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By John C. Calhoun, R. C. Newman

A report is made of experimental work performed on the capillary retention of water within porous solid systems, the displacement being accomplished with air and various organic liquids. A portion of the experiments were designed to measure the lowering of vapor pressure of water within a porous solid with subsequent conversion of such vapor pressure data to capillary pressure values. The form of the capillary pressure curve at high capillary pressures has been elucidated from this data. Certain theoretical approaches are presented to indicate the correlation between work done by previous investigators. The present work is correlated also with theory. Surface area values are calculated for the various core systems studied. INTRODUCTION Leverettl in 1941 presented a paper which gave the essential concepts of capillary behavior in porous solids. His presentation included both theoretical and experimental aspects of the problem. He defined the term "capillary pressure" and applied it to an ideal porous system. His work included the definition of a dimensionless quantity which was a function of fluid saturation and which could be correlated with porosity and permeability for clean, unconsolidated sands. His experimental work was performed by the drainage of water from packed columns of unconsolidated sands. Subsequently, other authors have presented experimental techniques which permit the determination of capillary pressure data on small core samples. Data have been presented on porous systems other than unconsolidated sand and with the use of liquids other than water. Notable among these are the works of Hassler, Brunner and Deahl,2 Bruce and Welge,³ Amyx and Yuster, and Purcell. Others have indicated the applicability of such data to field problems without regard to the theoretical aspects of the capillary pressure saturation function. Within the recent published literature there have also been reported studies of the correlations between capillary pressure data and other fundamental properties of porous solids. It was the intent of the present reported work to investigate the behavior noted by water and various other liquids within porous systems in an attempt to amplify existing correlations between capillary properties, surface properties, and other fundamental characteristics of porous systems. The experimental work described here was performed as two different investigations but due to its nature it is reported as separate phases of the same general topic. CAPILLARY PRESSURE AND VAPOR PRESSURE LOWERING It has long been recognized that the vapor pressure above the curved surface of a liquid is a function of the curvature of the liquid surface." The capillary pressure is also a function of the curvature of the liquid surface. Both capillary pressure values and vapor pressure lowering are, therefore, functions of the liquid saturation of a porous solid. A quantitative relationship between the vapor pressure lowering and the capillary pressure can be simply developed by considering a porous solid system containing water in equilibrium with its vapor. The capillary pressure at any height within the system is defined as Pc= Pv -P1.......(1) where PI is the pressure in the vapor phase and PI is the pressure in the liquid phase. Consider that both the water and its vapor are continuous phases within the system and that at any point the two phases are in equilibrium. The gradients in the liquid and vapor columns within the porous system are: PI = plgdh dPv = pvgdh By integrating these gradients from the point where h = 0 to the height h, values of PI and PI at the point h are found. Let the point where h = 0 be that where Pc = 0. At this point also Pv is equal to Pve, the equilibrium vapor pressure of the liquid above a flat surface. From the first of these integrations since p is independent of height: P = p1gh + P, From the second, by substituting pv = PvM/RT, where M is the molecular RT weight: Pv M Pvo- RT gh By combining the two last equations to eliminate h, one obtains: P1 RT Pv Substituting, values for Pv and Pi in equation (1) gives PyRT RT Pv which is approximately Pc=RT/Mp1 In Pvo/Pv .......(2) This equation relates the vapor pressure above a curved surface with the capillary pressure across the curved surface in terms of measurable quantities. The equivalent of this equation is given by Freundlich."

Jan 1, 1949

By H. E. Cline, E. F. Koch, J. L. Walter

It has been postulated and, in a few instances shown, that some kind of dislocation structure will be present at semicoherent interfaces to accommodate small lattice mismatches. In the present study of the NiAl-Cr eutectic, regular arrays of interface dislocations are observed at the boundary between the chromium-rich rods and the NiAl-rich matrix. The networks were examined by transmission electron microscopy and selected area diffraction. The rods and the matrix have a crystallographic relationship in which all directions and planes of the two phases are parallel. The dislocation networks are cmposed of a<100> dislocations lying on the intersections of the cylinders with (100) planes. Dislocations forming hexagonal rather than square arrays are also observed at certain areas of the network. The morphology of the network is consistent with the interpretation of mismatch being accommodated by interface dislocations in the cylindrical geometry. The measured spacing between dislocations was used to calculate an apparent lattice mismatch between the phases (˜0.35 PCt)interface network energy (-140 ergs per sq cm), and network strengthening (-10,000 psi). It has been proposed by Frank and Van der Merwe1 that dislocations should be present at the boundary between two semicoherent crystallographically related phases. The role of the interface dislocations would be to reduce the internal stresses, caused by the mismatch in atomic spacing across the interface. Such dislocations have been observed at the interface between expitaxially grown films and Substrates.2-4 Interfacial dislocations have also been observed at precipitate-matrix interfaces.&apos;-&apos; Directionally solidified eutectics have been shown to have semicoherent phases1&apos; and would, therefore, be expected to have interfacial dislocations as found by Weatherly at a lamellar fault in A1-A12Cu.11 The NiAl-Cr eutectic appeared to be a promising system to examine because both phases are cubic, the lattice mismatch is small, and the phases are crys-tallographically related. Furthermore, the eutectic is easily thinned for transmission microscopy. Indeed, interfacial dislocations were observed and this report describes the nature of the dislocation networks in the boundary between the NiAl-rich ma-trix-phase and the fine chromium-rich rods.21 I) EXPERIMENTAL PROCEDURE Ingots, 3/4 in. in diam and 6 in. long were made by melting in vacuum and casting under argon using 99.9 pct pure material. The composition, in at. pct, was 33 pct Ni, 33 pct Al, and 34 pct Cr. The ingots were then placed in A1203 crucibles on a water-cooled base, melted by means of induction, and withdrawn from the hot zone at the rate of 1 in per hr under argon.* * T his material was first directionally solidified in this laboratory by E. R. Stover Slices were taken perpendicular to the growth direction of the directionally solidified ingot for metallography and for transmission electron microscopy. The electron transmission samples were thinned mechanically, then thinned electrolytically in A-2 electrolyte* *A-2 electrolyte: 62 ml perchloric acid, 700 ml ethanol, 100 ml butylcellosolve, 137 ml distilled H20. until a hole appeared in the foil. 11) EXPERIMENTAL RESULTS A) Optical Microscopy. The microstructure, viewed on a plane perpendicular to the growth direction, is shown in Fig. 1. The structure consists of cells or colonies of parallel chromium-rich rods in the NiAl matrix. The cells occur when there are impurities present12 or, in a ternary eutectic, if the composition is slightly off the eutectic composition. The axis of the chromium-rich rods is parallel to the growth direction except near the cell boundaries. Here the rods may assume angles to the growth direction; however, examination shows that the crystallographic relationship between the rod and the matrix remains the same. Fig. 1 includes cell boundaries where the rods formed at a large angle to the growth direction. The variation of rod position across the cells made it possible to Fig. 1-Structure on plane perpendicular to growth direction. Rods near cell walls are at large angle to growth direction. Magnification 315 times.

Jan 1, 1970

By V. F. Hollister

The Queen Charlotte gold deposit (also known as the Specogna, Babe, or Cinola) was discovered in late 1970 by Efrem Specogna and Johnny Trico. They were prospecting along the trace of the Sandspit fault, and they sampled jarositic material that included veins from the fault zone. Their assays included some good gold values. They located the Babe Claims in 1971 and optioned them to Kennco Explorations Ltd. Kennco conducted stream sediment and soil geochem studies, geological mapping and drilling of 55.2 m (181 ft) in two drill holes. Kennco withdrew from the property, and by 1977, Cominco, Placer Development, Silver Standard, and Quintana Minerals had each successively worked on the deposit. Consolidated Cinola Mines bought the claims in 1977 and completed exploration of the deposit ultimately in a joint venture arrangement with Energy Reserves. Energy Reserves entered in late 1979, and by 1983, a total of 200 surface and 12 underground drill holes had been completed, totaling 28 600 m (93,832 ft). In addition, a 461.9 m (1515 ft) adit was driven in the ore body. Reserves published by Cinola aggregate 34 Mt (37 million st) of 1.7 g (0.060 oz) Au per tonne. All industry geologists working in the area agree that the Queen Charlotte gold is an epithermal gold deposit in porous volcaniclastic and clastic rocks that is genetically related to a Miocene-Pliocene rhyolite plug. The geologic description here follows the oral presentation made by G. G. Richards, J. S. Christie, and M. R. Wolfhard at a 1976 CIM meeting. Additional comments by the late C. S. Ney of Kennco Explorations are included with the Richards, Christie, and Wolfhard data to complete the geologic set- ting. The attached reprint by Champigny and Sinclair (1 980) provides additional data on the deposit. The Queen Charlotte (Babe, Specogna, or Cinola) gold deposit is located on Graham Island in the northern Charlotte Islands, at the fault boundary of the Skidegate plateau and the Charlotte lowlands. The Sandspit fault marks the physiographic boundary, and it is intruded by rhyolite porphyry at the deposit. Because displaced geochem anomalies, drain- age patterns, and topography suggest dextral and east side down movement for the fault, exposed east block rocks are younger than rocks west of the fault. The east block, which included the ore deposit, is a lowland largely masked by unconsolidated Pleistocene and Recent clastic rocks. Rocks west of the rhyolite plug, on the Skidegate plateau, are Cretaceous carbonaceous and calcareous shale unconformably overlain by a thin veneer of rhyolite tuff. The deposit is about 100 m (328 ft) above sea level. GEOLOGIC SETTING At the ore deposit, the Sandspit fault is a complex structure. However, lithologies on either side of the fault-controlled rhyolite porphyry plug are distinct. West of the rhyolite, the upper member of the Cretaceous Haida formation shale is the most common rock type. The member is composed of dark grey to black, poorly consolidated, and thinly bedded carbonaceous and calcareous shale. The sequence is silicified to an argillite or a hornfels near the rhyolite. West of the rhyolite porphyry plug, but not importantly involved in the mineralization, is a thin masking cover of rhyolite tuff. The tuff unconformably succeeds the cretaceous shale, but it is largely eroded in the mine area. East of the fault-controlled rhyolite porphyry plug is a thick section of conglomerate and sandstone of the Miocene- Pliocene Skonun formation. The ore body occurs within the coarse clastics, the rhyolite intrusive as the western boundary. Ore is entirely contained within the clastics. Original permeability of the clastic rocks was a major control for ore deposition and alteration, and for that reason, the Skonun formation is described in greater detail. The Skonun formation clastics unconformably overlie Haida shale. The Skonun is at least 300 m (984 ft) thick in the mine area, where it trends northerly and dips easterly 15º to 25º. The sequence is about 62 percent conglomerate, 3 1 percent coarse arkosic sandstone, and 7 percent interbedded siltstone and sandstone. Contacts between adjacent beds are generally sharp. Stratigraphic correlations between drill

Jan 1, 1985

By H. L. Hartman

The drop tester has proved an invaluable tool for the investigation of percussion drilling in the laboratory in "slow motion". It has allowed the process of rock penetration by impact to be studied a single blow at a time. In the present work, the relation of cratering to indexing has been determined under conditions simulating those in the bottom of the hole at atmospheric pressure. Indexed blows form craters which are influenced by others adjacent to them. Two unique effects are involved: (1) the provision of additional free faces in proximity to the point of impact and (2) the creation of subsurface damage by the previous blow(s). Both have a pronounced influence on the volume of rock removed per blow, which governs the rate of penetration in actual drilling. The emphasis in this study was placed on determining effects of index distance and impact energy on crater volume when blows were struck on a previorusly "drilled" or damaged surface, a situation most representative of down-hole conditions. The results indicated that (I) the optimum index distance on a damaged surface is greater than on a fresh, undamaged rock surface; (2) the volume of rock broken at optimum index distance is about the same for both surface conditions with die-shaped chisels but tends to be greater on a cratered surface with wedges; (3) the optimum index distance and maximum crater volume are proportional to the energy level; (4) at a given energy level, the volume of rock broken by dies generally exceeds that by wedges; and (5) maximum crater volume varies, approximately, inversely with width of die but is nearly independent of included angle of wedge. INTRODUCTION This is the third of a series l,2 of papers reporting on one phase of a continuing program of drilling research being conducted in the Rock Mechanics Laboratory at The Pennsylvania State U. The phase under consideration is crater geometry — blow energy relations in percussion drilling. While the previous papers have discussed mainly craters produced by single blows, indexed-blow studies are the subject of this paper. The basic mechanism of drilling under study here — that of penetration of a chisel-shaped bit subjected to impact — is the one employed in probably 90 per cent of all rock drilling in mining, percussion drilling. It also forms the fundamental action in nearly all oil well drilling with the so-called rotary (roller-bit) method. Here, the action is more complex, however, and may in actuality comprise rotary-percussion drilling. Certainly, the down-hole air and mud hammer drills, which superimpose percussion on rotation, belong in this latter category. In any event, impact blows constitute one of the principal mechanisms in the vast majority of drilling, mining or petroleum, and it is essential in drilling research to study percussion in all its basic aspects. Percussion drilling can be simulated in the laboratory by means of an impact drop tester. Striking one blow at a time with chisel-shaped bits, the drop tester permits study of most of the parameters in the drilling process except blow frequency and the interrelationship of certain variables. Single-blow craters, the simplest to produce, allow the determination of basic relationships, such as volume vs blow energy; while indexed craters most closely resemble the action in real drilling and provide data for the establishment of optimum operating criteria. Indexed-blow craters are those which are influenced by others in proximity. The simplest case to visualize, and the one studied in detail here, is that in which a given crater is formed adjacent and parallel to a previous crater, such that the second crater breaks into the first. A more complex situation usually exists downhole, where indexing is achieved by rotation of a radial-winged or rolling-cutter bit. But, admittedly, the phenomenon of indexing is more likely to be understood eventually if it is first studied in its simplest form, that related to parallel craters. Limited research has been conducted on indexed blows. The most complete study was that by Simon, 3,4 who proposed universal indexing curves to relate the important variables. His work, however, was conducted entirely with rows of craters formed on a

By John C. Calhoun, R. C. Newman

A report is made of experimental work performed on the capillary retention of water within porous solid systems, the displacement being accomplished with air and various organic liquids. A portion of the experiments were designed to measure the lowering of vapor pressure of water within a porous solid with subsequent conversion of such vapor pressure data to capillary pressure values. The form of the capillary pressure curve at high capillary pressures has been elucidated from this data. Certain theoretical approaches are presented to indicate the correlation between work done by previous investigators. The present work is correlated also with theory. Surface area values are calculated for the various core systems studied. INTRODUCTION Leverettl in 1941 presented a paper which gave the essential concepts of capillary behavior in porous solids. His presentation included both theoretical and experimental aspects of the problem. He defined the term "capillary pressure" and applied it to an ideal porous system. His work included the definition of a dimensionless quantity which was a function of fluid saturation and which could be correlated with porosity and permeability for clean, unconsolidated sands. His experimental work was performed by the drainage of water from packed columns of unconsolidated sands. Subsequently, other authors have presented experimental techniques which permit the determination of capillary pressure data on small core samples. Data have been presented on porous systems other than unconsolidated sand and with the use of liquids other than water. Notable among these are the works of Hassler, Brunner and Deahl,2 Bruce and Welge,³ Amyx and Yuster, and Purcell. Others have indicated the applicability of such data to field problems without regard to the theoretical aspects of the capillary pressure saturation function. Within the recent published literature there have also been reported studies of the correlations between capillary pressure data and other fundamental properties of porous solids. It was the intent of the present reported work to investigate the behavior noted by water and various other liquids within porous systems in an attempt to amplify existing correlations between capillary properties, surface properties, and other fundamental characteristics of porous systems. The experimental work described here was performed as two different investigations but due to its nature it is reported as separate phases of the same general topic. CAPILLARY PRESSURE AND VAPOR PRESSURE LOWERING It has long been recognized that the vapor pressure above the curved surface of a liquid is a function of the curvature of the liquid surface." The capillary pressure is also a function of the curvature of the liquid surface. Both capillary pressure values and vapor pressure lowering are, therefore, functions of the liquid saturation of a porous solid. A quantitative relationship between the vapor pressure lowering and the capillary pressure can be simply developed by considering a porous solid system containing water in equilibrium with its vapor. The capillary pressure at any height within the system is defined as Pc= Pv -P1.......(1) where PI is the pressure in the vapor phase and PI is the pressure in the liquid phase. Consider that both the water and its vapor are continuous phases within the system and that at any point the two phases are in equilibrium. The gradients in the liquid and vapor columns within the porous system are: PI = plgdh dPv = pvgdh By integrating these gradients from the point where h = 0 to the height h, values of PI and PI at the point h are found. Let the point where h = 0 be that where Pc = 0. At this point also Pv is equal to Pve, the equilibrium vapor pressure of the liquid above a flat surface. From the first of these integrations since p is independent of height: P = p1gh + P, From the second, by substituting pv = PvM/RT, where M is the molecular RT weight: Pv M Pvo- RT gh By combining the two last equations to eliminate h, one obtains: P1 RT Pv Substituting, values for Pv and Pi in equation (1) gives PyRT RT Pv which is approximately Pc=RT/Mp1 In Pvo/Pv .......(2) This equation relates the vapor pressure above a curved surface with the capillary pressure across the curved surface in terms of measurable quantities. The equivalent of this equation is given by Freundlich."

Jan 1, 1949

By M. J. Marcinkowski, E. N. Hopkins

An investigation has been made of the ß(fcc) — a(hexagonal) transformation which occurs in lanthanum using both electrical resistivity and transmission electron microscopy techniques. It has been shown that the ß phase can be retained below the transformation temperature by rapid quenching but that the sample immediately begins to transform to the a phase. The transformation is observed to nucleate in the vicinity of inclusions. Based on the above observations, a detailed model of the transformation has been advanced which involves the nucleation of an extrinsic stacking fault bounded by a pair of Shockley partial dislocations in the vicinity of some heterogeneity, i.e., an inclusion. The stress field of the resultant dislocation pair acts to nucleate extrinsic faults in adjacent planes and leads quite naturally to the B-a conversion with a minimum of strain energy induced in the crystal. LANTHANUM possesses an fcc structure ß) (8) upon cooling transforms to a hexagonal modification (a) in much the same way as cobalt. The one exception, however, is that the stacking sequence of the closest packed planes in a La is ABAC ABAC, and so forth,1 whereas in cobalt it is ABAB, and so forth, i.e., hep. Mainly on the basis of transmission electron microscopy techniques, there seems to be little doubt that the 0 — a transformation in cobalt involves a dislocation mechanism2 although its exact nature still remains obscure. Although the ß - a transformation in lanthanum is somewhat more complex than that occurring in cobalt, it was thought that its very uniqueness would be helpful in understanding fcc — hexagonal transformations in general. Such a general understanding of these transformations is important since they represent what are perhaps the simplest of the martensitic class of transformations. The experimental techniques used were those of electrical resistivity and transmission electron microscopy. EXPERIMENTAL PROCEDURE The lanthanum used in this investigation was prepared by the calcium reduction of lanthanum fluoride in a tantalum crucible under an argon atmosphere as described by Spedding et al. The residual calcium was removed by vacuum remelting in a tantalum container. Portions of the metal were then analyzed by emission spectroscopy as well as vacuum fusion. The amounts of the various impurities that were found are listed in Table I. A portion of the lanthanum ingot was swaged at room temperature into 0.030-in.-diam rod for the resistivity samples while the remainder was rolled into 0.010-in.-thick sheet for the transmission electron microscopy phase of this investigation. In order to eliminate the plastic deformation induced in the samples during fabrication, they were sealed in evacuated tantalum lined quartz capsules and annealed for 1 hr at 700° C. Specimen resistances were measured using the conventional "four-wire" technique described by MacDonald, 4 employing a type K-3 Universal Potentiometer and a standard 0.001-ohm resistor, both manufactured by Leeds and Northrup Co. By taking into account all of the possible errors in the apparatus, it was felt that the absolute resistivities of the approximately 0.87-in.-long specimens measured are reliable to 3 pct. Resistances from room temperature to 700°C were measured using a vacuum furnace. In order to avoid sample contamination by the thermocouple, chromel-alumel leads were spot-welded into a tantalum shield which in turn was welded to the lanthanum specimen. Resistances below room temperature were obtained by transferring the sample to a helium gas-filled quench tube and slowly dripping liquid nitrogen into a surrounding dewar flask. A steady reduction of temperature to about —190°C was completed in about 23 hr, and the resistances were measured at various temperature intervals. As will be shown shortly, rapid quenching from above about 350°C was sufficient to suppress the B -a transformation initially but subsequent annealing at lower temperatures leads to a partial ß --a conversion. To investigate this aspect of the transformation, the samples were suspended in the hot zone of a helium-filled furnace from which they could be rapidly dropped into the quench tube mentioned previously which was now

Jan 1, 1969

By R. B. Full

DURING the summer of 1949, the United Nations Scientific Conference on the Conservation and Utilization of Resources met at Lake Success. As summed up by one writer, the purpose was: "That everyone will try to learn how to feed more people from an acre of land." That objective is a stimulus to the phosphate rock industry as well as other industries. Phosphate rock was mined first in the Canadian province of Quebec where it was found as an apatite in pockets. In 1863, mining began near the Rideau Canal, first in open trenches and quarries until shafts were sunk. These operations were difficult since hard rock had to be drilled and blasted. Steam was the source of power. The phosphate rock was hand-selected and recovery ranged from 6 to 10 pct, averaging 70 pct to 85 pct bpl (bone phosphate of lime). Costs, f.O.b. Montreal, were $14 a ton, and selling prices averaged $17 a ton. In 1885, about 29,-000 tons were sold on this basis, but by 1892 the output fell to 8000 tons at an average price of $15 a ton at Montreal. South Carolina Deposits Phosphate rock was first discovered in South Carolina in 1837, but a mining company was not formed until 1867. It was immediately successful, and the industry continued to develop and ship an increased tonnage of land and river rock, shipments increasing from approximately 20,000 tons in 1868 to 537,000 tons in 1890, when the shipments began to decrease. In 1892 only 350,000 tons were shipped. In this field there were two types of deposits: land rock and river rock. More land rock tonnage was mined until about 1887 when river rock production began to equal it. The land rock was mined adjacent to and in the river marshes by pick, shovel, and wheelbarrow. Each worker dug daily a space 6 ft wide, 15 ft long and 6 ft deep, which was overburden, and then loaded about 3 cu yd of phosphate rock into wheelbarrows. His helper would wheel the barrows to small steam railroads up to 250 ft distant. Water was kept from the pits by steam pumps connected to railway cars. The phosphate rock was loaded into railroad cars, hauled and dumped into a log washer to which water was added, and run over trommel screens to eliminate the clay and loose sand. Steam shovels for loading were introduced about 1891. River rock was mined by floating dipper dredges and at low tide was loaded into barges by laborers using oyster tongs, the large lumps being hand-loaded. Barges and bateaus were unloaded by wheelbarrows which were wheeled to the same type of land rock washers. The washer product was piled with stacked pine cordwood in alternate layers and fired for drying. Usually this was done under sheds along the river bank. The dried rock then was transferred to ships, usually three or four-masted schooners. Cost of production of both land and river rock, including $1 a ton royalty paid to the state for state-owned property, was approximately $4.25 a ton averaging 60 pct bpl. The selling price was approximately $7 a ton f.O.b. In 1886 the courts handed down a decision permitting anyone to mine, and many additional companies were organized immediately. As a result, the selling price was lowered to a profit margin of 50Ø or less per ton. The South Carolina mines were eventually shut down when a more profitable source of phosphate rock was discovered in Florida. Florida Deposits Phosphate rock was discovered in Florida in 1882, and in 1883 a small quarry was opened near Hawthorne. In 1886 phosphate rock of good grade was discovered on Peace River, and the Arcadia Phosphate Co. was formed. In 1888 the company began shipments amounting to 3000 tons that year. During the latter part of 1888, hard-rock phosphate was discovered near Dunnellon. Exploration extended rapidly, and deposits of hard-rock phosphate were mined over a wide area so that shortly after 1900

Jan 1, 1952

By J. N. Breston, R. V. Hughes

Conclusions drawn by previous research workers with reSPect to the relation between Pressure gradients and/or velocity and oil recovery obtained by laboratory water flood tests have been in disagreement probably due to variable procedures and unnatural conditions and materials. The Bradford Laboratory of the Pennsylvania Grade Crude Oil Association as part of its secondary recovery research program has conducted nineteen water floods on two long cores of widely differing characteristics in an attempt to clarify this relationship and make it an aid in predicting flooding pressures in the field. Unlike previous research procedures the present experiments were conducted with the aim of duplicating field conditions as closely as possible by using long unextracted consolidated cores, a live crude, and natural brines for both flooding and, connate water content. Also, the pressure gradients and flooding velocities were representative of field conditions where similar sands were being flooded. Eleven floods on one core and eight floods on the other core showed increased recoveries and lower residual oil saturation with increased flood pressure gradients and flood velocities. A marked decrease in recovery was obtained from both cores at very low flood velocities. This pressure versus recovery relationship is shown to hold up to the point of water breakthrough and also up to the 100 and 1 produced water to oil ratio point. INTRODUCTION The possibility of water flooding oil sands was suggested by Carl1 of the Pennsylvania Geological Survey in 1880. It is not known when the practice was tried intentionally for the first time, but its beneficial effects were noted in the annual production rate of the Bradford field as early as 1907. The practice was illegal in Pennsylvania until 1921. Early water floods in the Bradford field usually consisted of shooting or splitting the casing secretly to permit subsurface waters to enter the producing sands under hydrostatic head. As it was noted that the benefits of water flooding seemed to be proportional to the quantity of water dumped into the well many also began to utilize surface sources after the practice became legal. It was probably during the middle 20&apos;s before many producers realized that the pressurehead of the water upon the producing sand determined the rate and quantity of water that would enter the sand. Hence, rate and quantity of production appeared to be a direct function of input pressures. By 1927 a few producers had ventured the installation of pressure pumps in order to increase water-input rates and production through the combination of hydrostatic and hydraulic pressures. The adoption of pressure flooding and the "five-spot" drilling pattern in the Bradford field were essentially simultaneous. Water-input pressures in 1930 seldom exceeded 300 p.s.i. at the well head or 1100 p.s.i. at the sand face. Since that time, water-flood producers in the Bradford-Allegany fields have gone to higher and higher pressure until today 600 p.s.i. at the well heads is called a low pressure flood. Many high pressure floods now operate at 1300-1400 p.s.i. at the well head. The limiting and advisable pressure at the sand face has been pronounced as that pressure just under what is required to lift the overburden or to cause formation parting: According to this rule any water flood operation utilizing well-head pressures nearly equal in pounds per sq. in. to 1.1 times the average depth in feet to the top of the producing sand would be considered as a high-pressure flood. Despite the higher pressure trends in the Bradford-Allegany field operations and the results of early laboratory water flooding research, the desirability and benefits of high input pressures are still questioned by many operators, particularly in midwestern water flood operations. The present paper recounts a series of 19 laboratory water floods using two long, consolidated cores of widely differing characteristics saturated with live crude and flooded with oil field brines in an effort to simulate field conditions under • various pressure gradients and flooding velocities. For both cores, higher recoveries and lower residual oil saturations were obtained at higher pressure gradients and flood velocities. This relationship is shown to hold up to the water breakthrough point and also up to the 100 to 1 produced water to oil ratio point.

Jan 1, 1949

By J. B. Stubbins, R. A. Blais

Extensive geological work was initiated — and continues — when operations of the Iron Ore Co. of Canada commenced in the Labrador-New Quebec area. Such geological operations include: mapping, test pitting, drilling, underground workings, volume factor and structure tests, and the calculation of ore grades and tonnages. Details of such work are given. Development is carried sufficiently ahead of mining to provide reliable tonnage and grade estimates and allow final mine planning. In order to make full use of geology in mining operations, the pit engineer combines the duties of geologist and mining engineer. The iron deposits of the Knob Lake range are located in the central part of the Labrador peninsula, a territory nearly twice the size of Texas, which is bounded by Hudson Bay on the west, Hudson Strait on the north, the Atlantic Ocean on the east and the Gulf of St. Lawrence on the south. The mining district proper is about 1000 miles northeast of Toronto. A 360-mile railroad links this mining area to the port of Sept-Iles on the Gulf of St. Lawrence. Schef-ferville, which is only a few miles from the open-pit mines, is the center of operations of the Iron Ore Co. of Canada. It has a population of nearly 5000. The nearest settlement is Labrador City, some 120 miles to the south, where this company is erecting a large plant for beneficiating its huge reserves of local low-grade iron ores. HISTORY The mineral possibilities of the area were recognized as early as the end of the last century, when A.P. LOW&apos; of the Geological Survey of Canada made his famous trek across the Labrador Peninsula. After mapping several belts of iron formation, Lovr recommended that the area be thoroughly prospected for iron. In 1929, two well known Canadian geologists, J.E. Gill and U&apos;.F. James, led a private expedition in central Labrador and discovered the first deposit of high-grade iron ore near what is now the Ruth Lake Mine. In 1936 the Labrador Mining and Exploration Co. was formed to 11ake over a prospecting concession of over 20,000 sq miles in central Labrador. An adjoining concession of 3900 sq miles in New Quebec was obtained in 1942 by Hollinger Consolidated Gold Mines, which had just Purchased the Labrador Co. The same year the M.A. Hanna Co. Purchased an interest in both exploration companies. From 1942 to 1950 extensive exploration was conducted by the Hollinger-Hanna technical staff to systematically appraise these vast concessions. More than 40 deposits of high grade ore were found and, by the end of 1950, the total ore reserves reached 418 million tons. In 1949 five American steel companies joined the Hollinger-Hanna interests and formed the Iron Ore Co. of Canada. Financing and full-scale construction were decided upon in 1950. This included the construction of a 360-mile railroad through very difficult terrain, the erection of two hydroelectric plants, the installation of terminal port facilities at Sept-IIes, the building of a modern town-site at Schefferville, the construction of crushing and screening plants, and the preparation of deposits for mining. Ore was first shipped in July 1954. Total open-pit mine production to date is 66 million long tons of direct-shipping ore. GEOLOGICAL ENGINEERING The above achievements would not have been possible without irtegrated teamwork of people of diverse skills and extensive use of geology. In their paper on the role of geologists in the development of this iron ore field, (Gustafson and Moss1 rightly emphasized the difficulties facing the early workers in the area. In an uninhabited land with no roads or railroads and no navigable rivers leading to the interior, everything had to be flown in. It was not until 1948 that aerial photographs and adequate base maps became available. In spite of these and other difficulties, an impressive amount of field work has been done since 1942. Nearly all this work has been directed by geological engineers and geologists. About 15,000 :sq miles have been geologically

Jan 1, 1962

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,&apos; 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.&apos; 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 H. Becke, D. Stolnitz, D. Flatley, W. Kern

Extensive solid solubilities of CdTe (zincblende-type struckre) and InTe (B37 type) in each of the rock salt-type compounds, PbTe and SnTe, have been observed. Partial phase diagrams have been determined by thermal analysis and X-ray metallography. The limiting mol fraction. X,, of the solute in the rock salt-type a phase and the corresponding eutectic temperatures, T,, are: (PbTe)l-x(CdTe)x: X,- 0.2, T, =866°C; (PbTe),-,(lnTe),: X, - 0.35, T, = 646"C; (SnTe),-,(CdTe),:X,- 0.11, T, = 784 "C; (SnTe),-,(lnTe),: X,-0.53, T, = 630°C. The lattice parameters of the a phase decrease linearly with X, even in (PbTe),-,(CdTe),, where a, (CdTe) = 6.481A > %(PbTe) = 6.459A. This is taken as proof that the cadmium atom enters an octahedral interstice of the tellurium atom sublattice; i.e., the formation of the a phase entails the direct replacement of lead by cadmium. The a, us X curve extrapolates to 6.16A at X = 1, in agreement with the value predicted for an ionic crystal of CdTe; it is also consistent with the reported lattice parameter It is well-established that the compositions of intrinsic semiconducting and semimetallic compounds conform to normal valence rules.1"5 The apparent exceptions can be explained by taking account of anion-anion covalences, as in CdSb, or of multiple cation valences, as in In Te.&apos;This empirical generalization is the basis of the chemical approach to semiconductors2 by which the properties of an intrinsic semiconductor are rationalized in terms of the ionic-covalent bonds necessary to saturate the valence-electron complement of the anion sublattice. A fundamental shortcoming of this approach is its disregard of long-range crystal interactions. It cannot, accordingly, deal with the phenomenon of charge conduction except through the use of ad hoc postulates. As an example, a crystal of CdTe would, in the valence-bond picture: be described in terms of electron pairs, each with the same discrete energy, localized between every cadmium and tellurium atom. This is, of course, contrary to the Pauli of the high-pressure rock-salt form of CdTe, corrected for decompression from 36 kbar. The free energy of formation of the a phase of pure CdTe at room temperature is calculated from the phase diagram to be +10 kcal per g-atom, in accmd with the value calculated from the transformation pressure. The standard enthalpy is +13 kcal per g-atom, and the standard entropy is +9 eu. The latter value implies the formation of extra classical particles, such as vacancies, interstitials, or nondegenerate charge carriers, but these alternatives are not consistent with the semiconducting properties and the densities of the a phase. The extrapolated values of the lattice parameters of (PbTe),-,(lnTe), and Spectively, for the rock salt-type modification of InTe. The corresponding interatomic separation is intermediate between monovalent and trivalent indium. The qualitative implications of the results are considered from the viewpoints of both valence-band theory and energy-band theory. principle, and is corrected by methods of molecular-orbital theory in which bonds are replaced by bands of molecular orbitals whose energies, E, depend upon a crystal-momentum vector, k.7 Each band is derived from a linear combination of atomic orbitals with two electrons required to saturate each molecular orbital in the band. In a crystal of N atoms containing z atoms in its primitive unit cell, there are 2 N/z states per band which lie in a region of k space bound by the Brillouin zone. In an intrinsic semiconductor, the bands can be grouped into valence bands which are normally filled and conduction bands which are normally empty. If the highest valence band and the lowest conduction band overlap anywhere within the Brillouin zone, the material is rendered semimetallic. The quantity defines the effective mass, m*, of an electron in a conduction band (or of a hole, i.e., an electron deficiency, in the valence band) and leads directly to the concept of charge mobility through the relation \x = et/m*, where e is the electron charge and t is the lattice relaxation time.

Jan 1, 1964

By P. S. Kotva

Dislocation substructures in superalloy matrices of varyzng co)npositions have been studied. In general, it has been found that the alloys can be classified into &apos;&apos;high", &apos;&apos;medium", and "low" stacking fault energy classes based on the type of dislocation substructure observed in the matrix and that the substructure can be correlated to the stacking fault energy. The effect of different types of dislocation substructure and dislocation reactions on the intragranulur precipitation of carbide phases has been studied. In a Ni-Cv-Mo-Fe matrix, precipitation of MC carbides in association with stacking faults has been observed. In most superalloys, solid-solution strengthening and precipitation hardening are the chief mechanisms employed to achieve strength. The latter contribution to strength is usually achieved by the precipitation of / in certain wrought alloys. Insufficient attention has been given to the problem of obtaining strength in su-peralloys by controlling precipitation of carbides on imperfections within the matrix. The present work was undertaken to investigate the dislocation substructure in various superalloy matrices, to study the effect of such substructure on subsequent precipitation of carbides in the matrix, and to investigate whether certain modes of precipitation of carbide phases found in austenitic stainless steels2"4&apos;6 would occur in nickel-base alloy matrices with dislocation substructures of the same type as those found in austenitic steels. 1) EXPERIMENTAL TECHNIQUES Five-pound heats of the various alloy compositions reported here were vacuum-cast. The ingots were given light deformation by rolling to break up the as-cast structure and then homogenized for 24 hr. HASTELLOY alloy X (nominal composition: Ni-2OCr-17Fe-8Mo-0.05C) was homogenized at 2150°F and In-cone1 625 (nominal composition: Ni-20Cr-5Fe-8Mo-3.5Cb-0.05C) was homogenized at 2280°F. Fabrication of 0.004-in. sheet was achieved by cold rolling with intermediate annealing treatments being carried out at the same temperature as those used for homogeniza-tion. Each solution anneal was followed by quenching. The aim of this procedure was to redissolve as much of the primary carbide phase as possible. Samples of the 0.004-in. sheet were cut and encapsulated in quartz capsules and then heat-treated in the tube furnaces. Thin foils were prepared using an ethanol-10 pct perchloric acid bath at 32°F and at a voltage of 22 v. A "window" technique was employed. Observations were made on a JEM-7 electron microscope operating at 100 kv. 2) EXPERIMENTAL RESULTS a) Types of Dislocation Substructure. Fig. 1 shows a schematic correlation between stacking fault energy, SFE, and the type of dislocation substructure observed in various matrices of nickel- and cobalt-base alloys. A precise quantitative determination of stacking fault energy is not implied in the figure but the correlation between stacking fault energy and the type of dislocation substructure obtained allows alloys to be divided into three classes in analogy with the classification employed by Swann and ~uttin~&apos; for binary alloys of copper. Class I alloys are associated with a "high" SFE and show a cellular substructure of dislocations as typified by the micrograph of a thin foil of pure nickel deformed 4 pct at room temperature in Fig. 2. With decreasing SFE the tendency toward cell formation is lessened and dislocations tend to be arranged in coplanar groupings. Examples of this class of alloys with "medium" SFE are provided by the mi-crostructure of solution-heat-treated, quenched, and deformed thin foils of HASTELLOY alloy X, "Waspaloy" (prior to any aging), and Inconel 625. Fig. 3 shows a thin-foil micrograph of an alloy of Inconel 625 composition, solution-heat-treated, quenched, and deformed 5 pct at room temperatures. No evidence of any cell structure can be obtained in materials of "medium" stacking fault energy, Fig. 3, even after severe deformation. The stacking fault energy of the alloy shown in Fig. 3 is, however, not low enough to make the dissociation of dislocations visually obvious. As stacking fault energy decreases further, with successive addition of solute in the matrix, there is an increased tendency toward dissociation of dislocations and cross slip becomes progressively more difficult. Eventually, when the stacking fault energy is "low" enough, complete dissociation of dislocations is seen to occur as shown in Figs.

Jan 1, 1969

By R. J. P. Lyon, A. E. Prelat, H. Lawrence

Introduction In 1977, the US Bureau of Mines awarded a grant to the state of South Carolina to explore the possibility of using Landsat multispectral scanner (MSS) data as an aid in monitoring surface mining activities in selected counties of the state. Work had been done in Aiken County prior to the grant by USBM and state personnel at the EROS Data Center using both the GE Image 100 and ESL IDIMS systems. The initial work on the 1:100 consisted of locating and measuring the areas of various kaolin mines. The results were excellent on location, identification, and accurate area measurements of several mines as compared with aerial photos of each mine. The effort also included locating and measuring the size of all mines (including sand and gravel) within two US Geological Survey (USGS) 7 % - min quadrangle maps. Line printer overlays using the IDIMS equipment and software resulted in the location of all known mines within an estimated error less than zt 91.4 m. Mine acreage was calculated by counting each symbol (which represented one pixel) and multiplying by 1.1 (the number of acres per pixel). [Fig. 1] shows a portion of one quadrangle overlay. [Table 1] gives a comparison of acreage measured for several mines from the 1-100 and IDIMS system vs. aerial photo measurements. The success of the preliminary work resulted in the South Carolina Land Resources Conservation Commission submitting a proposal to USBM for funding to expand the scope of work to other mineral mining operations within the state and determine if Landsat Imagery could be used to accurately locate and measure mining and reclamation activity on a continuing basis. Three separate tasks were proposed for selected kaolin mines in Aiken County: Task 1, to measure changes in active mine developments over the period 1974-77; Task 2, to measure reclamation activity, and, if time permitted, seasonal changes in mine signatures over the same period of time; and Task 3, to classify one complete mining operation (i.e., differentiate between active, spoil, overburden, water, reclaimed portions and surrounding terrain. The major effort was centered around J.M. Hubeis Richardson mine. Mining operations were progressing in a northerly direction and included three areas of reclamation: one prior to 1974; one started during early 1974; and one reclaimed during 1976. A discussion of all work done under the grant is available in the March 1979 Final Report listed under References. Computer compatible tapes (CCTs) containing MSS data from Landsat Path 18, Row 37, were purchased from the National Aeronautics and Space Administration (NASA) covering the period February 1974 through January 1977. The MSS data were processed on the General Electric Image 100 using parallelepiped classification at the EROS Data Center&apos;s Data Analysis Laboratory, Sioux Falls, SD, and at the Stanford Remote Sensing Laboratory, Stanford University, Palo Alto, CA, utilizing both an unsupervised classification (ISOMIX) and a supervised classification (sequential discriminant analysis). Studies at Stanford University Remote Sensing Lab (SRSL). In Feburary 1977, initial work was begun at Stanford using the STANSORT computer program running on a DEC PDP-10 (Honey, Prelat, and Lyon, 1974). This software is fully interactive and designed to study Landsat CCT data at high resolution (small areas) on a pixel-by-pixel basis (Lyon, 1977). Unsupervised Classification. The initial step was to locate the Richardson mine on the positive print of the full Landsat scene from CCT 1644-15252, dated 6/17/74. This was relatively easy due to a large abandoned kaolin mine and a long narrow pond clearly visible in the scene. Two unsupervised classifications of the Richardson mine were run using ISOMIX clustering (Honey, Prelat and Lyon, 1974). (ISOMIX essentially follows the interactive clustering procedures of ISOCLS Kan, Holley, and Parker. 1973). Although the classifications were successfully accomplished, it was apparent from the TV display that the results did not clearly define the mine areas. A supervised classification would have to be made in order to clearly separate each portion of the mine. Supervised Classification. This classification was done using the Stepwise Discriminant Program (BMDO7M) which is part of the BIOMED package (Dixon, 1970) and involved the following steps: Training group populations were selected and the digital

Jan 1, 1982

By N. J. Grant, R. Nordheim

An extensive study was made of the aging characteristics of alloys based on the 80 pct Ni-20 pct Cr composition hardened with aluminum and/or titanium, each up to 4 pct. Aging was followed by means of hardness and hot electrical resistance measurements as well as by X-ray and microscopy. Stress rupture tests at 1500°F were utilized as a check on the predicted behavior. THE titanium and aluminum hardened Ni-Cr alloys, exemplified by Nimonic 80 and Inconel X, constitute one of the more important groups of alloys developed to meet the demand for materials retaining their strength at elevated temperatures. For service in the temperature range 1200" to 1500°F, these alloys offer high creep resistance. With increasing service temperature, however, the strength of the simpler Ni-Cr base alloys falls off rapidly so that above 1500°F there is a significant loss of strength. The present investigation was undertaken with the hope that a better understanding of the factors controlling the precipitation hardening of these alloys would make it possible to increase the useful service temperature range. Primarily this investigation involved the study of the effects of titanium and aluminum on the hardening and the subsequent softening at elevated temperatures. The titanium and aluminum contents were each varied between 0 and 4 pct by weight at a constant nickel to chromium weight ratio of about 4:1. (Except when otherwise stated, all compositions are expressed on a weight basis.) The major part of the investigation was confined to alloys with less than 0.06 pct C. Recently several papers dealing with the identity of the microconstituents in the titanium and aluminum hardened Ni-Cr alloys have been published. Using X-ray analysis of the residues from anodic dissolution, Rosenbauml was only able to identify carbides and nitrides in Nimonic 80 and Inconel X. However, since Rosenbaum worked with alloys in the hot rolled rather than in the aged condition, his results are inconclusive. Recently Hignett&apos; reported that the hardening of Nimonic 80 was due to the controlled precipitation of Ni,(TiAl) having the cubic Ni3A1 structure. Taylor and Floydv-" published the results of an investigation of the nickel-rich corner of the Ni-Cr-Ti, Ni-Cr-Al, and Ni-Ti-A1 systems. In the Ni-Ti and the Ni-A1 systems the hexagonal Ni,Ti phase, 7, and the cubic Ni3A1 phase, -y&apos;, respectively, exist in equilibrium with the nickel-rich solid solution. The interatomic distances in the basal plane of Ni,Ti and the octahedral planes of the matrix are almost equal, thus explaining the Wid-manstaetten type structure formed when Ni,Ti precipitates from solid solution. When Ni:,Al precipitates from solid solution, it appears usually in globular form, often dispersed along rows corresponding to definite crystallographic directions. The 7 and phases are also the only intermetallic compounds which occur in the nickel ternary alloys with up to 25 pct Cr and 10 pct Ti or Al. Taylor and Floyd found that Ni,Ti takes practically no nickel, chromium, or aluminum into solution. Nial, on the other hand, dissolves a considerable amount of chromium and titanium and some nickel. Up to three out of every five aluminum atoms could be replaced by titanium in Ni,Al. This substitution caused a slight increase (less than 1 pct) in the lattice parameter. With respect to the effect of variation in the titanium and aluminum contents on the high temperature strength of Nimonic 80 type alloys, Pfeil, Allen, and Conway" reported that an 80 pct Ni-20 pct Cr alloy containing 0.20 to 0.30 pct A1 had the highest creep resistance when the titanium content was kept between 1.65 and 2.75 pct. Experimental Procedure The materials used for this investigation were electrolytic nickel, electrolytic or low carbon chromium, sponge titanium and 2s aluminum. The alloys were melted in an indirect carbon arc furnace under

Jan 1, 1955

By N. J. Grant, E. Gregory

The creep rupture properties of wrought aluminum powder products made from five grades of sintered aluminum powder were investigated at temperatures from 400° to 900°F for rupture times up to 1000 hr. The effect of stress concentrations on materials of this type was investigated by means of notched creep rupture tests. A tentative correlation was obtained between the creep rupture properties and the structure as revealed by electron micrographs. SEVERAL papers have been published recently concerning the production and properties of wrought aluminum powder products and their possible high temperature applications. Most of the published work in this field has come from abroad, notably Switzerland, and articles by Irmann and his colleagues were summarized in English recently.&apos;.&apos; Most of the papers published by Dr. Irmann are principally concerned with the retention of properties (by a product which is produced from extremely fine flake powder and is subsequently hot extruded) after heating to high temperature for prolonged times. The powder may be in atomized or flake form, and during hot working the applied pressure is reported to plastically deform the aluminum powder, thus breaking the oxide skin and welding the particles together. Irmann attributes the remarkable properties to the dispersion of oxide inclusions. Specifically, the product described by Irmann is one labeled SAP (Sintered Aluminum Powder) in which the initial flake powder is so fine that at least 50 pct of the flakes have one dimension of 2 microns or less. The composition of the starting aluminum shows in percent, Fe, 0.18; Si, 0.19; Zn, 0.06; Ti, 0.03; Cu, Mn, Mg, all nil; balance Al, approximately 99.5 pct. Aluminum is not the only material that has been found to have increased resistance to deformation at elevated temperatures when produced by powder metallurgy. It has been reported by Middleton, Pf eil, and Rhodes- hat platinum has a higher recrys-tallization temperature when produced by powder metallurgy and exhibits peculiar properties, many of which are similar to those of the aluminum powder products. Difficulties were encountered in explaining the reason for the strengthening in the case of platinum since the existence of the oxide is doubtful. The authors attributed the special properties to "a small amount of suitably dispersed porosity." This theory was supported by von -~eer-leder4 in the discussion to the paper, and the similarity between this method of hardening and that suggested by Rohner in his theory of age hardening was pointed out. R. de Fleury5 attempted to explain some of the properties in terms of the modulus of elasticity and elastic limit of alumina and aluminum while von Zeerleder examined the relationship between the yield strength and the reciprocal of the powder particle size. Boenisch and WiderholtQ dealt mainly with the corrosion resistance of the powder aluminum material and compared it with other aluminum alloys. The diffusion rates of other metals in SAP and pure aluminum have been compared by Seith and Lop-mann.&apos; They showed that the alloying metals diffuse particularly quickly in SAP possibly due to the very fine grain size. The properties of the Alcoa products were given by Lyle.&apos; The creep rupture properties of SAP and two of the Alcoa experimental powder products were compared by Gregory and Grant hnd it was shown that these products are vastly stronger at 900°F than are the best cast and wrought alloys at 600°F. Since the publication of these data, the authors have investigated two further aluminum powder products and it is the object of this paper to show how the high temperature creep rupture properties of the five materials vary with oxide content and with the structure as revealed by electron microscopy. Materials One of the five products, SAP, a sintered aluminum product, was supplied by the Societe Anonyme pourl Industrie de l,Aluminium, Neuhausen a/RHF, Switzerland, through Dr. R. Irmann, while the others, M276, M257, M293, and M255 were supplied by the Aluminum Company of America as experimental powder metallurgical products. M255- and M293 were made from coarse and fine atomized powders, respectively. The other materials were made from flake powders with significant differences in oxide content, the details of the type of powders used in the manufacture of these materials

Jan 1, 1955

By R. V. Hughes, J. N. Breston

Conclusions drawn by previous research workers with reSPect to the relation between Pressure gradients and/or velocity and oil recovery obtained by laboratory water flood tests have been in disagreement probably due to variable procedures and unnatural conditions and materials. The Bradford Laboratory of the Pennsylvania Grade Crude Oil Association as part of its secondary recovery research program has conducted nineteen water floods on two long cores of widely differing characteristics in an attempt to clarify this relationship and make it an aid in predicting flooding pressures in the field. Unlike previous research procedures the present experiments were conducted with the aim of duplicating field conditions as closely as possible by using long unextracted consolidated cores, a live crude, and natural brines for both flooding and, connate water content. Also, the pressure gradients and flooding velocities were representative of field conditions where similar sands were being flooded. Eleven floods on one core and eight floods on the other core showed increased recoveries and lower residual oil saturation with increased flood pressure gradients and flood velocities. A marked decrease in recovery was obtained from both cores at very low flood velocities. This pressure versus recovery relationship is shown to hold up to the point of water breakthrough and also up to the 100 and 1 produced water to oil ratio point. INTRODUCTION The possibility of water flooding oil sands was suggested by Carl1 of the Pennsylvania Geological Survey in 1880. It is not known when the practice was tried intentionally for the first time, but its beneficial effects were noted in the annual production rate of the Bradford field as early as 1907. The practice was illegal in Pennsylvania until 1921. Early water floods in the Bradford field usually consisted of shooting or splitting the casing secretly to permit subsurface waters to enter the producing sands under hydrostatic head. As it was noted that the benefits of water flooding seemed to be proportional to the quantity of water dumped into the well many also began to utilize surface sources after the practice became legal. It was probably during the middle 20&apos;s before many producers realized that the pressurehead of the water upon the producing sand determined the rate and quantity of water that would enter the sand. Hence, rate and quantity of production appeared to be a direct function of input pressures. By 1927 a few producers had ventured the installation of pressure pumps in order to increase water-input rates and production through the combination of hydrostatic and hydraulic pressures. The adoption of pressure flooding and the "five-spot" drilling pattern in the Bradford field were essentially simultaneous. Water-input pressures in 1930 seldom exceeded 300 p.s.i. at the well head or 1100 p.s.i. at the sand face. Since that time, water-flood producers in the Bradford-Allegany fields have gone to higher and higher pressure until today 600 p.s.i. at the well heads is called a low pressure flood. Many high pressure floods now operate at 1300-1400 p.s.i. at the well head. The limiting and advisable pressure at the sand face has been pronounced as that pressure just under what is required to lift the overburden or to cause formation parting: According to this rule any water flood operation utilizing well-head pressures nearly equal in pounds per sq. in. to 1.1 times the average depth in feet to the top of the producing sand would be considered as a high-pressure flood. Despite the higher pressure trends in the Bradford-Allegany field operations and the results of early laboratory water flooding research, the desirability and benefits of high input pressures are still questioned by many operators, particularly in midwestern water flood operations. The present paper recounts a series of 19 laboratory water floods using two long, consolidated cores of widely differing characteristics saturated with live crude and flooded with oil field brines in an effort to simulate field conditions under • various pressure gradients and flooding velocities. For both cores, higher recoveries and lower residual oil saturations were obtained at higher pressure gradients and flood velocities. This relationship is shown to hold up to the water breakthrough point and also up to the 100 to 1 produced water to oil ratio point.

Jan 1, 1949

By J. M. Blank, V. A. Russell

When the nucleation of silicon on a sapphire substrate is accomplished by gradually decreasing the substrate temperature while subjecting it to a constant impingement rate of hydrogen and silicon tetrachloride, the resulting deposit is characterized by widely separated islands of silicon scattered over an "open sea" of sapphire. Analysis shows that nucleation takes place mainly on sites of large adsorption energy, about 85 kcal per mole, and small surface concentration, about 108 cm-2. Crystal growth proceeds rapidly on these nuclei and results in enough depletion of Sicl4 from the ambient gas to suppress further nucleation. The technological importance of single-crystal films on dielectric substrates has prompted considerable work on the deposition of silicon on sapphire. This paper is concerned with the deposition of silicon, by the reduction of silicon tetrachloride with hydrogen, onto heated sapphire substrates. The apparatus consisted of a temperature-controlled container for the silicon tetrachloride along with gas lines and flow meters necessary to convey a hydrogen-silicon tetrachloride mixture to a reaction chamber constructed of quartz tubing. Heat for the substrate was provided by means of an inductively heated graphite susceptor. The observations pertinent to the present discussion were made with an American Optical Co. high-temperature microscope which allowed us to make motion pictures of the deposition process at a magnification of approximately 50 times. Two main categories of experiments were carried out: one on determination of critical condensation temperatures and the other on the deposition of epitaxial silicon films on the sapphire substrates. Critical condensation temperatures were determined in the traditional way by raising the substrate temperature well above that at which condensation could be expected at the impingement rates being studied and then gradually lowering the temperature until the condensation of the first silicon was observed. This was done initially with ellipsometry-type detection but it was soon discovered that the deposits were occurring as widely separated islands and groups of islands scattered over an "open sea" of sapphire. We have called these archipelago formations. They were most easily detected by optical microscopy. Data gathered from experiments of this type have been collected in Table I. Motion pictures of the formation of archipelago patterns show that the nucleation period lasts about 10 sec if the substrate temperature and impingement rate are kept constant. Essentially all of the nuclei are formed in a few seconds and all subsequent silicon deposition merely adds to the size of the established nuclei. After an archipelago formation has matured at a given substrate temperature and impingement rate, it is very difficult to stimulate any further nucleation in the open space between islands. Lowering the substrate temperature will occasionally stimulate nucleation but increasing the impingement rate hardly ever produces any more new nuclei. It should also be emphasized that the nucleation rates appear to be very small, about 104 cm-2 sec-1. They will receive special attention in the analysis section. Another series of experiments was performed employing a systematic variation of substrate temperatures and impingement rates approximating those expected to produce epitaxy. Sapphire substrates with surfaces normal to the 2233 direction were used. In contrast to the procedure that produces archipelago patterns, these films were deposited by raising the substrate temperature to a desired value at which time the silicon tetrachloride and hydrogen flow was begun. Of course, these depositions produced mainly films that were continuous. After removal from the deposition chamber, the substrate and silicon film were examined microscopically to determine the nature of the deposit and by X-ray diffraction to determine the extent to which a single-crystal film had been achieved. Results of these experiments are summarized in Table 11. Of interest for the present analysis is the fact that epitaxy appears to be confined to a fairly narrow temperature range between about 1050" and 1150°C. This also will be discussed in the analysis section. ANALYSIS In this section we shall apply nucleation theory to the data presented above with the objective of testing

Jan 1, 1967

By L. D. Lash, J. R. Ross

Discovery of scandium in the Vitro solvent extraction plant for uranium led to commercial recovery of the byproduct. Micro amounts of scandium were extracted with uranium by dodecyl phosphoric acid, but failed to follow ura-niuminto the hydrochloric acid strip solution and were eventually concentrated in the organic extractant. A fluoride strip system was developed to recover scandium from the solvent in concentrated form. High purity scandium oxide was then prepared in multi-pound lots by chemical separation techniques. The plant recovery operation, final product purification, and analytical procedures are described. Scandium is a pseudo-rare earth which is truly rare and expensive. It has special properties which may make it desirable even at the present price of $2750 per lb. Recently the price was lowered from $5000 per Ib which had prevailed since 1952, and it is anticipated that usage will be stimulated because of the lowered price. This metallic element is distributed widely in trace amounts in the rocks of the earth&apos;s crust. In addition to micro-amounts found in most uranium ores, concentrations of 50 to 100 ppm have been found in Colorado ferberite ore, lateritic nickel ore, heavy sandstone from Utah, Wyoming, and New Mexico, and various zircon sands and monazites from the western part of the U. S. Scandium has been found as an essential constituent of very few minerals, the most important being thortveitite, a scandium silicate. At the present time, this mineral commands a price more than twice that of gold. Chemically, scandium is in group 3A of the periodic table. It is closely associated with yttrium and the rare earths which it strongly resembles in its reactions. It has a valence of three and will form an insoluble hydroxide, fluoride, or oxalate under proper conditions, similar to the rare earths. Eight years before its discovery, scandium was predicted by Mendeleef who ascribed his eka-boron with properties nearly identical to the actual properties of scandium. Its position as the element with Atomic No. 21 and Atomic Weight 44.96 places it between calcium and titanium in Period 4 of the chart. The successful commercial application of scandium must depend on unique properties to justify use of this high cost substance. Greater consumption would allow additional price reductions, but scan- dium will remain a relatively high-priced commodity because of its inherent scarcity. Research reportedly has been oriented toward use of scandium as an agent to achieve high-temperature, low-density alloys with magnesium and tantalum.&apos; Also, the U.S. Air Force sponsored a project for production of research amounts of pure scandium metal.&apos; The oxide has been used experimentally in electronics, ceramics, and metallurgy. The various aspects of scandium are well covered in recent publications.s-5 CONCENTRATE RECOVERY Small amounts of scandium exist in uranium ores and are dissolved during an acid leach yielding up to 0.001 gpl Sc2O9. When Vitro converted their uranium plant from phosphate precipitation to solvent extraction: scandium was found to follow the uranium into the dodecyl phosphoric acid solvent (DDPA). However, scandium did not strip with uranium from the DDPA in hydrochloric acid, but remained in the solvent. Therefore, a concentration of scandium built up in the organic phase. Residues from the solvent were spectrographed by the U.S. Bureau of Mines and found to contain scandium. As a result of this discovery, provisions were made in the plant for recovery of scandium-bearing concentrates. Solvent extraction of uranium was added to a conventional acid leach process in a typical installation? The ore was crushed and ground, and then leached with dilute sulfuric acid. Addition of an oxidant such as sodium chlorate insured conversion of uranium minerals to a soluble form. At this point, the slurry was chemically reduced by a sulfide, such as sodium hydrosulfide, to remove substances such as ferric iron and molybdenum which were partially extracted by the solvent. The solids-liquid separation was accomplished by a four-stage counter cur rent decantation (CCD) thickener circuit. The uranium was extracted from pregnant liquor with 0.1M DDPA in kerosene and stripped with ION

Jan 1, 1961

By L. D. Mullins, W. R. Bartlett, R. H. Barham, W. L. Wahl

This paper describes an electrical model and its applicution to the analysis of four reservoirs in Saudi Arabia. The model has 2,501 mesh points and represents 35,000 sq miles of the Arab-D member. Details of modeling such as mesh size, control problems and standards of performance in matching reservoir history are discussed. The particular performance match achieved for the Arab-D rnember is presented. Details such as permeability barriers, aquifer depletion and iwerference between oil fields are given. The performance match realized in the Abqaiq pool is presented in detail. INTRODUCTION The resistor-capacitor network and associated control equipment described in this paper comprise an electrical analog of a reservoir system. Similar equipment has been used to study the transient response of reservoirs for many years. The unique feature of the model and application to be described is the extremely large size of the model and reservoir system, and the detail observed in simulating the reservoir with the model. The Arabian American Oil Co. first became interested in analog computers for simulation of oil reservoirs in 1949. Since that time, several models have been developed, each more elaborate and refined so that the reservoir system might be more closely simulated. The current model is the latest in a series designed, built and operated by the Field Research Laboratory of Socony Mobil Oil Co. in collaboration with Aramco. It has been and continues to be used to study the regional performance of the Arab-D member limestone reservoir. The Arab-D member is one of the Middle East&apos;s most prolific producing horizons.. THE MODEL The theory of simulating a reservoir system with an electrical system has been presented in the literature.1-5 Therefore, this paper will not discuss the theoretical aspect of the problem except to point out the correspondence between the fluid system and electrical system, as shown in Table 1. In general, the complete model is made up of input devices, output devices, central control and a resistance-capacitance (RC) network. At times, the RC network alone is referred to as the "model". However, it should be evident from the text which meaning is attached to the word "model". A discussion of the equipment follows. THE RESISTANCE-CAPACITANCE NETWORK The RC network consists of 2,501 capacitance decades interconnected through 4,900 resistance decades. The components are arranged to form a rectangular network of 2,501 mesh points in a 41- X 61-mesh array. Imposing the mesh grid system on the continuous reservoir system divides the reservoir into discrete areal segments. These discrete segments may be of various sizes. More precisely, the mesh size need not be uniform throughout the model. The RC network is fabricated in two sections which are connected at the top. An inside view of the "tunnel" formed by the two sections is shown in Fig. 1. The height and width of the tunnel are shown in the figure. Numerals appear along the bottom and along the back opening of the tunnel. These numbers denote the x and y co-ordinate positions of mesh points. Fig. 2 presents a rear view of one-half the model. The length dimensions of the model, as well as a rear view of the capacitor decades, are shown in this figure. The control dials used in adjusting the resistance and capacitance values on the model can be seen in the enlarged portion of the model shown in Fig. 3. The electrical capacity at any mesh point can range from 0 to 1.0 microfarads set to the nearest tenth of a microfarad. The electric resistance connecting any two mesh points can range from 0 to 9,990,000 ohms set to the nearest 1,000 ohms. External capacitors may be added to any or all mesh points if the need arises. The values of electrical resistance and capacitance are adjusted manually by manipulating the two types of decade units. INPUT EQUIPMENT A considerable quantity of equipment is used to control the input to the RC network. These input devices are

By Frank Doxey

AT Dominion Steel & Coal Corp. it has long been recognized that continued mechanization of mine operations is necessary in the Pictou, Cumberland, and Sidney coal fields of Nova Scotia. The varied physical conditions in these fields call for special consideration of individual cases before planning is finalized. Because standard equipment cannot be procured which would operate successfully, many experiments have been necessary over the years to keep pace with the progress made in other countries. There are two mines, producing 2000 tpd, located in the Pictou coal field. The field is badly distorted and crossed by many faults. Seams are highly inclined and irregular and vary in thickness from 5 to 40 ft. Entries are difficult to maintain because of squeezing of the coal. ribs and movement of the roof and pavement. Output from the three operating mines in the Cumberland field is 3000 tpd. The field is highly inclined, inclination varying from 12° to 32°. Overlying beds consist of shales and massive sandstone lenses of extreme toughness and are responsible for bumps when the stresses are relieved by extraction. At greatest depth these are among the deepest coal workings in the world. Depth of cover ranges from 2300 to 4000 ft. This prohibits room-and-pillar working and necessitates longwall operation. Working of contiguous seams concurrently to maintain output increases the already difficult conditions. The Sydney field, with a frontage of about 30 miles, is the most important of the Nova Scotia coal fields. With the exception of one small area it is now wholly submarine. Output is approximately 21,000 tpd. Seams are 21/2 to 8 ft thick, and cover in the areas varies from 600 to 2300 ft, with an average of 1500 ft from sea bottom to the top of the seam. The seams dip in a seaward direction, pitches ranging from 6" to 4.0". The shoreline is the last place of entry to the seams and distance from the bank to the working faces is generally over 3½ miles, in some cases as much as 6½ miles. Ventilation is a problem and requires the construction of large permanent airways. Getting and Loading Coal: In 1925, in view of heavy pressures exerted by thickness of cover overlying the seams, roadways and pillars of the room-and-pillar system being worked began to break up and coal was lost. It was decided that a change in the method of extraction in areas with heavy cover was necessary, and experiments were made with many short walls and longwalls varying between 90 and 250 ft. Trial and error proved that the best operating length was between 400 and 500 ft, delivering all coal to the dip, with roadways to the face following a level course. The change-over was gradual, and the technique of roof control developed with the system, so that falls to the face are now very infrequent. An advantage of longwall mining is that it yields 95 pct extraction, especially important in coal seams of high quality or in seams where faults or disturbances restrict the workable areas. This percentage of extraction is based on the fact that the longwall advancing system takes development faces where pitch permits instead of driving headings and leaving roadway pillars. This system yields high tonnage during development and limits loss in extraction to duff left during operations. Accompanying disadvantages, on the other hand, are the heavy construction cost of main roadways and the necessity of driving all new flank face roadways through the gob. If the main roadways are driven through the solid, and large enough pillars are left on each side for protection against flank face weights, then the width of solid coal is approximately 1700 ft. This represents 10.6 pct of the coal available, or 89.4 pct extraction of the whole. These pillars, however, are of such size that they provide a useful pillar drawing area as a final operation of the mine. It may be that although the seam cannot be generally mined by the room-and-pillar method, it can be adapted to

Jan 1, 1955