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By R. L. Perrine

The rise of drain holes drilled from a well to improve productivity is becoming increasingly common. This paper presents data on the productivity increase that may he expected. The data were obtained by use of an electrolytic tank mode1 of a reservoir. Parameter varied in the study to show their effect on productivity include the length, number, and arrangement of drain holes, formation thickness, and damage near the well-hore. The most important results are that very large increases in productivity can be expected only ill damaged wells. The distance, to which drain holes penetrate is of primary importance. Additional length is more effective than increasing the number of drain holes. INTRODUCTI O N In planning the use of drain holes to improve productivity, it is important to he able to estimate the increase in production that can be obtained for a given expenditure. It is also important to know what combination of parameters related to the use of drain holes can he chosen to give the largest production increase. This paper presents data on the productivity increase that may be expected, as obtained by use of an electrolytic tank model of the reservoir. In this study, :! number of parameters were varied to show their effect on productivity. These included the length, number, and arrangement of the drain holes. The presence or absence of a damaged zone of low permeability around the well-bore and the thickness of the producing formation were also considered. The productivity increase that might be expected due to drain holes is presented as the ratio: productivity of a well after drain holes are drilled and completed to the productivity of the same well in an undamaged state without drain holes. The symbol Q/Qo is used to represent this productivity ratio. Thus, the comparison in each case is with a formation of uniform and undamaged permeability. Additional notation includes I;, for the radial extent of the damaged zone, which is assumed to be cylindrical and concentric with the wellbore. Thus the effect of an actual block is approximated by a discontinuous varia-tion in permeability. For purposes of this paper, the permeability within the damaged zone, denoted by kb, is assumed to be 1/25 that in the remainder of the formation, or k. A necessary assumption in making comparative tests using an electrolytic model is that reservoir flow behavior can be approximated by single-phase, steady-\tate flow according to Darey's Law. In addition, the formation must be assumed to be homogeneous with equal horizontal and vertical permeability. The well-hore diameter in this study is assumed to be 11¾ in. and the drainage radius of the well equal to 500 ft. The drain holes are considered to have been completed without damage. THE ELECTROLYTlC MODEL 'She producing formation was modeled by forming a sheet of phosphor-bronze into a cylinder 40% in, in diameter to represent the boundary of the drainage area. This was enclosed in a waterproofed plywood box, and the box filled to an appropriate level with a dilute sodium chloride solution. Solution concentration was adjusted to give a total resistance from

Jan 1, 1956

By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami's reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."' A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. ' J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

By M. R. Lorenz

Efficient visible light emission from p-n junctions in semiconductors is currently achieved in the four materials, Sic, GaP, ]Ga1-xAs and GaAs1-x,. Recent advances in materials preparation and p-n junction formation are briefly reviewed. The radiative recombination processes in the different materials depend largely on the band structure and the impurity states of each material. The spectral distribution of the emission ranges from the blue in Sic, to green in Gap, yellow in Sic and red in Gap, Ga1-x AlxAs and GaAs1-x Px. The origin of the various processes are discussed. The conversion of the electrical power into optical power and the measurement of the conversion efficiency are reviewed. The currently maximum quantum efficiencies at 300°K are: 3 pct in GaP(red), 1 pct in SiC(yellow), 0.1 pct in GaP(green), 0.2 pct in Ga1-x AlxAs at 66001, and 0.1 pct in GaAs1-x Px at 6800. The brightness and the interplay of the quantum efficiency and the luminous efficiency are given detailed consideration. VISIBLE light generated by the application of a direct current to a semiconductor crystal was first observed by Lossev1 in 1923. Light emission came from naturally occurring junctions in Sic crystals but little was known then with regard to the mechanism of charge transport and light emission. Some nearly 30 years later and with a vastly increased understanding of semiconductors the phenomenon of electroluminescence was studied in more detail, for example in p-n junctions of germanium.2 In these early studies, the efficiency of converting the electron current into a photon current was very low and therefore aroused little interest toward practical application. More recently it became apparent that in certain materials, for instance GaAs, and under certain conditions, the conversion efficiency was not low at all.3 The subsequent discovery of the p-n junction laser4-6 provided the impetus for increased studies of electroluminescence. Light emitted from GaAs occurs in the infrared region of the electromagnetic spectrum and is not visible to the eye. At nearly the same time the use of GaAs1-xPx led to laser action at low temperatures which was visible to the eye.7 Later a red light emitting diode, made from Gap, was reportedS which emitted incoherent radiation at 300°K with an external quantum efficiency of about 1.5 pct. The fact that such efficient devices were obtainable led to a more concentrated effort in the search for highly efficient room-temperature semiconductor light sources. It is some of this later work on p-n junction luminescence with which we will be concerned here. Since our aim is centered on visible light, with hv =1.8 ev ( ?=7000?), only the wider band gap semiconductors are of interest, i.e., Eg 1 1.8 ev. Although many compounds meet this criterion, only a limited number of those are also good semiconductors, i.e. contain low resistance n and p regions. Some of the more promising candidates are listed in Table I. We will only be concerned with light generation from a p-n junction. This limitation excludes essentially the group II-VI binary compounds, although we will briefly review the case of ZnTe and the solid solution ZnTe1-xSex. As we will show they may contain a p-n junction but only of a special kind. Most of the discussion will deal with the four materials, Sic, Gap, Gal-xAlxAs, and GaAs1-xPx. These appear to be at the present time the best visible light emitting semiconductors. In the following sections we will briefly consider: 1) the electrical properties of p-n junctions; 2) some recent advances in materials preparation; 3) the formation of p-n junctions; and then in somewhat greater detail we will consider: 4) the various radiative recombination processes; 5) the measurement and observation of the external quantum efficiency; 6) the luminous efficiency; 7) the brightness of light emitting diodes (LED'S). THE P-N JUNCTION The p-n junction in a semiconductor crystal is the interface between two differently doped regions. More specifically the p region is doped predominantly with acceptor impurities and the n region contains predominantly donor impurities. The energy band structure of a degenerate p-n junction at thermal equilibrium is shown in Fig. l(a). The excess electrons on the n side of the junction are confined to this region by the barrier potential Eg. Similarly the excess holes on the p-side of the junction are confined to the p-region by a similar potential barrier. If we now apply a dc voltage V such that the p region is made positive and the n region negative, the barrier potential EB is reduced by the applied voltage, V and the junction is said to be forward biased. With the barrier potential lowered, electrons and holes can drift toward the p region and n region, respectively, see Fig. l(b). The current voltage characteristics of p-n junctions in most wide band gap materials can be described by the relation: J = Joexp(eV/BkT) [1] where the functional form of Jo is determined by the recombination mechanism. Jo is generally a complicated parameter which depends on a number of different factors including temperature, junction width, bias voltage, and carrier lifetimes. The parameter B also depends on the recombination mechanism but

Jan 1, 1970

By R. D. Pehlke, J. V. Gluck

AS a portion of a general study of liquid-metal thermodynamics, high-temperature galvanic cells were used to study the effect of added dilute solutes on the activity of zinc in dilute solution with molten bismuth in the range 450° to 650°C. 1,2 The cells were of the type The experimental procedures have been described previously.1 In the course of studies conducted in the bismuth-rich corner of the systems Bi-Zn-Au and Bi-Zn-Cu, marked discontinuities were observed in the electromotive force-temperature relations for a number of the experimental compositions. Above the discontinuity temperatures, the relations, which were linear, exhibited slopes similar to the binary alloy of the same mole fraction zinc, as shown in Figs. I and 2. Below the discontinuity temperatures, the slopes were markedly different, but the relations remained linear. In general, as the amount of the third eletnent was increased, the slope of the lower portion of the relations tended to become less positive. The slopes of electromotive force-temperature relations reflect the entropy of mixing of zinc and, therefore, the occurrence of a discontinuity marks the transition between two different equilibrium situations involving the solution of zinc. A number of other investigators3-5 have used such observations to determine liquidus boundaries in binary alloys. Since the upper portions of the ternary electromotive force-temperature relations of this study had the same slopes as the binary alloys, the discontinuities are interpreted as marking the transition between the single-phase liquid region and the underlying two- and three-phase regions. Reference to the Zn-Bi equilibrium diagram6 confirms that the binary alloys were single-phase liquids at the experimental temperatures. Fig. I shows the electromotive force-temperature relations for the alloys containing Bi-Zn-Au and Fig. 2 shows similar relations for the Bi-Zn-Cu alloys. In the lower portion of each figure, the temperature of the discontinuity is plotted vs the mole fraction of the added solute at the various levels of zinc concentra- tion. Cross-plots from these curves at constant temperature permitted the construction of the partial liquidus surface isotherms shown in Figs. 3 and 4.

Jan 1, 1967

By O. A. E. Jackson

In all three principal dunite dikes, minute disseminated grains of pyrrhotite are to be seen in the fresh rock in amounts less than 1 pct. Traces of nickel have been reported from many such specimens. Nickeliferous pyrrhotite is the principal nickel-bearing mineral, although olivine contains very minor amounts of nickel in solid solution, substituting for magnesium and iron. Such occurences are of no economic significance. Nickel analyses of possible economic significance (up to 3 pct Ni) have been returned from samples taken near the margins of the two large western dunite dikes. These samples were from schistose zones along and within the dike walls. The mineralized shear zones, up to 30 ft wide, strike N 30 W and dip from 65" to 90" west. They consist of layers of hard, fresh, green-gray dunite, mineralized with finely disseminated pyrrhotite. These layers alternate with layers of soft, black, oxidized schistose dunite up to 1 ft wide, well mineralized with pyrrhotite and tabular-fractured pentlandite in crystals up to 1/4-in. diam. Sulfides identified in polished sections were chiefly pyrrhotite and pentlandite, with much smaller amounts of chalcopyrite. There are two varieties of pyrrhotite. One develops a fine polish and conforms to published descriptions. The other is slightly darker and browner, does not polish as well, and displays flamelike growth or intergrowth structure when etched with nitric acid fumes. Pyrrhotite and pentlandite crystallized contemporaneously in the form of veins in the olivine and as fillings of the interstices of euhedral olivine crystals. Chalcopyrite replaces the other sulfides. The most striking feature of the deposits is their occurrence in intimately fractured and schistose zones in the dunite where faulting has been localized along the contacts of the sediments and the dunite dikes. Though far too little detailed work has been done to be certain, there appears to be a higher concentration of sulfides in the shear zones along the margins of dike apophyses, sediment reentrants, and strike and dip irregularities. Much more study would be required in order to submit a plausible theory of formation of the nickel deposits, supported by laboratory and field evidence. Results of the present study, especially localization of the metals by fracturing, certainly indicate that the nickel concentrations were brought about by precipitation of nickel sulfides from fluids that used the fractures as a means of ingress. Studies of nickel sulfide deposits throughout the world have demonstrated that such sulfides were deposited at considerable depths and at temperatures of several hundred degrees. This would rule out the possibility of groundwater as the transporting medium. The two possible sources of hot nickel-bearing fluids are quartz diorite and gabbro. The first possibility is that large volumes of fluids, expelled from the quartz diorite magma during its crystallization, obtained a supply of nickel by altering the nickeliferous olivine of the dunites. The likelihood of this process is lessened by the recognition that, although the dunites show some alteration to serpentine, talc, and trem-olite, they are for the most part remarkably fresh outside the schistose zones. The worldwide association of nickel with basic rocks, together with the presence of pyrrhotite in thin films on joint planes of the gabbro on Jumbro Mountain, favors the gabbro source. The writer extends thanks to C. Phillips Purdy, Jr., project chief of American Metal Climax Inc., for giving him the opportunity to study these deposits. He is also indebted to the officers of American Metal Climax Inc. and Discovery Mines Inc. for permission to publish this article.

Jan 1, 1961

By Robert R. Walden, LaMont West

KENTUCKY'S first acid-grade fluorspar flotation mill, shown in Fig. 1, was placed in operation Aug. 1, 1952, by the Pennsylvania Salt Manufacturing Co. at Mexico, Ky. During 1951 a critical shortage of acid-grade fluorspar developed and it became necessary for the company to produce part of its fluorspar requirements. In 1951 the company purchased the Crider and Lennen metallurgical fluorspar mill and an adjacent stockpile of tailing at Mexico, Ky. The tailing, assaying about 26 pct calcium fluoride, originated from log washer and jig mill concentrators in the area. As the mill did not have a fluorspar dryer or convenient rail facilities, the company leased the Burleson concentrator at Marion, Ky., where these facilities were available. At Marion, Ky., on the Illinois Central Railroad, dry acid-grade fluorspar is transported direct to the company's Calvert City, Ky., hydrofluoric acid plant.

Jan 5, 1954

By H. K. VAN POOLLEEN, W. Hurst, H. C. Bixel

In an earlier publication* I showed the development of the instantaneous point source solution for a well producing at a constant rate at the center of a system of two radial, adjoining sands of different permeabilities. I also showed how a wellbore radius could be incorporated if this were the development required. For the purpose of that paper and the point I wished to make, this solution served. It yielded a simplifying solution of sands in series identified by Eqs. VI-26 and VI-27. (These equations are reproduced in part by Bixel and van Poollen as their Eq. 3, Page 302.) I am well aware that the simplified solutions are approximations. The facts that these Ei-functions satisfy the diffusivity equation and meet the boundary conditions both at the well and at the interface between sands, and that the earliest time considerations yield zero pressure drop, are evidence that the solutions are good approximations. This was the purpose for these formulas, which I interpret that where the permeabilities are of finite order of magnitudes in the respective media, the relations give satisfactory answers. However, from the authors' point of view there are reservations, which leads me to consider their entire generalization as illustrated in their Figs. 1 through 14. What I understand from their storage capacity, relationship Fs, which is the ratio of the product of porosity and compressibility of Sand II to Sand I, that is employed here by the authors as a correlative means of identifying one figure from another, there is nothing in the exact mathematics that supports such a term as a means of correlation. This is taken out of context, unsustained that this applies. Here the mathematics are known, where the true correlation is the diffusivity term of one sand to another. This entails permeability that refers back again to the term M in their paper for the transmis-sibility of fluid from one sand to the other that should have also been a part of this storage capacity. In Figs. 8 through 14, which purported to show the simplified equation following this correlation, there are apparent discontinuities for M equal to or less than 0.1000 that differ from the trends for greater values of M. In this connection there is no reference radius given for this cumulative pressure drop in the paper that would permit me to make these calculations. However, what is clear for M equal to 0.1000 or less we are treated to almost a closed barrier at the interface; a condition entered by the writers without qualification. This across-the-board treatment of these simplified formulas, whatever the motive of the authors, enters into a range of permeabilities that even I as the contributor would have reservations that such could apply. Under comparable conditions I would be looking at a closed reservoir or some facsimile for such. The extent to which the approximation or the exact equations pertain is not evident in the generality offered by Bixel and van Poollen in their paper. Only when they or other writers show the comparison of the pressure distributions within the formations can one be able to judge the rational limits to subscribe to the simplified formulas.

Jan 1, 1969

By G. W. Josephson

GRANULAR mineral products used primarily to form a protective and decorative coating on the weather surface of composition roofing are called "granules," "roofing granules," or "slate." The latter term is a relic of the early days of the industry, when crushed slate was the dominant type of granule in use. Asphalt roofing is made by saturating and then coating a continuous strip of felt with specially compounded asphalts. Granules are embedded in the hot asphalt on the top of the sheet, and mica or talc is dusted on the back. After passing through press rolls, the strip is looped on a conveyor for cooling and then cut into shingles or packaged as roll roofing. HISTORICAL DEVELOPMENT Although the durability and protective qualities of asphalt and tar have been known since the earliest days of recorded history, it was not until 1780 that the first forerunner of present-day composition roofing was developed.' Large-scale expansion of the industry has taken place since 1900. At first the process consisted simply of dipping sheets of burlap or other fabric into a tank of molten tar or asphalt. The long strip of roofing was rolled up, for convenient handling, and the early experimenters soon found that it was necessary to dust the surface of their new "roll roofing" with some kind of material that would prevent the tarred surfaces from sticking together. Any finely divided, low-priced local material like sand or fine gravel served this purpose and from its application the roofing-granule industry grew. As time went on, other characteristics of a properly applied mineral surfacing were recognized. As with wooden shingles, tar and asphalt can be ignited by flying embers from nearby fires. It was found that by in- creasing the largest particle size to the maximum that could be success- fully embedded and by properly controlling the amount of smaller fractions retained in the grade, so as to cover the asphalt completely, a high degree of resistance to fire was attained.

Jan 1, 1949

By D. N. Collins, J. R. Stevens

New expressions in the technical assessment of mineral concentration processes have been defined as Concentration Efficiency: Concentration Index: where h is the percentage of head grade; c, percentage of concentrate grade; maximum percentage of concentrate grade obtainable at 100 pct recovery; and R, percentage of recovery. In developing these expressions, the basic requirements for the technical assessment of concentration operations have been defined and the various expressions suggested by others for asses-sing the results of such operations reviewed and criticized. The derived expression for E, depends on a simple combination of recovery (R) and a new term selectivity (s), where S is (c-h)/(c,,, -h), by definition. Limitations of the new expressions are discussed and examples given of applications to concentration operations. It is also shown that the formulae for E, and I, can be applied to scatter diagrams, multi-component systems, size-assay analyses, and classification data. Many methods of quantifying concentrating operations have been proposed. These include direct presentation of weights and assays together with the derived data for other items such as ratio of concentration, recovery, rejection losses, and enrichment ratio. These terms are now accepted mineral dressing nomenclature, and in the assessment of the results of concentration processes, concentrate grade and recovery are together the most widely accepted measures of concentration efficiency. For practical purposes when the concentrate grade is equal to or greater than a predetermined acceptable value, test or operation results may be assessed by the recovery figures alone. Similarly when recovery is within specification, the operation can be assessed by concentrate grade. The ultimate assessment and selection of a concentration operation is—admittedly with a few ex-ceptions—a matter of economics. There is however an intermediate stage in laboratory and pilot plant testing when evaluations must be made without the assistance of an economic yardstick. Numerous techniques are employed to facilitate such evaluations among which may be mentioned graphical plots of grade vs recovery, cumulative weight vs cumulative recovery, scatter diagrams, etc. The desirability of combining metallurgical results and product weights and assays into a single value has been recognized and discussed by many workers1-" with the resultant suggestion and use of such terms as Metallurgical Efficiency ,' Summation Index,' Selectivity Index,'- and Absolute Efficiency B None of these expressions completely satisfies all the requirements of a selectivity or efficiency formula and it is proposed in this report to define the terms, relating to the technical efficiency of a concentrating operation, concentration index and concentration efficiency. Examples are given of their application and a comparison is made of their use in relation to other formulae. All product grades in this paper will be referred to in terms of mineral percentages and a list of symbols is given in Table I. CONSIDERATION OF EXISTING FORMULAE A number of the existing efficiency and index terms used in quantifying concentrating operations are considered below. Metallurgical Efficiency:

Jan 1, 1961

By A. Berghezan, E. Bull Simonsen

A simple and general method is described for melting and zone refining refractory metals by induction heating on a specially shaped water-cooled copper crucible. The crucible is the essential part of the apparatus and is placed horizontally. It consists of either a copper plate, or a flattened tube, or of several parallel small diameter tubes all water cooled. The charge lies on the crucible, or whenever possible, is suspended above it. This assembly goes into a transparent quartz tube and the whole is passed through the coil of a radio frequency generator. Vaarious atmospheres can be used. No contamination is detected from the copper crucible. purification is obtained both by selective evaporation of impurities and by zone refining. METHODS of melting and refining relatively large ingots of all reactive and refractory metals as well as some semiconductor materials have been developed in this laboratory during the past several years using induction heating and cold crucibles. These methods are simple and permit the use of a variety of starting materials in preparing ingots of suitable shapes. Among these methods, two are of particular interest. One deals only with the problem of melting without contamination. In this method the induction coil has a specially designed shape and acts simultaneously as heating element and crucible. The second goes one step further, being designed for both melting and further purification of the refractory metals. The aim of this paper is to describe the second method which is of more general interest and of greater applicability to metallurgical problems. A) THE PRINCIPLE OF THE MELTING AND PURIFICATION METHOD As originally proposed by one of us1 the method consists of heating a charge of any refractory metal or semiconductor material to the melting point on a water-cooled copper crucible by passing both the charge and the crucible through the induction coil of a radiofrequency generator. Although both are subjected to the same induction field, one achieves the melting of a refractory metal on a copper crucible even when the refractory metal has a melting point of more than 2000°C above that of the crucible. This seemingly "odd" method works effectively for the following reasons. Because of its high electrical and thermal conductivity as compared with the material being melted, copper can be used as the crucible and kept at a low temperature while the material is heated by induction to its melting point. With water Silver and other highly conducting materials can also be used. If a nonconducting material is contemplated, e.g. SiO or a high polymer, a very thin wall should provide efficient cooling. cooling through ducts in the crucible its temperature can be kept between 40" to 70°C; thus its electrical resistivity is kept low, while the resistivity of the charge increases rapidly as its temperature is increased. B) APPARATUS The crucible is the essential part of the apparatus. It has been designed in various shapes depending on the atmosphere used, whether vacuum or an inert gas or hydrogen. In all crucible designs an effort was made to reduce its volume to "nothing but the cooling water" in order to avoid shielding the ingot from the induction field. In practice it is either a

Jan 1, 1962

By John Hays Hammond

The following notes are descriptive of a country as yet in its infancy as regards the advancement made in mining operations. Its inaccessibility and other militating circumstances have retarded progress in that direction. With the completion of the railroad, now under construction, having the city of Cali as its objective point, with the concomitant civilizing and developing consequences, it is certain that the slopes of the Cordilleras will prove to be a South American Eldorado. Deposits of coal, copper, and minerals other than those of the precious metals are known to exist in quantities which, under more favorable conditions of accessibility, etc., could be profitably mined. The Government of the United States of Colombia, I think, is disposed to encourage and foster mining enterprises. Articles designed for mining are admitted free of duty; the permanency of the government is, at least, as well assured as that of Mexico (which is not noted for its immutability), and a more sincerely friendly sentitment towards Americans prevails in the United States of Colombia than in Mexico. This paper is confined to a description of the property of the Cauca company's mines, and is intended rather as a preliminary notice than as an exhaustive report. The Cauca mining district is reached by the following route: New York to Aspinwall; to Panama; to Buenaventura, a port on the west coast of the United States of Colombia, distant thirty-six hours from Panama by steamer; to Cali in the State of Cauca. The State of Cauca is bounded on the north by the Atlantic Ocean, on the northwest by the State of Panama, on the northeast by the States of Bolivar and Antioquia, on the east by Brazil and Venzuela, on the south by the Republic of Ecuador, and on the west by the Pacific. Ocean. It has a territory of 41,443 square miles, which is about one-tenth of the entire territory of the United States of Colombia. Its population, including the 50,000 savage Indians of the Caqueta (some of whom are cannibals), is nearly 450,000 souls, or about one-sixth of the population of the Colombian republic. Of these, one-fifth are whites (Spanish' South Amer-

Jan 1, 1885

By L. J. Health

Synthetic rock with predictable porosity and permeability has been Prepared from mixtures of sand, cement and water. Three series of mixes were investigated primarily for the relation between porosity and permeability for certain grain sizes and proportions. Synthetic rock prepared of 65 per cent large grains, 27 per cent small grains and 8 per cent Portland cement, gave measurable results ranging in porosity from 22.5 to 40 per cent and in permeability from 0.1 darcies to 6 darcies. This variation in porosity and permeability was caused by varying the amount of blending water. Drainage-cycle relative permeability characteristics of the synthetic rock were similar to those of natural reservoir rock. INTRODUCTION The fundamental behavior characteristics of fluids flowing through porous media have been described in the literature. Practical application of these flow characteristics to field conditions is too complicated except where assumptions are overly simplified. The use of dimensionally scaled models to simulate oil reservoirs has been described in the literature. 1-3 These and other papers have presented the theoretical and experimental justification for model design. Others have presented elements of model construction and their operation. In most investigations the porous media have consisted of either u ncon soli da ted sand, glass beads, broken glass or plastic-impregnated granular substances—materials in which the flow behavior is not identical to that in natural reservoir rock. The relative permeability curves for unconsoli-dated sands differ from those for consolidated sandstone. The effect of saturation history on relative permeability measurements is discussed by Geffen, et a1.4 Wyga15 has shown quite conclusively that a process of artificial cementation can be used to render un consolidated packs into synthetic sandstones having properties similar to those of natural rock. Many theoretical and experimental studies have been made in attempts to determine the structure and properties of unconsolidated sand, the most notable being by Naar and Wygal.6 Others have theorized and experimented with the fundamental characteristics of reservoir rocks. This study was conducted to determine if some general relationship could be established between the size of sand grains and the porosity and permeability in consolidated binary packs. This paper presents the results obtained by changing some of the factors which affect the porosity and permeability of synthetically prepared sandstone. In addition, drainage relative permeability curves are presented. EXPERIMENTAL PROCEDURE Mixtures of Portland cement with water and aggregate generally are designed to have certain characteristics, but essentially all are planned to be impervious to water or other liquids. Synthetic sandstone simulating oil reservoir rock, however, must be designed to have a given permeability (sometimes several darcies), a porosity which is primarily the effective porosity but quantitatively similar to natural rock, and other characteristics comparable to reservoir rock, such as wettability, pore geometry, tortuosity, etc. Unconsolidated ternary mixtures of spheres gave both a theoretically computed and an experimentally observed minimum porosity of about 25 per cent.7 By using a particle-distribution system, one-size particle packs had reproducible porosities in the reproducible range of 35 to 37 per cent.6 For model reservoir studies of the prototype system, a synthetic rock having a porosity of 25 per cent or less and a permeability of 2 darcies was required. The rock had to be uniform and competent enough to handle. Synthetic sandstone cores were prepared utilizing the technique developed by Wygal.5 Some slight variations in the procedure were incorporated. The sand was sieved through U. S. Standard sieves. A 18-20 sand denotes that the sand passed the Number

Jan 1, 1966

By N. Van Wingen, Norris Johnston

Laboratory flood pot testing of California sands has progressed to a considerable extent in the past 18 months. Flood evaluations have been carried out on over 200 large core samples. Many of these were heavy oil sands of high permeability and completely unconsolidated in nature. The oil frequently formed a bank, though some of the oil was recovered in the subordinate phase of the flood, by viscous drag. Flood pot recoveries as high as 1400 bbl/acre ft have been recorded. Reservoir analysis suggests a conformance factor of 0.4 to reduce laboratory recovery to probable field practice. Oils with viscosities up to 1800 cp have been successfully handled in flood pot evaluations. The shallow, loose sands are not well adapted to the application of- high pressures to offset the high viscosities. INTRODUCTION Secondary recovery may be said to have started 60 years ago when accidental floods occurred in the Bradford sand in Pennsylvania. About 1921 artificially conducted water drives came into extensive use and since that time the great Bradford field has been almost completely subjected to water flooding. During the last 30 years, most of the known medium and deeper production in California has been discovered and is being exploited by primary recovery methods supplemented in some instances by high pressure gas injection. The California area is just beginning to feel the need for secondary recovery in view of an unprecedented market demand and the rapidly rising cost of new pool discoveries. With the presently recognized desirability of secondary recovery in California, there must also be appreciated a number of serious differences between the water flooding problems here as compared to the territory east of the Rockies. California sands are generally thicker, and are frequently soft and argillaceous. The oils are often heavier and asphaltic. Much of the oil is below 15°API, occurs at shallow depth, is cool and free from appreciable dissolved gas, which results in relatively high reservoir oil viscosity. Secondary recovery is particularly beneficial where primary recovery has been poor and where no natural water drive exists. These conditions apply particularly to the heavy, shallow, clean production from soft, often argillaceous California sands so abundantly found at depths less than 1500 feet. Often, too, there is a totally insufficient supply of water of satisfactory quality to inject at a reasonable cost. Also, the crude oils are priced far below the premium Bradford crude. Although these and a number of minor problems beset the operator desirous of starting secondary recovery, great progress has been made in the past few years in finding how to adapt previous Mid-Continent and Eastern experience to water flooding in California. There are about nine projects for subsurface injection of water which can be said to classify as secondary recovery operations. Subsurface water disposal would so classify when the sand receiving the water is a nearby oil producer, as is often the case. When water is injected subsurface into a barren sand, the operation does not classify as secondary recovery. Several of the most active operators avail themselves extensively of preliminary engineering and laboratory work to guide their decisions, while others enter small scale flooding operations directly in the field. It is the laboratory work pertinent to several of the California secondary recovery projects that this paper discusses. PURPOSES OF LABORATORY FLOODING TESTS Experience in areas where water flood operations have been carried out has indicated that careful engineering planning is an important requisite for subsequent economically successful field operation. Floods that fail are more frequently those where operations were instigated without a prior engineering investigation to determine the effectiveness of the injection fluid as an oil displacing medium. Laboratory data are essential in the evaluation of an oil property for secondary recovery possibilities. Success or failure of secondary operations can under certain special circumstances be determined directly by cores and their subsequent routine analysis. This is particularly the case where flushing of the cores in the course of coring is negligible and where the results of the analysis can be compared with existing secondary recovery operations. Where these conditions cannot be' fulfilled, the application of core analysis is more limited. In such event, the results obtained by water flooding core samples in the laboratory have been found to be of prime importance. Cores may be flooded "raw" as taken from the well or in the event flushing and depletion of the cores in the process of drilling are major factors the fluid content may be artificially restored prior to the flooding. Laboratory studies should also be made to determine the suitability of the water selected for injection. Thus interaction between injected and formation water may cause precipitates to be formed which may plug the sand. Even more important, especially to California operations, is the possibility of the hydration of formation clays by the injection water. The aims of flood pot and associated tests are basically to determine the residual oil saturation after flood, the water-oil throughput ratio and to establish whether an oil bank is formed. Additional information which can be obtained from flood pot tests pertains to the pressure differential required to effect displacement, the relative permeability to oil in the oil bank and the relative permeability to water in the watered out region behind the bank.

Jan 1, 1953

By John T. Norton

In recent years, the damping capacity of metals has come to be recognized as an important index of certain types of structural change. In a number of instances, this property has proved to be particularly sensitive, but insufficient work has been done to permit a general interpretation. There is considerable question at the present time as to just what factors are responsible for the internal dissipation of energy when a metal is carried through a cycle of stress, and these factors must be ascertained if the value of the damping method as a metallurgical tool is to be determined. Since internal stresses are among the chief causes of dissipation of internal energy, or damping capacity, it was thought that a study of the changes in damping during the recovery and recrystalliza-tion of a cold-worked metal might throw some light upon the subject, particularly if the damping changes were correlated with other properties that are better understood. Probably more work has been done on the recrystallization phenomena of alpha brass than on any other metal, so this was chosen as the material for the present investigation. Damping measurements on brass have been made by Förster and Köster.1 They showed that the annealing of a brass that had been cold-drawn to 50 per cent reduction produced a rapid fall in the damping, a flat minimum occurring at approximately the temperature of recrystallization. The damping remained at a low value until grain growth was well under way and then it increased rapidly with increasing grain size. Köster and Rosenthal2 continued the work in greater detail. They pointed out that the damping decrease does not correspond to the hardness drop but occurs at a lower temperature, suggesting that the relief or redistribution of internal stresses has a large effect while the actual recrystallization effect is small. They also show the increase in damping at the higher annealing temperatures. Their curves are reproduced in Fig. 1.

Jan 1, 1940

By John T. Norton

In recent years, the damping capacity of metals has come to be recognized as an important index of certain types of structural change. In a number of instances, this property has proved to be particularly sensitive, but insufficient work has been done to permit a general interpretation. There is considerable question at the present time as to just what factors are responsible for the internal dissipation of energy when a metal is carried through a cycle of stress, and these factors must be ascertained if the value of the damping method as a metallurgical tool is to be determined. Since internal stresses are among the chief causes of dissipation of internal energy, or damping capacity, it was thought that a study of the changes in damping during the recovery and recrystalliza-tion of a cold-worked metal might throw some light upon the subject, particularly if the damping changes were correlated with other properties that are better understood. Probably more work has been done on the recrystallization phenomena of alpha brass than on any other metal, so this was chosen as the material for the present investigation. Damping measurements on brass have been made by Förster and Köster.1 They showed that the annealing of a brass that had been cold-drawn to 50 per cent reduction produced a rapid fall in the damping, a flat minimum occurring at approximately the temperature of recrystallization. The damping remained at a low value until grain growth was well under way and then it increased rapidly with increasing grain size. Köster and Rosenthal2 continued the work in greater detail. They pointed out that the damping decrease does not correspond to the hardness drop but occurs at a lower temperature, suggesting that the relief or redistribution of internal stresses has a large effect while the actual recrystallization effect is small. They also show the increase in damping at the higher annealing temperatures. Their curves are reproduced in Fig. 1.

Jan 1, 1940

By W. A. Wood, H. L. Wain, R. I. Garrod

The mechanical behavior of recrystallized chromil~m of high purity has been studied, principally in torsion and to a lesser extent in tension, at temperatures between —196oand 350oC. Depending upon the conditions of test, the material may show brittle or ductile behavior or an intermediate or subduc-tile state having some of the characteristics of each. This latter state existed at temperatures between approximately ±50°C and was characterized by a) extensive creep at stresses well below the normal fracture stress, b) nonelastic loading/unloading effects during creep, c) strain softening under cyclic loading, and d) final failure of a brittle type. Suggestions are made on the dislocation processes and interactions which give rise to subductile behavior The ductile-brittle transition in bee metals has been studied mainly by tension and bend tests. These methods, however, favor crack propagation which may follow too closely on initiation for detailed study of the transition itself. For work of this nature, therefore, other modes of deformation less favorable to crack propagation may be preferable. This paper describes a study of the ductile-brittle transition in chromium which is based mainly on torsional testing although a few subsidiary experiments were made in tension. It appears to reveal at the transition an intermediate state that cannot properly be described as either brittle or ductile. Torsional tests on chromium have been made by other workers1 but not, as here, primarily for study of this intermediate state. EXPERIMENTAL The chromium, in the form of swaged rod, was prepared by techniques already described.' The particular material used was one in which the main impurities were 0.03 wt pet 0 and 0.006 wt pet N and one in which transition from ductile to brittle states in torsion conveniently fell at about room temperature. For torsion, test specimens were from 5/16-in.-diam rod to provide test portions 1-1/4 in. long by 7/32 in. diam, a twist of 1 deg thereby corresponding throughout this paper to 0.0015 surface shear. The specimens before test were annealed for 2 hr at 1200°C in vacuo, which left them with a re-crystallized grain size of about 0.01 mm, and then electropolished. They were tested under dead-weight loading in an apparatus in which they could be surrounded by a furnace or cooling chamber, tests in practice being made at various temperatures between -196" and +350°C. For tension tests, cylindrical specimens were prepared in a similar manner and tested at room temperature under dead-weight loading. RESULTS (TORSION) Subductile State. The state described above as intermediate between brittle and ductile may be perhaps best defined by reference to torque/twist curves at various temperatures. These are grouped in Fig. 1. Below about -50°C the material was brittle, in the sense that it exhibited little plastic deformation under stress and fractured by cleavage along planes of maximum resolved tension, which in torsion produces the well-known helical type of fracture. The deformation is typified by the curves for -196" and -150°C in Fig. 1; it shows a slight but progressive deviation from linearity above a certain torque, here about 50 lb-in., until fracture occurs at about 95 lb-in. A feature to which it is desired specially to call attention is that under none of the loads did the specimens show significant creep.

Jan 1, 1964

By Arthur F. Taggart, T. C. Fitt, A. W. Thomas

IT was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a. component of the pulp, of a mass solubility of the general order of a fraction of a milligram to 15 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.2 The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. EXPERIMENTAL Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well beyond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipita-

Jan 1, 1943

By Henry Schaefer

Solution by electric analogy of performance problems of reservoirs containing oil and gas has heretofore depended upon a process of successive approximations based on material-balance calculations, because of variation in fluid compressibility. By the addition or subtraction of electric condenser capacity, the analogy network can be adjusted automatically for changing compressibility due to evolution of gas in the reservoir. The addition of a condenser is accomplished by an electronic circuit, which is described; subtracting a condenser is done by merely opening the electrical circuit by means of a relay. Introduction V. Paschkis and H. D. Baker1 first developed in this country a method of applying the analogy of flow of electric current in noninductive circuits to solution of heat-flow problems and suggested its application for certain other problems, such as flow of fluids or mass transfer and chemical diffusion. Necessary details for applying the analogy to flow of fluids in porous media were developed by IV. A. Bruce;= he classified3 the types of analysis and predictions that can be made by the analogy in class I, when the reservoir contains oil but no gas for the period under consideration; in Class 2, when both oil and gas exist in the free state in the reservoir sometime during the period under consideration. Duplication of bottom-hole pressure history and predictions for class I reservoirs can be obtained directly by electric analogy. Until now, the solution of problems pertaining to reservoirs in class 2 was obtained by successive approximations along with material-balance calculations. The object of this paper is to present a method for simplifying the application of electric analogy to class 2 reservoirs, resulting in a solution of these problems as direct as is possible for class I reservoirs. This is accomplished by an electronic control circuit, which adjusts the analogy network for changing compressibilities of fluids contained in the reservoirs. Analogy Network In electrical phenomena the analogy to two-dimensional fluid flow in a porous media is that of current flow through an ideal conducting sheet. This sheet, perfectly insulated on both sides, has resistance and capacitance uniformly distributed throughout its area but is of negligible inductance. The need for having the surface boundaries perfectly insulated is that good correspondence may be had with a permeable fluid-conducting stratum bounded above and below by impermeable media. 111 actual application the ideal conducting sheet, which has distributed parameters, is replaced by a network having lumped values of resistance and capacitance—the resistances are series elements and the capacitances are shunt elements. The larger the number of lumped

Jan 1, 1947

By Henry Schaefer

Solution by electric analogy of performance problems of reservoirs containing oil and gas has heretofore depended upon a process of successive approximations based on material-balance calculations, because of variation in fluid compressibility. By the addition or subtraction of electric condenser capacity, the analogy network can be adjusted automatically for changing compressibility due to evolution of gas in the reservoir. The addition of a condenser is accomplished by an electronic circuit, which is described; subtracting a condenser is done by merely opening the electrical circuit by means of a relay. Introduction V. Paschkis and H. D. Baker1 first developed in this country a method of applying the analogy of flow of electric current in noninductive circuits to solution of heat-flow problems and suggested its application for certain other problems, such as flow of fluids or mass transfer and chemical diffusion. Necessary details for applying the analogy to flow of fluids in porous media were developed by IV. A. Bruce;= he classified3 the types of analysis and predictions that can be made by the analogy in class I, when the reservoir contains oil but no gas for the period under consideration; in Class 2, when both oil and gas exist in the free state in the reservoir sometime during the period under consideration. Duplication of bottom-hole pressure history and predictions for class I reservoirs can be obtained directly by electric analogy. Until now, the solution of problems pertaining to reservoirs in class 2 was obtained by successive approximations along with material-balance calculations. The object of this paper is to present a method for simplifying the application of electric analogy to class 2 reservoirs, resulting in a solution of these problems as direct as is possible for class I reservoirs. This is accomplished by an electronic control circuit, which adjusts the analogy network for changing compressibilities of fluids contained in the reservoirs. Analogy Network In electrical phenomena the analogy to two-dimensional fluid flow in a porous media is that of current flow through an ideal conducting sheet. This sheet, perfectly insulated on both sides, has resistance and capacitance uniformly distributed throughout its area but is of negligible inductance. The need for having the surface boundaries perfectly insulated is that good correspondence may be had with a permeable fluid-conducting stratum bounded above and below by impermeable media. 111 actual application the ideal conducting sheet, which has distributed parameters, is replaced by a network having lumped values of resistance and capacitance—the resistances are series elements and the capacitances are shunt elements. The larger the number of lumped

Jan 1, 1947

By R. E. Collins

The existence of fluid migration across fixed boundaries in oil and gas reservoirs has been known for many years. Several techniques have been developed in the past for estimating The rate of migration across fixed boundaries as an aid in planninng field development and in the valuation of oilfied properties. The principal de/errc7nt to the use of these techniques lies in the rather extensive reservoir and field data required for ca1cula1ion.s of fluid migration. For this reason, a new, simplified procedure has been developed which makes possible the calculation of fluid migration with a minimum of field and resrvoir data. This new technique is based on certain. solutions of the differential equations describing flour in the reservoir which assume, for the portion of the reservoir of interest, that the formation can be approximated by a homogeneous rock of uniforrn thickness, that only a Single mobile fluid phase exists, and {hut fluid production at the well is solely a result of expun.rioti of rile resersoir fluds. The results of the, present work are compiled in a set of curves. These curves can he used to calculate both rule and cummulative fluid migration when the abovc assumptions ore ju.r/ifiril. The only data required for such calcu1ations are the production hisrories of all wells in the field, the permeability and porosity of the reservoir., the, compressibility and viscosity of the fluid. and the shape of the reservoir, INTRODUCTION The migration of fluids across fixed boundaries in oil and gas reservoirs has long been recognized as an engineering and economic problem, but no methods for estimating the extent of migration during the development stage of a reservoir have been published. The investigation reported here has been directed toward providing a simple technique for estimating the extent of such migration and has therefore been restricted to the simple case of a homogeneous reservoir of uniform thickncss containing compressible liquids. It is assumed that only a single mobile fluid phase exists and that fluid production at the wells is solely by expansion of the reservoir fluids. Obviously, few, if any. reservoirs conform to these assumptions during their entire productive life. On the other hand, most reservoirs approximate fluid expansion reservoirs during their initial stages of primary production. Consequently, the present work should be applicable during the field development of most reservoirs, regardless of whether or not they ultimately are gas cap, dissolved-gas, or water-drive reservoirs. The mathematical analysis of this problem has been outlined in the Appendix, while the results of the investigation are presented in the following discussion. DISCUSSION OF CALCULATION PROCEDURE SLNGLE Well, Ini-iimite Reservoir The procedure for calculating fluid migrations is based on solutions of the partial differentia1 equations describing the flow of a homogeneous compressible liquid in a homogeneous reservoir of uniform thickness. This differential equation has the form of the well-known diffusion equation. The equation, as applicable to our problem, is where p is fluid density, is porosity, EL is viscosity, c is compressibility,* and k is permeability; .r, y and t are the space coordinates and time. Derivation of this equation is given in the Appendix. The analytical solution of this equation for a single well of negligible radius producing at a constant rate. q, from a reservoir of infinite areal extent for a time, 1. can he readily obtained. From this solution the rate of flow and also the cumulative flow across a straight line segment of length, 1, at a perpendicular distance. 6. from the well can be computed. One end of the line must be on the perpendicular joining the well to the