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By John A. Brown

Granules are used primarily as roofing material. From the earliest times, man has been faced with the basic problem of providing protection for himself, his family, and his property against the ravages of the weather. Basically, this problem is no different today than in the past, except that today the trend is to demand shelter which is also colorful and distinctive. There has been a gradual evolution from the thatched roof to the modem ranchstyle home. In his search for a more permanent and more attractive roof, the home owner has utilized many mineral materials. All granules, whether slate or colored granules, are referred to by the asphalt roofing industry as "Slate Granules." Early Roofing Materials The development of mineral roofing in the United States followed two trends: first, the slate industry, and second, the bituminous products. The early colonists were familiar with slab slate construction from Europe and it was natural for them to continue with this type of roofing. As early as 1780, the forerunners of the present bituminous products were finding favor. Those early products consisted of saturating burlap or similar material with crude tar or pitch. This type of roofing was soon improved by dusting a variety of materials on the surface of the roofing to prevent adhesion while in rolls. Such factors as fire resistance and protection from the actinic rays of the sun soon followed. This started the general pattern which is still followed today, that is, saturating felt materials and supplying a uniform grade of crushed mineral to the surface. In commercial and public buildings, metal roofs found early favor. The attractive green color of verdigris-coated copper became a symbol of churches and institutions of learning. Aluminum roofing has become economical for large structures and is finding limited popularity in rural areas. Tile, asbestos, and cement materials, being weather resistant, found early acclaim and are still popular. Today, by far the most widely used roofing materials in the United States are asphalt products. Two important characteristics-economy and weatherability-account for their popularity. Influence of Building Trends on Roofing The postwar building boom in 1947 had many attractive features for the American people. The ranch-style one story type of home seemed well suited for suburban developments which sprang up in such profusion. As the roof in modern home construction is one of the most conspicuous aspects of its architecture, the home owner could now express his tastes not only in paint and landscaping, but could also select an attractive and harmonious roof color. Variety of Minerals Used Many naturally occurring minerals are used today in the roofing industry. Most widely used (and most noticeable to the public) is the granulated mineral surfacing applied to asphalt products. Selected natural colored granules as well as artificially colored granules are

Jan 1, 1960

By M. I. Sherman, J. D. H. Strickland

PRELIMINARY experiments in these laboratories showed that whereas pyrite1 produced only sul-fate the action of aqueous chlorine solutions on most other sulfide ores resulted in the formation of a mixture of sulfate and elemental sulfur, the production of the latter being favored by a very dilute solution of oxidant. The reactions taking place were obviously complex and only a detailed kinetic study could be expected to clarify the position and enable a prediction to be made of conditions leading to the rapid formation of metal salt and the economically desirable elemental form of sulfur. Galena was chosen for the first investigation as it is of widespread occurrence and is representative of a simple cubic lattice sulfide containing the monosulfide unit, S2-. Experimental Procedure The apparatus and general technique used in this work have already been described.' Analyses for chlorine and sulfate were carried out by the same methods as those used for pyrite. The lead in 1 ml aliquots of solution was determined polarographi-cally, after destroying chlorine with hydrazine hy-drochloride and making solutions 0.5 molar with hydrochloric acid. A large sample of Kansas galena, assaying at better than 98 pet PbS, was crushed and wet sieved to give fractions of —10 + 14, —20 + 28, —28 + 35, and —48 + 65 Tyler screen. The particles were almost perfect cubes and the apparent surface Per gram was calculated assuming each particle a cube Of side equal to the mean mesh opening. A volume shape factor, calculated as for pyrite, was exactly unity. The main apparatus was unsuitable for direct visual examination of the ore particles during the reaction. For this purpose a small cell from a Spekker Absorptiometer optical flats 1 cm apart) was l by a greased microscope slide after filling with oxidant solution. One or two ore particles were placed in the cell and the solution was stirred by a glass covered speck of iron wire activated by an external rotating magnet. The surface of an ore particle was examined under a binocular microscope at between 10 and 40 magnifications. Results Experiments were made under a wide variety of conditions, the form of presentation of the data being illustrated by Fig. 1, where the concentrations of chlorine, sulfate, and sulfur are plotted against time. The fictitious concentration of solid sulfur is used for convenience and is the molarity of sulfur which would be recorded if the elementary sulfur formed during the reaction were dissolved in the liquid iii the reaction vessel. As some lead sulfate is occluded with the sulfur on the ore particles the amounts of sulfur and sulfate formed during a reaction cannot be calculated

Jan 1, 1958

By Richard J. Gonzalez

The petroleum industry includes varied and extensive operations required to supply increasing quantities of refined petroleum products and natural gas that are essential for the economic progress of an expanding population Petroleum has provided the power for the transformation from the "horse and buggy days" to the age of jets and space exploration, and for the remarkable improvement in productivity per worker in agriculture and manufacturing. Without increasing quantities of oil and gas, the world would face painful readjustments to more expensive forms of energy and lower standards of living Petroleum operations start with exploration, development, and production activities that supply the basic crude oil and natural gas Pipelines, ships, barges, and trucks first transport the raw materials to processing centers and then move the finished products to the ultimate consumers. Processing plants extract liquids from natural gas and refineries convert crude oil into a wide range of products These products include transportation fuels, feedstocks for conversion into numerous products (such as fabrics, rubber, and plastics), light fuels for heating, lubricants, and heavy residual materials (industrial fuel oil, asphalt, and coke) The final activity of wholesale distribution and retail marketing moves products into millions of homes, farms, industrial plants, and motor vehicles The use of coal exceeded that of oil and gas until 1946 in the United States and until 1968 in the rest of the world. However, oil and gas have proved to be such convenient and attractively priced fuels that they now supply three-fourths of the total commercial energy (including coal, hydroelectric, and nuclear power) used in North America and more than one-half in the rest of the world. LARGE SCALE OF OPERATIONS By the beginning of 1970, world crude oil production exceeded 43 million bbl daily, -equivalent to more than 2200 million tpy In addition, natural gas and the liquids recovered from processing natural gas supply about 40% as much energy as crude oil Production of oil and gas provide by far the highest value of all mining operations. In the United States, the value of oil and gas production in 1969 of $13 8 billion exceeded the $13 0 billion value for all other minerals The rate of expansion in use of petroleum has been extremely rapid since World War II World crude oil production doubled from 7,500,000 bbl daily in 1946 to more than 15,000,000 bbl daily by 1955 It doubled again to 30,000,000 by 1965, and will double again by 1975 The use of natural gas has increased greatly in the United States and also in Europe, as important discoveries in the Netherlands and the North Sea and technology for moving liquefied natural gas from Africa provided attractively priced supplies

Jan 1, 1976

By John E. Conley

The slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. Use of Waste Slates for Making Aggregates The lightweight-aggregate industry has been discussed elsewhere4,5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. Requirements for Raw Materials As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of ally low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig, I illustratcs the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By B. F. Tillson

HAVING been asked to talk about recent devel-opments in mining equipment, I chose the sub-ject of small units of storage-battery locomo-tives which recently have been developed with the idea of motorizing transportation in the mines as far as possible, replacing the manual labor of hand-tramming. Metal mines are probably less advanced in this field than coal mines, where transportation of large ton-nages on any one level is quite common. Of course, metal mines, where large tonnages are handled on any one level, are as advanced as coal mines, and storage-battery locomotives for main haulages are used quite commonly in such metal mines, but the mines having levels at many intervals in the depth of the orebody, or a number of intermediate levels in which a consider-able amount of hand-tramming has to be done, and small metal mines in which the size of the orebody does not seem to warrant the initial capital expenditure for the driving of main haulage levels and installation of rock and ore chutes and raises for the delivery of the broken ore and rock to the cars have been at consider-able disadvantage in replacing manual labor by some mechanical means of transportation. Several years ago the field was canvassed among the manufacturers of electric-locomotive equipment and the conclusion was reached that the art had not been devel-oped to the advantage of metal miners who desire to replace small units of labor by locomotive equipment. The need for such small locomotives is all the more em-phasized by the development in the past few years of mechanical mucking-machines (loading equipment for filling the cars from muck piles on the level). Any me-chanical loader is a liability instead of an asset unless means are also provided for keeping the material away from the loading-machines. Therefore the transporta-tion system must be equal to the capacity of a loading-machine, otherwise the latter is idle such a large per-centage of its time as to prove an unprofitable invest-ment. So there is a need for portable, small haulage units to handle small mine cars in many metal mines, and, naturally, units are desired which can be so readily shifted from level to level as to facilitate their free use. Of course, in mines in which each level comes to the shaft it is not such a difficult problem, but many mines have a great many intermediate levels which must be approached through raises, timber slides or other small openings required to transfer ore and to get timber and other supplies to those levels.

Jan 5, 1927

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Zinc difhsions in gallium arsenide having surface concentrations as low as 5 x 10'' atoms per cu cm have been attained. A multiple-difhsion sequence is employed during which zinc enters the gallium arsenide from a silicon dioxide film in a solid-to-solid diffusion step. The technique is illustrated for the case of a zinc surface concentration of -1 x 1017 atoms per cu cm and a junction depth of 1.2 p. Radiotracer measurements of -0.1-p layers of gallium arsenide are used to delineate the resulting profile. A diffusion coefficient for zinc in pyrolytically deposited silicon dioxide is reported. ZINC is frequently used as an acceptor impurity in gallium arsenide. As examples, p-n junctions are formed using zinc-diffused layers in solar cells, lasers, and varactor diodes. For these purposes surface concentrations of 10'' to over loz0 zinc atoms per cu cm are desired and readily obtained from a vapor source. Diffusion of zinc into gallium arsenide to yield surface concentrations of about 1017 atoms per cu cm, however, is more difficult. For instance, oldstein' reports that large changes in the vapor density of zinc produce only small changes in surface concentration. Such low surface concentrations are necessary in forming the diffused base of a gallium arsenide double-diffused n-p-n transistor in order to obtain an adequate emitter efficiency. An alternative approach to zinc diffusion which can provide reduction in surface concentration of several orders of magnitude is the introduction of the diffusant from a solid source. This can be conveniently accomplished by using oxide films of the type generally employed for selective diffusion masking. Such oxides also serve to prevent the dissociation of the gallium arsenide surface at the high temperatures of diffusion. DIFFUSION PROCEDURE Fig. 1 illustrates the diffusion sequence which is employed for obtaining zinc surface concentrations in the range from 5 x lom to 1 X 10" atoms per cu cm. The description of technique will be given for the instance of -1 x 1017, which is typically utilized in double-diffused gallium arsenide transistor investigations at this laboratory. Tin- or germanium-doped gallium arsenide wafers drawn from crystals grown by horizontal Bridgman or Czochralski techniques are used, with bulk concentrations ranging from 1 to 3 X 10" carrier atoms per cu cm. Each wafer is chemically polished on the (iii) arsenic face using a mixture of five parts concentrated sul-furic acid, one part water, and one part 30 pct hydrogen peroxide at room temperature, followed by rinsing in deionized and quartz-distilled water. Pyrolytic silicon dioxide was chosen as the oxide coating because of the high quality of the films obtainable, the ease of their preparation, and the excellent control over film thickness and uniformity.

Jan 1, 1964

By W. C. Ellis, M. E. Fine

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949

By James K. Stanley

PREFERRED orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.1 In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurgical literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanical properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important in- formation, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational under- standing of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing 'stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required-it is only necessary punch or machine a disk of the sheet material and insert it into the testing device.

Jan 1, 1943

By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By William Hurst

This is a presentation of the diffusivity theory for the calculation of the water drive on an oil reservoir in which the history of reservoir pressure with time are the essential parameters for the determination of the rate and cumulative water encroachment into a field. The main body of the paper is essentially the application of the principles underlined here to actual field data. It consists of the work plots of the radial-flow case, and includes a discussion of an illustrated problem for which the water-drive calculations are treated in conjunction with the volumetric-balance equation. The appendix is a mathematical treatment of the linear, radial, and spherical cases of water influx into a reservoir. Introduction The evaluation of oil reserves and the prediction of pressure behavior with different rates of production are related to the volumetric balance of the fluids entering and leaving the space occupied by the oil and gas originally present in the formation; that is to say, important information can be gleaned from a volumetric study of the oil, gas, and water produced from a formation as it affects the extent of change in volume of oil zone, the gas cap, and the amount of water influx from the adjoining water sands. It is not the purpose of this paper to enter into a discussion of the equation of volumetric balance, in which such pertinent information as subsurface sampling and the measurement of reservoir pressures play a predominant part, as this has been discussed in detail by others.1,2 However, there is an inherent difficulty that has limited the general application of this equation to a study of oil reservoirs; that is, the insufficient knowledge of the analytics for expressing the water drive on a field as a function of reservoir pressure. This to a large degree has been overcome and it is the purpose of this paper to present this theory in such form as to be applicable for reservoir calculations. Water Drive If the amount of oil originally in place and the gas space are known, it is a relatively simple matter to determine, by the volumetric equation, the cumulative water influx into a reservoir from the adjoining water sands. Often, however, the oil reserve as well as water influx must be 'determined, and in order to be able to make this calculation it is essential to assign a mathematical relationship for the varying water term that is compatible with conditions known to exist in the formation and gives an accuracy acceptable for engineering calculations. Various equations have been employed empirically by different investigators in making reservoir studies of water drive. One form used by Schilthuis2 expresses the rate of water influx into a reservoir at any time as proportional to the pressure

Jan 1, 1943

By J. D. Rice, H. H. Rachford, G. H. Bruce, D. W. Peaceman

The problem of unsteady-state gas flow through porous media leads to a second-order non-linear partial differential equation for which no analytical solution has been found. In this paper a stable numerical procedure is developed for solving the equation for production of gas at constant rate from linear and radial systems. An electronic digital computer is used to perform the numerical integration using an implicit form of an approximating difference equation. Solutions are presented in graphical form for various values of dimension-less parameters. The solutions are compared with the laboratory study of gas depletion in a linear system. INTRODUCTION Production of fluids from porous rock reservoirs is essentially a transient process. Transient gradients develop as soon as production begins, and further withdrawals continue to cause disturbances which propagate throughout the reservoir, each adding in some way to the prior ones. A correct mathematical analysis of this behavior is complicated by the fact that the transient or unsteady-state flow of compressible fluids must be described by difficult second-order partial differential equations. As a practical matter, three distinctly different cases arise: 1. Flow of single-phase liquid 2. Flow of gases 3. Multiphase flow The first of these has been found to give a linear second-order equation similar to the well-known heat flow equation. where 7 is fluid density, 8 is time, and a a constant for the system, provided d 7 = r cdp, where the compressibility, c, is constant over the range of pressure, p, considered. Solutions of Equation (1) for both linear and radial flow are available in several forms.2'3' On the other hand. the second case, which is the flow of gas, gives a non-linear second-order equation, the solution of which is not known. Although a number of approximate solutions have been proposed, each is limited in value by the associated simplifying assumptions. Inasmuch as the analysis of transient flow is limited to liquid systems, a solution of the second case is necessary if further progress is to be made in studying underground fluid movement. For this reason a solution of Equation (2) was undertaken by means of numerical integration of approximating difference equations. BASIC DIFFERENTIAL EQUATION Equation (2; is derived by combining the equation of continuity, the perfect gas law, and Darcy's law to give the basic differential equation Strictly speaking, the fluids present in a gas reservoir are not perfect gases. Furthermore, there are indications that over certain velocity ranges, Darcy's law is not applicable. It would not be practicable. however, to attempt to obtain numerical solutions which would take into account all the possible variations from these laws which could occur in actual systems. The

Jan 1, 1953

By P. A. Beck, A. Merlini

Quantitative texture determinations were made for rolled and for rolled and annealed strips of 3, 6, and 10 pct Zn brasses. The main components of the rolling texture gradually shift over a wide composition range from the orientation characteristic of copper to that of 70-30 brass. At least the main features of the corresponding gradual changes in the annealing texture may be accounted for qualitatively on the basis of the oriented growth theory of annealing textures. All the oriented nucleation-type theories are notably less successful in accounting for the observed textures. EARLIER investigations by von Goeler and Sachs,' Dahl and Pawlek,' and Brick, Martin, and Angier" suggested that the annealing texture of copper is more sensitive to the addition of solute elements than the rolling texture. It was reported3 that the cube texture changes over into a brass-type recrys-tallization texture on addition of about 1 pct Zn, while the deformation texture changes only at about 5 pct Zn. Such behavior would be difficult to reconcile with any theory of annealing texture formation that relates the annealing texture to the deformation texture. In particular, the oriented growth theory of the cube texture" is based on a certain orientation relationship between the cube texture and the main components of the deformation texture which could not be reconciled with the reported behavior of low brasses. It was, therefore, of interest to re-examine these textures by means of the quantitative methods now available. The deformation and annealing textures of rolled a brasses with approximately 3, 6, and 10 pct Zn have been determined in terms of (111) and (200) pole figures. Experimental Methods The chemical analyses of the Cu-Zn alloys of commercial purity used in the present work are given in Table I. Chill-cast bars of the tabulated compositions were rolled and annealed according to the following schedule: I—rolling from 1.2 to 1.02 in. thickness, 15 pct reduction area, annealing 15 min at 450°C; 2— rolling from 1.02 to 0.867 in. thickness, 15 pct reduction area, annealing 15 min at 450°C; 3—rolling from 0.867 to 0.600 in. thickness, 31 pct reduction area, annealing 2 hr at 540°C; 4—rolling from 0.600 to 0.400 in. thickness, 33 pct reduction area, annealing 2 hr at 480°C. In the final straight rolling of 96.25 pct reduction area, the strips were reversed end to end after each pass. The final annealing temperature was determined for each alloy by annealing specimens of the cold-rolled strips in salt bath for 5 min at varying temperatures. The results of the hardness measurements are given in Fig. 1, where the final annealing temperature used for each alloy in determining the annealing texture is indicated by a cross.

Jan 1, 1956

By E. F. Ketterer, D. B. Collyer, A. B. Wilder

AISI constructional alloy steels are a series of steels in which a numbering system signifies the chemical composition limits. SAE (Society of Automotive Engineers) and AISI (American Iron and Steel Institute) use basically the same numbering system. The steels contain, in part, alloy additions of chromium, molybdenum, nickel, and vanadium. They are used widely in the automotive industry but have not been adopted for high temperature service. The purpose of this investigation was to study changes in microstructure observed in typical AISI constructional alloy steels in the welded and un-welded conditions after exposure for 34,000 hr at 900" and 1050" and, in several instances, 1200°F. The tensile and creep rupture properties after exposure for 10,000 hr were also evaluated. The investigation is a continuation of the work previously discussed. Little was known concerning the existence of graphite in medium or low carbon steels before 1943. It is important to note that continued exposure at elevated temperature is required in order to develop graphite in steels. Interest in the presence of graphite in steel, and also in changes in the properties of steels after long service at elevated temperatures, developed after 1943 when a failure of a welded joint of high temperature piping was associated with the graphitization of a relatively low carbon content steel with 0.50 pct Mo,8,0 Numerous investigations have beeen made in recent years studying the relationship of this type of failure to changes in properties. Attempts have been made to evaluate the performance of a number of steels, particularly in the heat-affected zone of welds. It was the unfortunate failure of a weld-heated zone in high temperature piping in the steam-power industry which focused attention upon possible failures, and upon the need for improved steels for high temperature piping service. Investigation by the National Tube Div., U. S. Steel Corp., Lorain Works, has included a wide variety of steels in an attempt to learn the effects of numerous factors and elements upon the long time performance of steels, although many of the compositions studied will never be used at elevated temperatures.1,4-7 Included were the well established AISI steel series, which offered opportunity to test moderately high carbon content steels as well as observe the effect of nickel, chromium, molybdenum, etc., upon the properties of these well known steels. The properties of the AISI steels were also studied for comparison with the previously reported properties of the Cr-Mo steels, now used by the steam-power industry.5,7 Materials and Testing Procedure The AISI alloy steels in Table I were exposed for 10,000 and 34,000 hr at 900°, 1050°, and 1200°F.

Jan 1, 1958

By William Hurst

This is a presentation of the diffusivity theory for the calculation of the water drive on an oil reservoir in which the history of reservoir pressure with time are the essential parameters for the determination of the rate and cumulative water encroachment into a field. The main body of the paper is essentially the application of the principles underlined here to actual field data. It consists of the work plots of the radial-flow case, and includes a discussion of an illustrated problem for which the water-drive calculations are treated in conjunction with the volumetric-balance equation. The appendix is a mathematical treatment of the linear, radial, and spherical cases of water influx into a reservoir. Introduction The evaluation of oil reserves and the prediction of pressure behavior with different rates of production are related to the volumetric balance of the fluids entering and leaving the space occupied by the oil and gas originally present in the formation; that is to say, important information can be gleaned from a volumetric study of the oil, gas, and water produced from a formation as it affects the extent of change in volume of oil zone, the gas cap, and the amount of water influx from the adjoining water sands. It is not the purpose of this paper to enter into a discussion of the equation of volumetric balance, in which such pertinent information as subsurface sampling and the measurement of reservoir pressures play a predominant part, as this has been discussed in detail by others.1,2 However, there is an inherent difficulty that has limited the general application of this equation to a study of oil reservoirs; that is, the insufficient knowledge of the analytics for expressing the water drive on a field as a function of reservoir pressure. This to a large degree has been overcome and it is the purpose of this paper to present this theory in such form as to be applicable for reservoir calculations. Water Drive If the amount of oil originally in place and the gas space are known, it is a relatively simple matter to determine, by the volumetric equation, the cumulative water influx into a reservoir from the adjoining water sands. Often, however, the oil reserve as well as water influx must be 'determined, and in order to be able to make this calculation it is essential to assign a mathematical relationship for the varying water term that is compatible with conditions known to exist in the formation and gives an accuracy acceptable for engineering calculations. Various equations have been employed empirically by different investigators in making reservoir studies of water drive. One form used by Schilthuis2 expresses the rate of water influx into a reservoir at any time as proportional to the pressure

Jan 1, 1943

By John E. Conley

THE slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5 ¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. USE OF WASTE SLATES FOR MAKING AGGREGATES The lightweight-aggregate industry has been discussed elsewhere4.5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. REQUIREMENTS FOR RAW MATERIALS As pointed out by Hughes,4 the light-weight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of any low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig. I illustrates the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By J. J. Arps, T. G. Roberts

Since the introduction of the relative permeability concept in the middle thirties1,2 various investigators have shown3,10,11,12,15 how the basic equations for the flow of oil and gas through porous media can he utilized to compute the recovery from depletion type or solution gas drive type reservoirs under certain conditions, when the necessary physical data pertaining to the reservoir rock and its reservoir fluids are known. In the study by Muskat and Taylor" in 1945, the effects of viscosity, gas solubility, shrinkage, and the permeability-saturation characteristics of the producing formation on the production histories and the recovery of gas drive reservoirs were analyzed. Each parameter was varied a limited number of times, while keeping the others constant. The work was not carried to the point where the data could be used directly to estimate the primary recovery in those cases where certain rock and fluid characteristics were known or could be assumed. Since the publication of this classic study, the work by Beal in 194616 and Standing in 1952'" has established general correlations of oil viscosity and shrinkage with gas solubility and oil gravity. In addition. a considerable number of relative permeability relationships for different types of reservoir rocks has been published2,5,13,17,19,20. Also, the burden of the numerical work required in the solutions of the differential equation has. during the last few years, been greatly reduced with the availability of modern electronic computing facilities. The purpose of this paper is therefore to present the results of a large number of such recovery computations covering the normal range of variation of the main parameters such as the type of rock, the API gravity of the oil, and the amount of gas in solution. As is to be expected, the ultimate recovery is found to increase with the oil gravity. except for the higher solution gas-oil ratios. Within the normal range of solubilities, the ultimate recovery generally appears to decrease with the amount of gas in solution for the higher oil gravities, and to show a slight increase for the lower oil gravities. Intermediate oil gravities seem to fall between the two trends. The type of reservoir rock, as identified by its relative permeability relationship, appears to have a very pronounced effect on the ultimate recovery. In general, sands and sandstones show higher recoveries than limestones and dolomites, although certain intergranular limestones seem to show a higher theoretical recovery than unconsolidated sand. The recovery from sands and sandstones generally decreases with increasing cementation and consolidation, while the recoveries from limestones and dolomites are highest for the intergranular type and lowest for the fracture type porosity.

Jan 1, 1956

By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu' of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith' deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-' make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.' It has received confirmation in the recent work of Dench and Kubaschewski,' and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968

By G. H. Alani, H. T. Kennedy

One of the major difficulties in predicting the performance of oil reservoirs from their early pressure history lies in the uncertainty of estimating the volume of the liquid hydrocarbons contained in them. As a first step in filling this need, an equation was developed to determine the Inolal liquid volume of pure hydrocarbons over a wide range of temperature and pressure. The second step consisted of adapting the equation to apply to mixtures, with the heary hydrocarbons expressed as c The equatious are similar in form to van der Waals equation. hut the constants a and b tire considered as furnctions of temperature. In addition to the gas constant R, there are four constants characteristic of each hydro- When comptired with experimental values jound in the literal the. the average absolute deviation in the calculated molal volumes is found to be a Maximum of 0.33 per -cem for any of the pure liquid hydrocarbons studied. This maximum deviation was that found when comparing the calculated and observed values over a temperature range of 86° to 482°F and a pressure range from the bubbl-point ro 10,000 psis. The equations expressing the correlation for. mixrurrc were developed from 647 experimental measure-rilents of volume on 47 bouom-hole samples covering ; temperature range of 72" to 250°F and a pressure znge from bubble-point ro 5,000 psig. The average absotute deviation was found to he 1.6 per cent with the maximum for any measurement of 4.9 per cent. INTRODUCTION Accuratc information of the pressure-volume-temper-iiture behavior of hydrocarbon liquids is of considerable importance in the field of both applied and theoretical science and, especially, in the solution of petroleum reservoir engineering problems. These PVT relationships can be expressed graphically, in tabular form or as equations of state. Equations of state for gases have been developed based on the ratio of pressure, temperature and volume to the pressure, temperature and volume at the critical points of the hydrocarbons. These equations have been successful in yielding values fairly accurate for reservoir engineering purposes. For liquids, however, relations of this type are more complex and have not yielded useful results. The composition of reservoir liquids is normally expressed in terms of the moles of hydrocarbons C,? C,. C,. elc, per mole of mixture. The composition must include the fraction of a mixture such as C,,, which cannot be separated with reasonable time and effort into specific hydrocarbons. Although there are several equations of state having variable degrees of accuracy applicable to pure liquid hydrocarbons, none includes a means for estimating the volume of mixtures as a function of temperature. pressure and composition expressed in this manner.

By T. H. Alden, H. W. Schadler

The strain rate dependence of the flow stress of the eutectoid Zn-Al alloy has been determined as a function of mechanical processing, microstructure, and temperature. The best superplastic properties result from the ultrafine, equiaxed structure produced by solution treatment and isothermal transformation at 0°C. Lamellar structures produced by isothermal transformation and coarse equiaxed structures produced by annealing also exhibit strain rate sensitivity in excess of 0.5, but at higher stresses and lower strain rates than the finest structure. Solution treatment and isothermal transformation eliminate the effect of prior processing history. Small composition variations in the binary alloy do not influence the mechanical properties. Below the eutectoid transformation temperature (.275C) increasing temperature lowers the flow stress at all strain rates. The data do not favor any of the present proposals for the mechanism of superplastic flow. ALLOYS of zinc and aluminum, near the eutectoid composition, have been investigated for: 1) the flow stress-strain rate and elongation behavior,1, 2) the transformation kinetics,3 and 3) structure,3"5 but the structure sensitivity of the mechanical properties is poorly understood. Using a near eutectoid alloy water-quenched from 380°C, Backofen et aL2 estab- high and increases with increasing strain rate. They found a correlation between strain rate sensitivity and tensile elongation as expected from the increased resistance to necking that a high strain rate sensitivity provides.296 The large elongation at high strain rates is attractive for metal forming. Since most other superplastic alloys7-l3 do not show high strain rate sensitivity at such a high strain rate (for the exception see Ref. 12) there is the possibility of a unique deformation mechanism for this alloy. The sensitivity of the mechanical properties of the eutectoid alloy to thermal history1 suggests a structure sensitivity that has not been demonstrated. Gar-wood and Hopkins3 identified a lamellar product for material transformed between 200" and 260°C. The size of the lamellae decreased with decreasing temperature. They also demonstrated that an unresolved transformation product formed below 200°C. A granular two-phase material was resolved for specimens quenched to below 150°C by Mitbauer and sauerwald4 who observed coarsening of the structure after annealing. The role of grain boundaries in superplastic deformation is suggested by the strong effect of grain refinement in encouraging this phenomenon at high strain rateS7-11, 13 and is emphasized in several proposals about rnechanism7, 8, 12 and in a theory14 of high-temperature deformation. Alden8 showed metallographic evidence that grain boundary sliding is occurring extensively at strain rates where m is large but less at high strain rates where normal plasticity is observed. Holt and Backofen10 have shown that sliding also oc-

Jan 1, 1969