell, or they can be determined by means of high-pressure displacement experiments. This paper describes the equipment and procedure which have been developed for the determination of miscibility by high-pressure displacement experiments. These methods have been applied to the displacement of a West Texas reservoir oil with mixtures of dry gas, ethane and propane. In conjunction with the displacement experiments, triangular phase diagrams have been constructed for mixtures of the oil with dry gas and propane and with dry gas and ethane. The effect of injection-gas composition on conditions for miscible displacement in high-pressure sandpacks and cores has been the subject of several published papers.2-5 The experimental methods used in these investigations were such that displacements were unstable, and the effects of fingering and/or gravity layover are clearly evident in the results. Miscibility conditions were probably correct in spite of the instability phenomena, but the experiments evidently were time-consuming, and limited data were reported. Systematic high-pressure flow studies which would support a correlation of miscibility conditions have not been reported; however, Wilson5 has proposed the use of pseudocritical temperature of the injection gas as a parameter and Benham, et al,6 have based a miscibility correlation on observed and calculated equilibrium data.

By J. F. Evers, S. Sadiq, F. W. Preston, G. W. Swift

Proper scaling of unsteady-state flow in laboratory gas reservoir models can be achieved if the permeability/fractional porosity ratio is less than 0.5 md. Porous media meeting this specification can be obtained from mixtures of sand and Portland cement provided (1) the water/cement ratio is in the range of 0.35 to 0.40, (2) the sand/cement ratio is in the range of 1/1 to 2/1, (3) the sand grain size is in the range of 48-100 to 18-28 mesh, (4) the mortar curing time is 7 days or more and (5) the cured mortar is dried under vacuum to reduce the temperature level employed during the drying process. The areal homogeneity of the mortars tested is reasonably good, although significant trends in vertical permeability were noted. The Klinkenberg and non-Darcy coefficients of mortar are such that proper scaling of these effects in the laboratory model could be expected. INTRODUCTION A long term deliverability prediction for a gas well is generally based on data determined from flow tests that are of short duration relative to the producing life of the well. These data, together with an estimate of gas reserves in place, form the basis for establishing the parameters of the mathematical model used to predict performance at future times. Results obtained from a mathematical model represent only an interpretation of the physical process being modeled. Experimental verification of the production process from discovery to abandonment is needed where production occurs under carefully controlled conditions. Ideally, one might consider such an experiment to be conducted in the field. Even if the cost of such an experiment could be justified, the time required would make it impractical to consider. However, if the time scaling problem could be handled properly, an experimental model of the gas reservoir production process could provide the necessary data to study the mechanisms of the production process in a reasonable time period. An experimental model has been designed and constructed using the data of this study as a basis. The model reservoir system consists of one producing well located at the center of a right-circular cylinder of porous material. Ten to 15 observation wells are located at strategic offset positions from the producing well. These wells, and the producing well, are fitted with pressure transducers so that the pressure-time history can be recorded at various radial and azimuthal positions in the drainage area during the entire production life of the system. Time is scaled in the model so that the time required to produce gas from discovery pressure to abandonment pressure is about 2 hours. This compares with a 20-year producing life in the model&apos;s field counterpart and gives a time scale factor of approximately 1:100,000. DESIGN CRITERIA To establish design criteria for the experimental model, the reservoir is considered to be a finite right-circular cylinder of radius rr, and height h with a producing well of radius rw located at the center and completed through the producing formation. This reservoir consists of a porous medium which has a uniform permeability k and gas porosity and the gas contained in the reservoir has density p, viscosity µ and molecular weight M. Initially, the pressure at all points within the reservoir is uniform at po. and the reservoir temperature is T. Since the reservoir production process has been demonstrated to occur in two distinct transient modes for either Darcy or non-Darcy flow,l it is

By P. R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,&apos; and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.&apos;.&apos; Bunker Hill Co. of Kellogg, Idaho, supplied the ore sample used in these tests. The sample was typical of the ore milled in 1949 and contained 4.52 pct Pb and 1.08 pct Zn. A flotation test made by the author with potassium ethyl xanthate as a collector, the same flotation reagents, and the same grind employed in regular Bunker Hill mill practice was the standard for comparing results with the compounds and derivatives of guanidine. The compounds and derivatives of guanidine are only fair collectors of galena. However, if potassium ethyl xanthate were used in the galena float, its presence later in the sphalerite float would make it impossible to introduce another type of collector and be certain which collector contributed the result, so the compound or derivative of guanidine under test was used in both the galena and sphalerite floats in Table I. On both the galena and the sphalerite in the Bunker Hill ore, the depressing action of sodium cyanide and zinc sulfate is much greater with collectors of the guanidine type than with the xanthates. If the depressing agents are left out when a guanidine type of collector is used, but a pH of 8.6 is maintained with either lime or sodium carbonate, the depressing action is approximately the same as in the standard xanthate test. Consequently the depressing agents, sodium cyanide and zinc, were not used in the galena floats of tests 1226, 1228, and 1286, Table I, so the galena floats would be on a comparable basis with the standard xanthate test. As shown by the tests in Table I, the loss in the tail when diphenyl guanidine is used is 8.3 to 9.3 pct, as compared to 17.6 pct with potassium ethyl xanthate, or a recovery of 2.3 to 2.0 lb more zinc. Concentrate grade is 13.7 pct with potassium ethyl xanthate and increases to 22.9 and 31.8 pct with diphenyl guanidine, showing a much higher selectivity. Unless the Barrett&apos;s No. 4 coal tar creosote is considered to be a collector, no collector other than diphenyl guanidine is present in the tests, Nos. 1226, 1228, and 1286. Tests 1218, 1253, and 1263 in Table I1 were run to check the effect of the depressing agents used in flotation of the galena (sodium cyanide and zinc sulfate) upon subsequent flotation of sphalerite by diphenyl guanidine. Urea was substituted for potassium ethyl xanthate in tests 1253 and 1263 because it is a good collector for galena and a poor one for sphalerite, and the effect of the depressing agents is more marked with urea than with potassium ethyl xanthate. Test 1205 checks the effect of urea alone without any depressing agents when used for the flotation of galena. Table I1 shows that diphenyl guanidine as a collector for sphalerite is compatible with other flotation reagents used in floating galena. When the depressing agents sodium cyanide and zinc sulfate are used in the galena flotation step, the amount of lime in the sphalerite flotation must be increased (compare 1253 and 1263). Table I11 gives some of the compounds of guanidine which were tested and compared. Some of the compounds and derivatives of guanidine* are solu- * Diphenyl guanidine is in commercial production and is available on the market. ble in water and others are not. Those tested were fed dry. When an organic collector is promising, its compounds and derivatives should be tested and their comparative collecting power recorded. Eventually, in this way, it may be possible to discover some of the essential chemical characteristics of a good collector. For example, it is interesting to compare the diphenyl and dibutyl derivatives in Table IV with those of urea in Table 111, Example 3, U. S. Patent 2,664,198. All are good collectors. Table I shows some of the effects of lime on recovery of sphalerite by diphenyl guanidine. Table V

Jan 1, 1960

A. 0. ASHMAN, Palmerton, Pa. (written discussion *.).-Mr. Newcomb&apos;s paper has interested me greatly, as I have had numerous experiences along this line. I do not think enough emphasis can be put on his warn-ing to keep platinum couples free from contact with quartz tubes, as silica shows a tendency to alloy with platinum to a surprising degree even at low temperatures. I have frequently had evidence of silica contamination in a perfectly good tube, in which there was seemingly no possibility of a reducing atmosphere. This is rather important as it seems to be common practice to insulate, as well as protect, the wires by means of- capillary silica tubing, thus allowing the entire wire to be in contact with the silica. The best way to mount a couple in a silica protecting tube is by means of double-bore porcelain insulating tubes, the protecting tube being slightly longer than the couple so as to leave a space between the couple and the end of the tube. In this way there is no possibility of contamination from silica. In no case should silica capillary tubes be used to insulate platinum wires. Mr. Newcomb states that there is still much to be desired in pyro-meter protecting tubes; this is in keeping with my experience. From a practical standpoint there is not a satisfactory pyrometer tube on the market for high temperatures; with all clue respect to the many improve-ments and good work recently done in this line. I believe that the whole future development of pyrometry is dependent on the development of suitable refractories. With suitable refractories, for example, Darling&apos;s1 work with liquid couples could be developed to a practical basis, making possible the use of base-metal couples to replace platinum.

Jan 12, 1919

By H. Rosenthal, A. L. Jamieson

Stress-corrosion cracking of copper-base alloys is of considerable importance and has been the subject of many investigations which employed various accelerated tests and long-time service tests. The outstand¬ing accelerated tests used are variations of either the mercury cracking test reported by Rogers in 1905( 1)2 or the ammonia test reported in 1910(2). The ease of applica¬tion of the mercury test is probably the reason industry adopted it. Subsequent investigation of this test(3,4) revealed that a minimum threshold stress was necessary before mercury cracking could develop. Since season cracking has been found in some instances in caliber 0.3o ammunition which has passed the mercury test, it is evident that the threshold stress value of the mercury test may be too high for dis¬tinguishing between acceptable and un¬acceptable caliber 0.30 cartridge cases. This condition has naturally led to the study of an ammonia test with its ability to cause cracks with almost any stress level. But the lack of a definite threshold value means that standards are necessary for evaluating the results of the ammonia test.

Jan 1, 1945

By Robert A. Bauer

This study showed that diametral point-load testing performed parallel to the bedding planes of highly anisotropic sedimentary rocks produced inconsistent results that cannot be used to accurately estimate uniaxial compressive strength. Axial point-load values from tests performed normal to bedding planes and evaluated by the T500 index produce good correlations with the uniaxial compressive strength values obtained for five different rock types. A strong correlation also existed between the moisture content and the uniaxial compressive strength of the tested lithologies. A combination of axial point-load and moisture content indices produces the best correlation with the uniaxial compressive strength test results.

Jan 1, 1984

By Owen W. Ellis, Telfer E. Norman

The use of cadmium as a base for bearing metals is one of the most interesting recent developments in this field. It has caused a strong demand for cadmium and a marked rise in its price. It appeared to the authors, therefore, that the situation might be relieved for users if acceptable substitutes could be developed. A preliminary investigation has revealed that to some extent mercury may be substituted for cadmium. Whether its use is justified cannot be stated at this time. Most of the authors&apos; work has indicated that the addition of mercury to alloys of cadmium and nickel detracts from their desirable physical properties; but this work has not been extended to cover service tests, which might reveal that the addition of low percentages of mercury to the cadmium-base alloys would improve their performance. The results of tests made by the authors are therefore briefly summarized for this paper. Table 1 gives the proportions of the metals used in preparing the alloys. After preparation of these alloys, th composition was checked by chemical analysis. Particular care taken to ensure that the nickel content did not vary appreciably from 1 per cent.

Jan 1, 1938

By Owen W. Ellis, Telfer E. Norman

The use of cadmium as a base for bearing metals is one of the most interesting recent developments in this field. It has caused a strong demand for cadmium and a marked rise in its price. It appeared to the authors, therefore, that the situation might be relieved for users if acceptable substitutes could be developed. A preliminary investigation has revealed that to some extent mercury may be substituted for cadmium. Whether its use is justified cannot be stated at this time. Most of the authors&apos; work has indicated that the addition of mercury to alloys of cadmium and nickel detracts from their desirable physical properties; but this work has not been extended to cover service tests, which might reveal that the addition of low percentages of mercury to the cadmium-base alloys would improve their performance. The results of tests made by the authors are therefore briefly summarized for this paper. Table 1 gives the proportions of the metals used in preparing the alloys. After preparation of these alloys, th composition was checked by chemical analysis. Particular care taken to ensure that the nickel content did not vary appreciably from 1 per cent.

Jan 1, 1938

By J. M. Eldridge, P. Balk

Phosphosilicate glass films were formed, by reacting gaseous P2O5 with SiO2, over a large range of temperature (800° to 1200°C) and gas phase composition (nearly two orders of magnitude of effective P2Ospressure). The film compositions generally corresponded with the liquidus curve, delineating the maximum solubility of the tridymite Phase of SiO 2 in phosphosilicate liquid solution at the temperature of film formation. It is shown that the P2O5 concentration of the phosphosilicate liquid film tends to decrease by reaction with the underlying SiO 2 layer until the liquidus curve is reached. The validity of the thermodynamic argument used in this explanation is supported by the results of a determination of the composition of borosili-cute films, prepared by reacting gaseous B2O3 with SiO2 at different temperatures. The kinetics of phosphosilicate film formation were described by a model predicated on a steady-state diffusion of P2O5 through the film. UNDERSTANDING of the processes leading to formation of phosphosilicate and borosilicate glasses is of great importance for producing passivating layers on FET devices. Passivating films with optimum characteristics are preferably formed in a separate step, independent of the doping of the semiconductor.&apos; The results of an investigation carried out to gain improved insight into the mechanism of glass formation are presented in this paper. It would be expected that application of the known Pz05-Si02 and B 2 O 3-SiO2 phase diagrams should be useful in extending understanding of the glass-forming processes. However, the question of the propriety of treating thermally grown SiO2 in these binary oxide systems by the methods of equilibrium thermodynamics must be considered when this application is attempted. Although Sah et a1.&apos; and Allen et al. 3 investigated the kinetics of formation of phosphosilicate glass (PSG), they failed to adequately relate their diffusion models to the occurrence of experimentally observed phases in the PSG/SiO 2/Si system. Horuichi and yamaguchi4 investigated the diffusion of boron through an oxide layer and described their results in terms of a model similar to that of Sah and coworkers. More recently, Kooi 5 and Snow and Deal6 reported the compositions of PSG films formed by depositing P2 O 5 onto SiO2. These compositions apparently coincide with those at the liquidus curve delineating the maximum solubility of crystalline SiO2 in phosphosilicate liquid solutions. These authors did not discuss the thermodynamic implications of their results on the structure of thermally grown SiO2 films. The structure of thermally grown Sio2 films and that of vitreous silica are generally thought to be quite similar. Since the solubility of a substance depends on its structure, it is relevant that the solubility of vitreous silica in water7 is highly reproducible, like the solubility of thermally grown SiOz in phosphosilicate liquid. Furthermore, the vitreous silica-water system appears to be in true thermodynamic equilibrium (viz., the same solubility value can be approached from both supersaturated and under-saturated solutions). Sosman7 suggested that a type of two-dimensional lattice may form at the silica/solution interface, resulting in the observed solubility behavior that is characteristic of a crystalline solid. An alternative explanation may be that vitreous silica has a microcrystalline grain structure. Other investigators have suggested that vitreous silica has essentially the structure of B cristobalite,&apos; or is composed of microcrystals of p tridymite or cristobalite, or a mixture of both. Presumably the grain size would be sufficiently large to minimize any appreciable contribution of the grain boundaries to the solubility of the crystalline matrix. The present investigation was carried out to clarify the significance of the boundaries in the Pa,-SiO, and B2O3-SiO2 Systems in determining PSG and BSG (borosilicate) film compositions. Furthermore, the kinetic data for PSG film formation were extended, using a wider range of formation parameters than were previously reported. One model describing the kinetics of film formation will be presented that is compatible with the thermodynamics of the Pa5-Si02 system. EXPERIMENTAL PROCEDURE Glass Film Preparation. SiO2 films (1000 to 8000A thick) were obtained by oxidation of silicon substrates in dry O2 at 1100°C. PSG and BSG films were prepared by exposing these layers to gaseous oxides obtained by reacting high-purity POC13 and BBr3, respectively, with O2. A double-columned saturator was used to ensure complete saturation of the N 2 carrier

Jan 1, 1969