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By Martin Rubenstein

CdS crystals have been grown from a number of metallic solvents such as bismuth, tin, lead, and cadmium. Etching studies have shown that plastic deformation occurs if the crystals are not removed from the solvent prior to the solidification of the solvent, on cooling. The deformed crystals show a umique exciton fluorescence as a function of edge dislocation density. If one grows the CdS in the eutectic alloy of the above four metals (commonly called Wood's metal) the crystals can be removed from the solvent with hot water and no plastic deformation occurs. In this paper, the liquidus solubility measurements of CdS, as a function of temperature, are presented. The data were obtained using a high -temperature filtration technique. CADMIUM-SULFIDE crystals have been grown from a number of metallic solvents1 such as cadmium, bismuth, tin, and lead. Liquidus solubilities of CdS in cadmium,2 bismuth,3 and tin4 have already been measured. Crystals of CdS, in all four metals, have been grown by solution growth: 1) by cooling a saturated solution and 2) by a solution transport method.1'"1 CdS crystals grown in these four solvents have a few characteristics in common: 1) 1.8°K photolumines-cent emission consisted mainly of the radiative recombination of the bound exciton commonly known as I,, 2) slip lines which could easily be seen by the naked eye, and 3) edge dislocation densities in the order of l05 per cu cm.1 It was decided that these slip lines and the high edge dislocation densities were caused by a plastic deformation of the CdS crystals. It was felt that this plastic deformation did not occur during the growth of the crystals nor during the cooling of the solution, but did occur when the solvent which was in contact with the crystals froze. If these assumptions were valid, the slip lines and the high number of dislocations could be reduced or eliminated by removing the crystals from the solvent before the solvent froze. Since crystals of CdS had already been grown separately in such solvents as bismuth, lead, tin, and cadmium, it was felt that crystals could be grown in a eutectic mixture of these four metals. In this work a eutectic (or near eutectic) mixture of bismuth, lead, tin and cadmium in the proportion 50, 26.5, 13.5, and 10 wt pct, respectively, was used to grow CdS crystals. Such a mixture has a melting point of about 70°C and is close in composition to the alloy commonly known as Wood's metals. If the crystals could be grown from this mixture of solvents, and if hot water (>75°C) could be used to separate the crystals of CdS from the metallic solvent, it was hoped that CdS crystals could be grown with little or no plastic deformation which had been ob- served when crystals were grown from these solvents uncombined. CdS crystals were grown from this low melting eutectic mixture of bismuth, lead, tin, and cadmium using the solvent transport method. CdS powder and the appropriate amount of metals were sealed in a quartz tube under a pressure of about 5 X 10-6 torr. This ampule was then placed in a vertical position in a furnace. The temperature was raised to about 900°C. The furnace was designed so that the top of the liquid column within the ampule was between 10° to 40°C higher than the bottom of the liquid column. These temperatures were measured on the outside of the quartz ampule. The ampule was maintained at temperature for 7 to 14 days (depending on the temperature at which transport was taking place) and then the furnace temperature was lowered until the temperature was about 125°C. The ampule was then removed from the furnace, placed in water maintained at about 90°C, and opened in this 90°C environment. The crystals could then be removed from this two-phase liquid (Wood's metal and water) by mechanically picking them out. Alternatively, the crystals could be quantitatively removed by adding an excess of mercury to the mixture of metals, crystals, and hot water. The hot solution of metals and the hot water could be evacuated using a small diameter tube connected to a vacuum. Small amounts of mercury and water could be removed by heating the crystals in vacuum. Crystals prepared using this technique showed no evidence of slip. However, some of these crystals did show edge dislocation densities as high as l04 per cu cm. Some few selected crystals showed no dislocations. Single crystals of CdS were grown as large as 5 by 5 by 0.5 mm. The ampules for the growth of these crystals were 13 mm O.D., 11 mm I.D., 150 mm! LIQUIDUS SOLUBILITY MEASUREMENTS The CdS starting materials was G.E. 118-8-2 powder which was fired in H2S at 1000°C, and then a vapor transport technique5 was applied to produce a "sound" mass of CdS. The Wood's metal was prepared by weighing out bismuth, lead, tin, and cadmium in the proportions of 50, 26.5, 13.5, and 10 wt pct, respectively. The bismuth, cadmium, and lead were from the American Smelting and Refining Co. (ASARCO) and all had purities of 99.999+ pct. The tin was 99.9999 pct spectroscopic grade from the Vulcan Materials Co. The appropriate mixture was placed in a quartz tube, evacuated to a pressure of 5 X 10-6 torr, melted to a liquid, cooled to room temperature under this same vacuum. This ingot was then placed in another quartz tube, evacuated to 5 x l0-6 torr, and sealed off under vacuum. The ampule was then horizontally placed in a furnace. The temperature was raised to 600°C, and over a period of several hours the ampule was vigorously shaken several times. The ampule was then removed from the furnace, and the metallic liquid was

Jan 1, 1970

By O. M. TUPPER

REQUIRING a finer ground clay than that obtainable with a dry pan or hammer mill, the Clay Corporation of California installed a five-roller, low- side Raymond impact mill at its Lincoln plant in 1925 and since then has been economically grinding fire clay with a moisture content as high as 15 per cent. This was one of the first, if not the first, of this type of mill to be used in the grinding of clay on the Pacific coast. The pulverizer consists of a die-ring, lying in a horizontal plane, enclosed in a sheet-iron housing. A vertical shaft supports a spider from which five rolls are suspended in such a way as to always have them bearing on the die-ring. The vertical mill shaft is driven by means of beveled gear and pinion from a horizontal shaft which is connected by belt with a 60-hp. motor with suitable pulleys to give a speed of 175 r.p.m. A large fan which has a speed of 1100 r.p.m. and is belt connected to a 40-hp. motor is connected to the mill housing. The discharge end of the fan is in turn connected to a cyclone dust collector.

Jan 1, 1929

By W. A. Burns

Vertical flow is an important mechanism in many petroleum reservoirs. Yet no adequate method has heretofore been proposed for determining the in-situ vertical permeability in a reasonable length of time. Core measurements of vertical permeability do not necessarily represent effective in-situ values. Cores may be representative of only localized pockets of high or low permeability, and total reliance on cores might cause one to overlook the presence of vertical fractures altogether. Conventional single-well tests, interference tests, and pulse tests commonly are used to determine horizontal transmissibility, khh/u, but generally are not designed to measure vertical trans-missibility or other groups containing vertical permeability, ku. A new well test described here provides a measure of in-situ vertical permeability as well as the previously measurable horizontal permeability. This "vertical test" determines the vertical diffusivity, kv/gcu, and horizontal transmissibility, khd1/u (where dl is the length of injection or production perforations). The test is basically a short-term interference or pulse test normally lasting less than a day. Conventional down-hole equipment is used between two isolated sets of perforations in the same well, as shown in Fig. 1. A "layer-cake" description of a reservoir can be obtained by running two or more vertical tests in the same well, each over different vertical intervals. Each test can be analyzed for the effective vertical and horizontal properties of the interval tested. In addition, a vertical well test can determine the effective- ness of a shale barrier or tight zone by testing across it. Field use to date of vertical testing has confirmed its utility in reservoir description. Mathematical Basis Interpretation of vertical tests for ku and kh is based on comparison of measured pressure response with computer-generated response. Pressure behavior during a vertical test in a homogeneous, anisotropic, infinite-acting reservoir (infinite in radial extent and bounded in both directions vertically) is given by the diffusion equation for slightly compressible fluids with negligible gravity effects.l A schematic diagram of the problem is presented in Fig. 2, and an analytic solution, based on the image

Jan 1, 1970

By P. K. Leung, S. R. Allada, P. M. Dranchuk, D. Quon

The alternating direction explicit procedure (ADEP) makes use of the boundary conditions to reduce multi-dimensional problems to a series of one-dimensional problems. The method, previously applied to reservoirs containing only an under-saturated oil, has now been extended to cover the case of natural gas reservoirs. l his involves solving a non-linear partial differential equation, application of the procedure is straightforward and no calcuIational problems were encountered. INTRODUCTION There has been a growing interest in formulating mathematical models of petroleum and natural gas reservoirs — models which permit the engineer to examine and evaluate the physical and economic consequences of various alternative production policies. The tremendous reduction in the cost of solving such models in recent years has made possible their use as an almost routine management tool. This reduction is the result not only of improved computer hardware but also of the development of more efficient mathematical techniques. The present paper is concerned with the application of a recently proposed numerical method (ADEP) to two-dimensional gas reservoirs. STATEMENT OF THE PROBLEM Given a two-dimensional Region R, bounded by a closed Curve C (Fig. 1) such that the behavior on Curve C is known, the differential mass balance for each fluid phase in R, neglecting gravitational effects and assuming Darcy's law for fluid transport, can be written as:

Jan 1, 1967

By W. Rostoker

Single isothermal sections were constructed for the titonium-rich corners of the systems Ti-Fe-O, Ti-Cr-O, and Ti-Ni-0 with a view to locating the shape and disposition of the ternary intermediate-phase fields for the compounds isomorphous with Fe3W3C. IN a previous note,' it was reported that a group of ternary intermediate phases existed which occurred in the general composition range Ti,X,O-Ti&O where X was one of the following elements: copper, nickel, cobalt, iron, or manganese. In two instances, binary intermediate phases occurred (Ti²Cu and Ti²Ni) which appeared to be isomorphous. The X-ray diffraction patterns of the phases could be indexed on a cubic lattice whose cell edge was of the order of 11 kX. Karlsson2 stated that the line extinctions and line intensities indicated that these phases were isomorphous with Fe³W³C and therefore belonged to the space group Oh. This author also noted that no unique phase of this type occurred at the composition Ti,Cr,O. This latter statement was accepted as true at the time the previous technical note was written.' However, work continued along these lines and that reported here has shown that a phase isomorphous with Fe³W³C does exist in the vicinity of the composition Ti³Cr³O but not at or near Ti4 Cr²O. The lattice parameter of this phase was found to be 13.01 kX. Metallographic examination of both as-cast and annealed specimens of these supposed ternary oxide phases disclosed structures which were far from single phase in many instances. It was considered a point of some interest to locate more positively the composition coordinates of the single-phase fields. To this end, single isothermal sections for the systems Ti-Fe-O (1000°C), Ti-Cr-0 (1000°C), and Ti-Ni-0 (900"C) were constructed. Phase relationships were studied by both X-ray diffraction and metallotrra~hic methods. Allovs were prepared as 10 g buttons by melting in a noncon-sumable electrode, water-cooled copper crucible arc-melting furnace using a helium atmosphere. Oxygen was introduced quantitatively by the use of weighed amounts of TiO² or TiO. Iodide titanium and the purest available alloying metals were used. All results are discussed in terms of the nominal composition of the melts. Previous experience with making oxygen-rich alloys had shown that oxygen losses were not significant if a homogeneous melt was produced. Weight-loss measurements were used to check loss in metallics during melting. Anneals were conducted in evacuated Vycor bulbs, and annealing times ranged from 24 hr at 1000 °C to 48 hr at 900°C. To achieve equilibrium in certain sluggish alloys, seven-day anneals were used. Debye-Scherrer powder patterns were taken in a 14 cm diam camera using filtered CuK radiation (K² = 1.541232 kX; K., = 1.53739 kX). Specimens were prepared by crushing and screening previously annealed buttons. In general, the X-ray diffraction results were used to identify the major phases, while the metallographic examinations were more useful in indicating the number of phases present. By the use of the combined results and general fundamental rules governing ternary equilibrium, it was possible to construct isothermal sections in good detail. In some instances where auxiliary lattice-parameter data were available, it was possible to lay down tie lines and to locate more positively corners of three-phase fields. Isothermal Section of the System Ti-Fe-O at 1000°C The binary systems Ti-O³ and Ti-Fe4 have been published. Binary phases, TiO, TiFe, and TiFe2, are likely to be encountered in the titanium-rich corner of the system. The structures are NaCl (Bl), CsCl (B2), and MgZn, (C14) types, respectively. Although preliminary X-ray diffraction studies indicated the presence of a ternary phase in the composition range Ti,Fe,O-TiJ?e,O, metallographic examination of two specimens at these compositions revealed the presence of other phases. Thirty-eight alloys were used to delineate the phase boundaries of the isothermal section illustrated in Fig. 1. The five almost single-phase ter-

Jan 1, 1956

By P. Niessen, W. C. Winegard, C. J. Beingessner

DURING the last 10 years, several grain-growth studies have been made using zone-refined metals with controlled amounts of solute to elucidate the interaction of solute with moving boundaries. In all these studies, it was more or less implicitly assumed that the alloys used were, after recrystallization and grain growth, homogeneous within the grains with respect to solute and lattice defects. This note deals with observations made on microstructures originating from solidification of dilute alloys and from grain growth. Briefly, the experimental procedure used in these studies was the following: zone-refined cadmium and master alloys were melted and cast in Pyrex under vacuum to produce bars 14 mm in diam and about 150 mm long. These bars were cut into 8-mm-thick slices which were mechanically and chemically polished. The specimens were then deformed 30 pct in compression and given a 1-week anneal at 260°C in argon. After this anneal, a second deformation produced completely recrystallized samples 4 mm thick. The time-temperature controlled anneals were carried out in a bath of silicone oil. After the grain-growth anneal, the specimens were polished in Gil-man's' solution (33 g CrOs, 6 g NazSO, in 100 ml of water). Several etches were used depending on the alloy investigated, but mostly a mixture of concentrated HC1 and HNOj (98:2 vol) was employed. In all the alloys examined, the ease with which substructures could be revealed depended strongly on the crystallographic orientation of the surfaces of the grains. However, very frequently the microstructures to be discussed here etched up over broad areas comprising several grains. Fig. 1 is a micrograph of a Cd-0.05 at. pct Mg alloy annealed for 100 sec at 270°C. Different substructures are seen in this photograph. A denotes the now existing grain boundaries. The well-defined lines and points marked B are the remains of a solidification substructure. The lines are boundaries between cell colonies, and the points are nodes located on regular two-dimensional cells. This cellular structure has the same appearance as that found by weinberg2 for rapidly quenched Zn-Au alloys. The "ghost boundaries", marked C, are very similar in appearance to a grain boundary array in a polycrystalline sample. Repeated polishing and etching showed that all the substructures observed were three-dimensional. To date, the ghost boundaries have been clearly observed in all samples containing 0.005, 0.01, 0.05, and 1 at. pct Mg, and in samples containing 0.01 at. pct Zn. Attempts to outline these ghost boundaries in cadmium alloys containing 0.01 at. pct Ag and Au were only partially successful. In these alloys, parallel lines, having a resemblance to the ghost boundaries in the Cd-Mg and Cd-Zn alloys, were observed, but it was not possible to obtain complete arrays of ghost boundaries which extended over several grains. It is possible that a different etch than that presently employed would reveal the ghost boundaries in the Cd-Au and Cd-Ag alloys as clearly as in the Cd-Zn and Cd-Mg alloys. A close examination of the ghost structure showed that it consisted of linear etch-pit arrays, Fig. 2. The ghost boundaries were resolvable even in grains which showed over-all faceting due to the etching, as seen in the corner of Fig. 2. The general appearance of the ghost structure suggests that it originated during grain growth. This is supported by the observation that the mesh width in the ghost-boundary array generally increased with increasing final grain size. To test whether the ghost structure was formed during the long homogenizing anneal or during the grain-growth anneal, some as-cast samples were deformed and given a grain-growth anneal. This anneal was terminated by air cooling or

Jan 1, 1967

By Jack L. Taylor

As expected from similar crystal structures and favorable atomic size factors, titanium, vanadium, and molybdenum are completely soluble in one another above the transformation temperature of titanium. The fl phase parameters of the continuous solid solution are shown graphically. Limiting compositions for retained fl phase have been determined. VANADIUM and molybdenum both have body-centered-cubic structures at all temperatures and, from the atomic diameter comparison factor, 3.9 pct, would be expected to form a complete series of solid solutions. The existence of complete solubility has been confirmed by work' at the Jet Propulsion Laboratory. Furthermore, vanadium and molybdenum have favorable atomic size factors to form complete binary solid solutions with the B phase, high temperature form of titanium, which also has body-centered-cubic structure. Pietro-kowsky and Duwez' and Hansen et al." have established the existence of the complete series of solutions in these binary systems. It would be logical, therefore, to expect that p-titanium, vanadium, and molybdenum would be completely soluble in one

Jan 1, 1957

By W. A. Wood, H. M. Bendler

Cylindrical fatigue specimens of OFHC* copper were subjected to alternating torsion while under axial tension. The superimposed tension strongly influenced the fatigue life of the specimens as well as causing characteristic changes in the structure of the fissures that form and develop throughout the life of the specimen. A further effect of the superimposed tension is a continuous extension of the specimen throughout its life in a manner formally similar to creep at elevated temperatures. RECENTLY, studies of the structural changes leading to fracture of metals by fatigue have been made by a technique which reveals, in section, the lattice distortion arising from slip movements inside the metal and the disturbances built up by these slip movements at the metal surface.1'2 According to this approach, fatigue develops as follows: a) fine slip movements concentrate in bands, producing little strain-hardening and thus permitting abnormal totals of plastic strain before fracture and, therefore, abnormal amounts of lattice distortion along each slip band; b) both forward and backward slip movements occur in each band which, according to their distribution across the band, may build up surface disturbances that include sharp notches; c) these notches early in the life of a specimen penetrate the distorted slip zones and transform them into deep, fine fissures; d) the fissures on continued cycling locally saturate the metal and cause local collapse in the form of a microcrack. Thus, the significant consequence of fatigue or cyclic

Jan 1, 1962

By K. J. Gill, P. Chiotti

Thermal, metallographic, and vapor pressure data were obtained to establish the phase diagram for the thorium-zinc system. Four compounds corresponding to the stoichiometric formulas Th2Zn, ThZn2, ThZn4, and Th2Zn17 were observed. The melting points of these compounds under constrained vapor conditions were found to be 1055°, 1105°, 1095°, and 1015°C respectively. Four eutectics exist in this system with the following eutectic temperatures and thorium contents in wt pct: 1040°C, 89 Th; 945°C, 79 Th; 1045°C, 55 Th; and 995°C, 35 Th. The standard free energy, enthalpy, and entropy of formation for the compounds were determined from zinc vapor pressure data. ALTHOUGH the thorium-zinc system has been of technical importance in the commercial production of thorium and more recently of interest to some proposed pyrometallurgical separations processes for reactor fuels or blanket materials no detailed investigation of this system has been made in the past. Some previous work has been reviewed by Hanssen.1 The existence of four compounds, Th2Zn17, ThZn4, ThZn2, and Th2Zn has been established and their crystal structures have been studied by X-ray diffraction techniques.2-4 Smirnov et al.,5 determined the solubility of thorium in zinc and investigated the two-phase region between Th2Zn17 and zinc. They calculated some of the thermodynamic properties for these alloys from emf measurements on the cells Th/ThCl4(fused)/Cl2, C and Th2Zn17(s)+ Zn (l)/ThCl4(fused)/Cl2, C. The possibility of reaction between the anode materials and fused thorium tetrachloride to produce a lower valent thorium salt would have to be resolved in order to evaluate the results obtained. The purpose of the present investigation is to establish the phase diagram for the thorium-zinc system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure and Ames Lalboratory thorium. The major impurities in the thorium in parts per million were oxygen—1250, carbon—350, iron—100, nitrogen-75, and silicon—70. The metals in the form of several small massive pieces, total weight about 30 g, were cleaned with acid, washed with water and acetone, and dried just prior to their use for alloy preparation. Tantalum containers were found to be suitable for all the alloys studied and were used throughout this investigation. The metals were sealed inside of small 1-in.-diam tantalum crucibles by welding on preformed tantalum covers. A small thermocouple well made from 1/8-in.-diam tantalum tubing was welded in the bottom of each crucible. These crucibles were enclosed in

Jan 1, 1962

By W. C. Hagel, H. J. Beattie

Seven austenitic alloys of varions base compositions and minor-alloy additions were solution-treated, aged systematically between 1200oand 1800oF, and examined by X-ray and electron metallography. Intragranular preczpitations of µ, Laves, s, ?', Ni3Ti, and x phases were observed as a function of composition and aging time and temperatwre. Phase solubility limits were detevtnitzed within 100Fo intervals. These inter metallic compounds fall into two distinct general classes, and whichever class predomznates depends on base composition. It has become increasingly evident that multicom-ponent austenitic alloys are well characterized by their precipitation processes. Since certain groups of elements act as one, the relationships among these processes are reasonably simple; complete identification of such processes is usually attainable by a systematic aging study with a combination of techniques centered on microscopy and diffraction. Several nickel- and cobalt-base alloys illustrating cellular precipitation and its interaction with general precipitation were reported previously.1 The group of alloys covered in the present paper demonstrates precipitation-hardening reactions involving two distinct classes of intermetallic compounds where the predominating class appears to depend on base composition. This dependency ties in with a crystal-chemistry regularity first observed some twenty years ago by Laves and Wallbaum but never amplified to our knowledge. Results of electron-microscope and X-ray diffraction studies on systematically aged hot-rolled alloys known commercially as S-816, S-590, Rene-41, Incoloy-901, M-308, and M-647 are reported here. Some of these alloys have previously undergone minor-phase analyses by other investiators. Alloy S-816 was investigated by Rosenbaum, Lane and Grant,3 and Weeton and Signorelli.4 Rosenbaum found only CbC in hot-rolled bars. Lane and Grant found CbC and a small amount of M6C in the cast structure and stated that both carbides form during aging, most of the precipitation being CbC. Weeton and Signorelli found CbC, M23C6 and a weak indication of a phase after a slow step-down cooling cycle from 2250°F. Rosenbaum also investigated hot-rolled samples of S-590 and identified CbC and M6C. Preliminary information on Rene-41, gained partly from the present work, was reported by Morris.5 Long-time precipitation phenomena in Incoloy-901 at 1350°Fwere investigated by Clark and Iwanski.B heir raw data re- semble those of our present heat with 0.1 pct B, while their interpretation of these data resembles our interpretation of data from another heat with only 0.001 pct B; they made no statement as to boron content. No previous minor-phase studies of alloys M-308 or M-647 have been reported. EXPERIMENTAL METHODS Table I gives alloy compositions in both weight and atomic percent. Specimens were solution-treated from 1700º to 2200ºF, aged at logarithmic-time intervals up to 1000 hours between 1200 and 1800 F, and examined in accordance with procedures previously described in detail. ' ' Phase extractions were carried out in electrolytic cells containing 800 ml of either 7 pct HC1 in denatured ethanol or 20 pct H3PO4 in water. After electrolysis for 48 hr at 0.1 to 0.2 amp per sq inch, residues were separated by filtration or centrifuging. X-ray powder patterns of residues were recorded on a diffractometer for accuracy and on film for sensitivity. Lattice parameters were calculated by least-squares analyses of indexed sin 8 values, and relative abundances were estimated from intensities of strongest lines of each phase. These phase abundances denote relative amounts with respect to each other rather than to the alloy. Mechanically polished specimens were etched in a freshly mixed solution of 92 pct HC1, 5 pct H2SO4, and 3 pct HNO3. Parlodion replicas for the electron microscope were chromium-shadowed in high vacuum at a glancing angle of 20deg. All electron micrographs are reproduced here with the shadowing source above. The correspondence betweenelectronmicrostructures and phases identified by X-rays was established by a high redundancy of correlation between relative amounts at different stages of aging and examination above and below critical transformation or solubility temperatures. EXPERIMENTAL RESULTS S-816 and S-590—The phases found in S-816 and S-590 after various aging and solutioning treatments are listed in Table 11. These data and the observed

Jan 1, 1962

By William B. Hughes

The rubber-sleeve core barrel was developed to improve core recovery from unconsolidated sands, where it is most difficult to obtain cores with conventional barrels. The use of a rubber-sleeve core retainer, together with other departures from clsual design, has required a considerable amount of testing to prove its op-erability. Tests run in shallow experimental holes and in drilling wells in the U. S. and Vemzuela have, to a large extent, proved the operation of the barrel. Internal mechanism troubles, such as sandbinding of the sleeve, have been largely overcome. Cores have been recovered from completely unconsolidated sands where conventional coring has almost been abandoned because of poor recovery. In addition to retaining the core until brought to the surface, the barrel gives a "packaged-ar-cut" core, which is coilverzient for handling and transportatiorz. In the initial work, drag blade cutters, roller cutters, and tungsten carbide insert cutters were usrd for cutting unconsolidated sands. Further bit head development is presently being conducted using diamond heads in unconsolidated sands where shaler, hard sands, and limestones are encountered in adjacent formations. Thir work should render the barrel capable of cratting and recovering most types of formations, possibly including broken and frac- tured fornlations. This development is being carried on in cooperation with a diamond bit manufacturer. INTRODUCTIO N For many years the oil industry has needed greater recovery of cores from unconsolidated formations. Conventional equipment has been used to core unconsolidated sands with little success. Specifically, a core barrel was needed which would recover unconsolidated sands in a condition that would give useful reservoir information. DEVELOPMENT OF 'THE RUBBER-SLEEVE CORE BARREL Basic Requirements of Unconsolidated Sand Corino The basic need was defined as a core barrel that would obtain a continuous unconsolidated core with sand grains in place as deposited in the formation. A preliminary survey of coring equipment and search of the literature pointed out the weaknesses of conventional core barrels. Laboratory tests using unconsolidated sand in a metal tube simulated actual sand movement into the core barrel during conventional coring. In conventional barrels the core sometimes crumbles and bridges, or fails under compressive column action, becomes oversize, and wedges against the walls of the inner barrel. The core barrel requirements established by the surveys and preliminary tests are as follows. 1. The core should be held to- gether as it is cut so it cannot crumble and bridge against the walls of the coring tool, care being taken not to permit damage from fluid circulation. 2. The core should be continuously supported as it is cut so it will not have to support itself in compression. 3. The core should be packaged in the barrel to retain an undisturbed condition during the trip out of the well. The packaging should be such that the core can be removed from the barrel and shipped to the core analysis laboratory without physical disturbance or alteration of fluid content by exposure to the atmosphere. Operation of the Rubber-Sleeve Core Barrel The rubber-sleeve core barrel (Fig. 1) meets the basic requirements for the recovery of unconsolidated sands.

By D. Turnbull, H. N. Treaftis

Precipitation of tin from Pb-Sn alloys (lead-rich) occurs by the nucleation and growth of hemispherical cells which consist of tin lomelloe interspersed in the depleted solid solution. Nucleation and growth of these cells and the tin interlamellar spacing at various compositions and temperatures have been investigated. The interlamellar spacing increases approximately as the reciprocal of the logarithm of the supersaturation ratio. For constant initial tin concentration the concentration of cell nuclei increases with decreasing temperature to a limiting temperature-independent value. The kinetic results support the view that the cell growth rote is governed by the diffusion of tin along the cell boundary. In the main, the results confirm the authors' earlier deductions, drawn from resistometric and calorimetric data, about the precipitation mechonism. IT has been shown1, 2 that tin (ß) precipitates from lead-rich (a) PbSn solutions by the nucleation and growth of cells (cellular or discontinuous precipitation). These cells consist of tin lamellae, with a spacing 1, interspersed in a depleted a solution. Reorientation of a also accompanies cell growth. The kinetics of cellular precipitation of tin from lead have been measured by resistometric2, 3 and ca1orimetric1, 3 techniques. The time-transformation isotherms (t equals time; x, volume fraction of specimen transformed) of the initial rapid precipitation, which drains about 60 pet of the tin from solution, have been described by a kinetic law having the form x = 1 —exp (—bt n) [I] where n usually has the value 3.0. It was shown" that this law and the other kinetic facts can be explained satisfactorily if it is assumed that the cells grow at a constant rate and that all the cells nucleate in a time negligible in comparison with the period of cell growth before impingement. Thus, for hemispherical cells b = (2/3)pNG3 [21 where G is the rate of cell growth in cm per sec, and N is the number of cell nuclei per unit volume. The rapid rate of cell growth at low temperatures can be accounted for"' if it is assumed that the dissolved tin drains to the lamellae edges by diffusion along the sweeping cell boundary rather than by diffusion through the a crystal (volume diffusion). For cell growth governed by cell boundary diffusion it was shown, approximately G=2(X° - X° / X° ) DBA / l2 where A equals the thickness of the cell boundary; D R, the coefficient of diffusion of tin atoms within the boundary; and X° and X, are the atom fractions of tin in the supersaturated and saturated solutions, respectively. Zener8 had already shown that, where

Jan 1, 1959

By M. R. Tek, L. K. Thomas, D. L. Katz

Threshold displacement pressures are needed to determine how much overpressure can be used in storing natural gas. An experimental technique for determining threshold pressures by displacing water with gas from samples saturated with water is presented. Threshold pressures for eight low permeability samples were measured. Threshold pressure data obtained in this work, plus data on higher permeability samples reported in the literature, are correlated with porosity, permeability, surface tension and formation resistivity factor. Mercury injection pressures also were measured and correlated with air-water threshold pressures. Threshold pressures were found to be independent of time. An aerial photograph of gas emerging from the top of a core shortly alter its threshold pressure has been exceeded shows that the gas bubbles are uniformly distributed across the face of the core. Channeling will occur, however, when an increased gas phase permeability is reached, A porous medium can be re resealed alter its threshold pressure has been reached, provided it has not been desaturated below a fixed saturation. Its new threshold pressure will be lower than when the sample is 100 percent saturated with water. INTRODUCTION The degree of overpressure in excess of the discovery pressure that a gas storage reservoir can withstand is determined by the ability of its caprock to contain gas, providing the pressure does not exceed the structural limit of the reservoir. The retention of gas in a reservoir by a caprock saturated with water is a result of the capillary forces acting at the gas water interface. Without the presence of water in a caprock, gas would leak out of the reservoir at a rate determined by the permeability of the caprock to gas. The ability of a caprock to contain gas is expressed in terms of its threshold displacement pressure, which is defined as the minimum pressure needed to initiate the displacement of a wetting phase by a nonwetting phase from a porous medium 100 percent saturated with the wetting phase. The gas industry must be able to predict how much "overpressure" a gas reservoir can withstand before leakage occurs by gas displacing water from caprock overlying the reservoir. This is of economic importance since the storage capacity of a gas reservoir is proportional to its pressure. The discovery pressure for most reservoirs is found between the upper and lower limits1 shown in Fig. 1. Discovery pressures in excess of their hydraulic pressure gradient are attributed to the compaction of an isolated shale formation by the overburden.2.3 The lower limit of 0.433 psi/ft corresponds to the weight of the overburden, the gradient of the rock itself. Somewhere between

Jan 1, 1969

By H. C. H. Darley

The principal causes of unstable boreholes* have been known for many years. For example, in a paper published in 1938, Halbouty and Kaldenbachl listed nearly all the classes of troublesome shales that we know today. Much progress has been made since then, but we still have difficulty in identifying the cause of hole problems and consequently in selecting the right technique for combatting them. This subject was discussed at length by Kelly2 in a recent paper and much valuable information was provided. In the Shell Laboratory it was felt that there was a need for a better understanding of the basic mechanisms underlying the various forms of hole instability, and accordingly, a study was undertaken. This entailed reviewing the physics and chemistry of shales, developing tests for characterizing shales, and constructing a model to study borehole stability. Full simulation of underground conditions was not attempted; for example, we used reconstituted shale specimens, and often simple solutions or suspensions rather than practical drilling muds. Such procedures are necessary in order to establish mechanisms, but caution must be exercised in applying the results to the more complex conditions in the field. Part I — Compaction Swelling and Dispersion of Shales Compaction of Sediments Shales are formed by the compaction of sediments. Water is expressed as sediments are buried by subsequent layers, and the degree of compaction is proportional to the depth of burial, provided the water is able to escape easily to permeable formations. The younger sediments, when recovered at the surface, soften and disperse when mixed with water; the older shales have undergone diagenesis (alteration of the clay minerals, secondary cementation, etc.), and remain hard and unaffected by water. In this paper we shall apply the term "shale", as the drilling engineer does, to everything from clays, which are highly reactive to water, to completely lithified materials such as claystones and slates, which are completely inert. However, because these materials behave quite differently when encountered in the drilling well, it is desirable to develop a simple means of characterizing them. The feature that distinguishes the various shales is their dispersibility in water —soft clays disperse readily, harder shales disperse slowly when agitated, the lithified materials will not disperse at all unless milled. In the dispersibility test used in our study, a weighed amount of dry shale particles in the 12-to-100-mesh-size range was placed in a tube filled with distilled water and allowed to soak for 16 hours. The

Jan 1, 1970

NEW MEMBERS The following list comprises the names of those persons who became members during the period Oct. 10, 1916 to Nov. 10, 1916. ANCHOR, HANS C., Supt., Dome Extension Mines Co., Ltd., South Porcupine, Ont., Canada. BABCOCK, EARLE J., Dean, College Of Min. Engrg., State Univ. Of N. Dak., Grand Forks, N. Dak. BIDDIS0N, P. McDONALD, Construction Engr., The Ohio Fuel Supply Co., 52 W. Gay St., Columbus, 0. BOISE, PAUL T., Asst. Mgr., Stimpson Equipment Co., Felt Bldg., Salt Lake City, Utah. BOURNE, RALPH H., Vice-Pres Whiting Foundry Equipment Co., Harvey, Ill. BROWN, EDWARD OTTO FORSTER, Min. Engr., 706-707 Salisbury House, London, E. C., England.

Jan 12, 1916

Jan 1, 1968

By A. E. Anderson, H. J. Hilll

Laboratory data for 155 field muds and 77 .shales have been used to develop correlations to estimate the net streaming potential component of the SP. Analysis of these data and comparison with field tests show that streaming potential corrections must be made to obtain an accurate estimate of the electrochemical potential for use in the determinntion of formation water resi-iiviy. The self-potential curve is related to formation water resistivity, and considerable effort within the oil industry has been directed toward clarifying this relationship. The Schlumbergers and Leonardon1,2 recognized that two types of potentials, electrochemical and electro-kinetic, resulted in the net potential variation in the borehole. Most of the later papers have dealt with the electrochemical component and its controlling parameters. The investigations of Wyllie,2" Salisch' and Moore5 provide the most extensive sources of data on streaming potentials across mud cakes. These authors observed streaming potentials of sufficient magnitude to be of critical importance in SP interpretation, if it is assumed that streaming potentials develop only opposite permeable beds. Streaming potentials across shales have been reported by Schenck and by Gondouin, et al.7 Since SP magnitude is the difference in potential opposite shale and sand beds, these authors suggested that the net streaming potential component may be negligible. The present investigation was initiated to evaluate empirically some of the parameters controlling the magnitude of the net borehole streaming potential and to determine whether useful relations between mud properties and net streaming potential could be established. Field muds were used in this investigation. These muds were characterized by the amount and type of chemical treatment utilized for five days before Sampling. Filter loss, mud resistivity, mud density and filtrate resistivity were determined for each mud with conventional methods and apparatus. Mud filtrate pH was estimated with Hydrion pH paper for the appropriate range. Streaming PotentIals Across MuD Cakes Commercial calomel-saturated KC1 electrodes are subject to potential changes attributed to contamination of the very small fiber-tip bridge by particles of clay from the drilling mud.3 To minimize this difficulty, a large diameter bridge (Fig. 1) was constructed with saturated KC1-agar gel and a filter disc of microporous porcelain. Experiments showed that streaming potentials across this bridge are less than 0.2 mv at pressure dif-

By J. D. Allen

In the coal preparation plant at U.S. Steel Corp.'s Concord mine in Alabama, the product moisture was reduced from about 20% to 9% through the development of a workable flowsheet for dying the clean coal. Some of the high points of the conversion of the Concord washer from vibrating screen dewatering to centrifuge drying are presented in this article. The coal preparation plant at the United States Steel Corp.'s Concord mine near Bessemer, Ala., began operations in June, 1950. The basic cleaning circuit consisted of a Chance cone for cleaning the 2-in. x 3/8-in. fraction and concentrating tables for cleaning the -3/8-in. coal fraction. Dewatering of the final product was accomplished with 35-mesh vibrating screens. However, because Concord coal is very friable with 85% passing 3 mesh and 25% passing 28 mesh (Fig. I), a considerable quantity of fines passed through the dewatering screens. To recover these fines, the dewatering screen effluent was sent to two 70-ft-diam hyd rose para tors from which the underflow returned to the dewatering screens and the overflow went to a 175-ft-diam thickener for water clarification, as illustrated in Fig. 2. As might be expected, there was considerable recirculation of the -35-mesh coal in this system. This degraded the coal and led to higher moistures. It also resulted in a fines bleed-off of plant water and thickener underflow to a fine-coal settling pond. In 1961, vacuum filters were installed to supplement the screens and to recover the fine coal lost in the bleed-off. The above system resulted in a product moisture of about 20%. Further reduction to approximately 11% was accomplished by drainage from railroad cars during transit to the coke plant. Control of the moisture at unloading was poor because of variations in operating levels and railroad car availability, but since the Concord coal constituted a relatively small percentage of the over-all coal mix at the coke plant, its high moisture and fluctuations did not seriously hamper coking operations. Early in 1964, however, the proportion of Concord coal was increased with a resulting increase in the moisture of the total coal mix, and this caused difficulties in the coke plant. The increased participation of Concord coal also brought about a shortage of railroad cars which raised the moisture content to a point where the coal became almost impossible to handle. In an effort to alleviate this problem, U.S. Steel initiated a research program to develop a flowsheet for reducing the moisture to approximately 10% and to determine whether the resulting product would be satisfactory for the coke plant. Under this program, an experimental flowsheet for evaluating both a vibratory centrifuge system and a solid bowl centrifuge system was drawn up as shown in Fig. 3. A horizontal vibratory centrifuge was installed to reduce the moisture in the dewatered coarse coal, and a four-cell, flotation machine was installed to clean the -65-mesh portion of the 3/8-in. x 0 table raw coal feed. Several shortcomings in the above circuits were apparent. For one thing, large quantities of repulping water were required. Furthermore, since about half of the flotation feed was of a size consist that could have been cleaned on the tables, these circuits would result in an unnecessary increase in reagent costs and facilities. Maintenance of the hydro separators and pumps for pumping the underflow to the filters,

Jan 1, 1969

By Edward Hart

Having occasion several years since to make ferrous sulphide, I attempted to do so by fusing a mixture of coal-brasses (FeS2) and dried ferrous sulphate. A very nice-looking sulphide was obtained; but on attempting to use it, I found that it was insoluble in dilute hydrochloric and sulphuric acids. The subject was laid aside at the time, but has since been taken up; and some curious results have been obtained, which I believe are new. I have made the material by all of the following methods and the product seems to be pretty much the same, however obtained : (a) FeS2 heated to fusion. (b) FeS2, and FeSO4 heated to fusion. (c) FeS2, and Fe2O3 heated to fusion. (d) FeS2, and FeCO3, heated to fusion. (e) FeSO4, and S heated to fusion. (f) Fe2O3 and S heated to fusion. Obtained in this way the mass after cooling breaks easily and is very nearly black in color. On the upper surface of the fused cake the color is generally reddish or brownish black. When this is treated with dilute sulphuric or hydrochloric acid, it refuses to dissolve; but if touched with the point of a file or any piece of wrought-iron, solution of the sulphide takes place with the evolution of sulphuretted hydrogen. If the iron is removed the evolution of gas ceases, and only begins again when the iron is again brought into contact with the fused sulphide. The same thing happens if the iron is connected with the sulphide by means of a platinum wire. But in all the samples of fused sulphide I have obtained, if the iron is allowed to remain in contact with the sulphide for a certain time (which varies with different samples of the fused sulphide) and is then removed, solution of the sulphide continues. Zinc, tin, and magnesium have the same effect as iron. In hydrochloric acid aluminium acts more rapidly even than iron. In sulphuric acid it has little if any effect. Copper in HCl, when brought in contact with the fused sulphide, dissolves quietly without evolution of gas. The solution of copper chloride formed becomes,as it flows down over the sulphide, converted into copper sulphide.

Jan 1, 1887

By L. H. Simons, H. H. Spain

I NT RODUCTION Theory indicates that linear water-floods should exhibit scaling and stabilization properties in both oil-wet and water-wet porous media'. Experimental verification of these proper-ties in oil-wet media was obtained some time ago', and more recently, Perkins', employing a high permeability unconsoli dated sand and a low oil-to-water viscosity ratio, has obtained flooding data in a water-wet medium which follow the pattern of scaling and stabilization. Also, Root and Calhoun3 have found similar trends in the displacement of gas by liquids from unconsolidated sands. In general, however, the experimen-tal evidence appears still somewhat conflicting since scaling and stabilization of water floods in water-wet media has not been observed in most of the studies to date'.".'. The purpose of this paper is to provide a more comprehensive picture of waterflood behavior in water-wet media and to corroborate the validity of the scaling and stabiliza-tion concepts. The need for differentiating between the intrinsic nature of water-oil displacements inside a porous medium and perturbating secondary end effects is discussed, pertinent experimental procedures are outlined and the results of flooding tests conducted at low and at high oil-to-water viscosity ratios on con- solidated, water-wet Alundum cores are analyzed. END EFFECTS IN WATER-WET MEDIA Outlet End Effects The peculiar feature of the outlet end effect in water-wet cores is that it not only results in an excessive wetting phase saturation at the outflow face,'.' but that it also retards the moment of water breakthrough: i.e., causes an undue delay in the appearance of water in the produced effluent. Conditions existing in a water-wet core when water first arrives at the outflow face are schematically shown in Fig. 1. At this flooding stage the saturation distribution, Fig. la, has not yet been distorted by the outlet end effect. A water-invaded pore at the outlet core face, opening into the oil-filled void space between the end of the core and the end plate of the flooding cell, is illustrated in Fig. lb. The curvature of the water-oil interface is concave toward the outlet, and the pressure on the water side of the interface is lower than on the oil side by an amount equal to a certain capillary pressure (Fig. lc). Before the water (of this particular pore) can be produced from the core, it is apparent that the pressure in the water phase must exceed that in the oil outside the core. Accordingly. when water first reaches the outlet face, it will not leave the core but will accumulate inside, and only oil will be produced. Eventually, as the water injection is continued. sufficient pressure is built up in the water to reverse the curvature of the interfaces in the outlet pores, and only then will water be produced from the core. This stage, illustrated in Fig. 2. corresponds to the conventional "water breakthrough" observed in flooding experiments. For purposes of discussion, it is convenient to distinguish between the flooding stage at which water first arrives at the outlet face of a core (Fig. 1) and the stage at which water is first produced from the core ( Fig. 2). The former will be referred to as "water arrival" and the latter water breakthrough. In oil-wet media