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By Oliver B. Hopkins

The Peruvian production increased over 3 million barrels from 1933 to 1934—from approximately 13¼ million barrels to over 16¼ million barrels—bringing the cumulative production of the country up to 171 million barrels. Most of this production, as well as most of the increase in 1934, came from La Brea-Parinas Estate, the property of the International Petroleum Co., Limited. In 1932 Peru stood eleventh among the oil-producing countries of the world, but in 1933 her production exceeded that of Trinidad, Argentine and Colombia, which placed her in eighth position. In 1934 Peru's production was exceeded by that of Colombia by about one million barrels, and by that of the Argentine by about 1½ million barrels, thus placing her in tenth position. After several years of relative inactivity in drilling and exploration there was a noticeable increase during 1934 in both of these lines of activity. Oil Fields La Brea-Parinas Estate.—Production on the La Brea-Parinas Estate. reached a significant total of 85,080 bbl. as early as 1891. It increased to over one million barrels in 1912, and to over 10 million barrels in 1929, and in 1934 it reached an all-time high of over 14 million barrels. The total production from 1890 to 1934 was 133,784,609 barrels. Practically all the drilling on the property has been done with cable tools, but during 1934 three strings of rotary tools were introduced. One was a heavy outfit for drilling a deep test and the other two were lighter outfits for deepening wells in the newer section of the field, where the gas pressure was too high to permit safe drilling with standard tools. During 1934 a total of 28,127 ft. was drilled, 66 wells were deepened, and 6 new wells were completed. At the end of the year 2844 wells had been drilled on the Estate, of which 1814 were still productive. The remaining 1030 wells represent abandoned producers or dry holes. The total area that has been productive up to the present time is estimated at 13,369 acres. An interesting article on the various phases of operations of the International Petroleum Co. was written by Arthur Iddings and published in The Oil and Gas Journal (Dec. 27, 1934).

Jan 1, 1935

By Don H. Baker

THE need for new or improved refractory materials has caused metal phosphides to be given renewed scrutiny. Some metal phosphides show high-temperature inertness, are exceptionally hard, and exhibit a marked resistance to chemical attack. Various metal phosphides have been prepared for study by direct combination of the elements,'-' by reaction of metal or metal compounds with phosphine or phosphorus trichloride,'"' by thermal decomposition of a metallic phosphate or phosphite,"-'8 and by molten salt electrolysis.19 Electrolytic preparation of phosphides of titanium, manganese, and chromium from their oxides is reported in this paper. An externally heated 3-in.-ID by 6-in.-deep graphite cell, that served as the anode as well as a container for the electrolyte, was used in these investigations, and a suspended, centrally positioned graphite rod served as the cathode. A closely fitting silicon carbide furnace liner minimized atmospheric oxidation of the crucible. Electrolyses were performed for predetermined periods and current settings. Preliminary research had indicated the more efficient current and potential settings that could be used. Upon completion of the deposition period, the deposit was hot-stripped from the cathode. The mass of crystalline deposit, plus occluded and adhering salt, was crushed to minus 10 mesh and hot-leached in dilute hydrochloric acid. The leached crystalline material was water-washed, dried, and sampled for analysis. Products were identified by X-ray diffraction and standard analytical procedures. Electrochemical studies were initiated to establish the optimum conditions necessary to produce manganese phosphide (MnP), titanium phosphide (Tip), and chromium phosphide (CrP). Among the factors studied were the operating temperature, the imposed current, and the electrolyte system. If the temperature, or imposed current, was too high, deposition of phosphorus resulted, and if either were too low, partially reduced lower oxides were deposited. The operating conditions established for repetitive high-quality production of metal phosphides of the MP structure are presented in Table I. The metal phosphide crystals varied in size, but all had a definite metallic appearance. Typical are the crystals of CrP shown in Fig. 1. Evaluation data and analysis of the crystals are presented in Table 11. Efforts to measure resistivity of these three compounds over the temperature ranges of 250o to 400°K were hampered by the small physical size of the crys-

Jan 1, 1968

The National Research Council was organized in 1916 at the request of the President by the National Academy of Sciences, under its congressional charter, as a measure of national preparedness. The work accomplished by the council in organizing research and in securing cooperation of military and civilian agencies in the solution of military problems demonstrates its capacity for larger service. The National Academy of Sciences is therefore requested to perpetuate the National Research Council, the duties of which shall he as follows: 1. In general, to stimulate research in the mathematical, physical, and biological sciences, and in the application of these sciences to engineering, agriculture, medicine, and other useful arts, with the object of increasing knowledge, of strengthening the national defense, and of contributing in other ways to the public welfare. 2. To survey the larger possibilities of science, to formulate comprehensive projects of research, and to develop effective means of utilizing the scientific and technical resources of the country for dealing with these projects. 3. To promote cooperation in research, at horse and abroad, in order to secure concentration of effort, minimize duplication, and stimulate progress; but in all cooperative undertakings to give encouragement to individual initiative as fundamentally important to the advancement of science. 4. To serve as a means of bringing American and foreign investigators into active cooperation with the scientific and technical services of the War and Navy Departments and with those of the civil branches of the Government. 5. To direct the attention of scientific and technical investigators to the present importance of military and industrial problems in connection with the war, and to aid in the solution of these problems by organizing specific researches. 6. To gather and collate scientific and technical information, at home and abroad, in cooperation with governmental and other agencies, and to render such information available to duly accredited persons. Effective prosecution of the council's work requires the cordial collaboration of the scientific and technical branches of the Government, both military and civil. To this end representatives of the Government, upon the nomination of the National Academy of Sciences, will he designated by the President as members of the council, as heretofore, and the heads of the departments immediately concerned will continue to cooperate in every way that may be required. THE WHITE HOUSE, WOODROW WILSON. 11 May, 1918.

Jan 7, 1918

By H. E. Howe, A. A. Smith

The creep properties of lead alloys have been studied by a number of investigators but most of the work has been done on extruded material and the amount of data available on rolled alloys is surprisingly limited. Greenwood1 and his collaborators investigated various rolled commercial leads containing relatively small amounts of impurities, Phillips2 likewise studied rolled commercial leads, although he did include a few alloys— such as tellurium lead and one per cent antimonial lead. But as far as the authors are aware no data on the creep properties of so-called "hard leads"-—i.e., containing from 4 to 8 per cent antimony—have been published. In this paper some data are presented on a few antimonial lead alloys and compared with a copper-bearing lead. Preparation OF Specimens All the alloys used in this investigation were cast at a temperature of 400°C. into an open cast-iron mold preheated to Ioo°C., the resultant casting being % by I by 10 in. The copper-bearing alloy was cold-rolled by 10 per cent passes to a thickness of 0.100 in. Creep specimens 16 in. long were prepared by clamping the strips between wooden blocks and machining the edges of the strips parallel by means of a plane. Careful manipulation gave parallel specimens with no reduced section and with a minimum of distortion. The antimonial lead castings were hot-rolled in 10 per cent passes at a temperature of I50°C. to a thickness of 0.400 in., the heating being carried out in an electric oven after each pass through the rolls. After the castings had been broken down to 0.400 in., they were allowed to cool to room temperature and then cold-rolled to 0.100 in. with the usual Io per cent passes. Sufficient time was allowed after each pass for the strips to cool to room temperature. The apparatus and method of measuring strain have been adequately described in a previous paper3 and essentially the same practice was used in obtaining the present data. Time-extension curves for only two alloys are given, since these are typical of all. Figs. I and 2 show the time-extension Curves for the copper-bearing alloy A at 30°C. and loo°C., and Figs. 3 and 4 show

Jan 1, 1945

By David Donoghue

THE. years 1901, 1910, and 1924 may be considered as the beginning of new eras in the history of the oil industry of the Gulf Coast of Texas and Louisiana. Spindletop, in 1901, with its enormous cap-rock production revealed the possibilities of the salt domes. The lateral sand development at Vinton, in 1910, renewed interest in the then known domes which were non-producing, or were producing from the cap rock or from sands above the cap rock. The discovery of three domes, Nash, Orchard and Long Point, in the year 1924, by means of the torsion balance and the seismograph, is the beginning of intensive explorations of the Gulf coastal plain by geophysical methods. Domes other than those mentioned have no doubt been found during the last few months of the year but tests have not been drilled to confirm the evidence of the instruments. DISCOVERY OF DOMES BY GEOPHYSICAL METHODS The Rycade Oil Corpn. operated the first torsion balance on the Gulf Coast in October, 1922, and the Roxana Petroleum Corpn. brought in one of these instruments and began work in December, 1922. The U. S. Coast and Geodetic Survey made some gravity observations at Damon Mound, in 1923, with a pendulum apparatus. In March, 1924, the Marland Oil Co. placed the first seismograph on the Gulf Coast and the Gulf Production Co. followed with one in May. In June, 1924, the Gulf Production Co. began operations with a torsion balance. The Atlantic Oil Producing Co., The Texas Co., and others have experimented with several types of instruments involving various principles. During the next few years, a great advance in geophysical methods may be expected, especially if one of the newly discovered domes should be productive. The first dome discovered was the Nash, in Fort Bend County, Tex., about 6 mi. east of Damon Mound. A slight elevation and two shallow wells containing sulfurous waters made the locality somewhat interesting from the standpoint of surface indications, and the torsion-balance measurements indicated the presence of a dome. On July 20, 1924, the Rycade Oil Corpn. No. 1 Wisdom encountered lime at a depth of 634 ft. and anhydrite at 639 ft. The hole was abandoned on Sept. 8, 1924, at 769 ft. in anhydrite. A cavity in the anhydrite caused much delay and the final abandonment of this test.

Jan 3, 1925

By A. H. Bell

The results of repressuring (or gas-drive) have been very encouraging to the several companies doing experimental work along these lines in California. The most notable examples are the Shell and the Union Oil companies at Dominguez, the Marland Oil Co. at Seal Beach, and the California Petroleum Corpn. at South Mountain. The results of the Marland test at Seal Beach are interesting in that re pressuring was started while several wells were still flowing; also, on account of the high pressures required to overcome the hydrostatic pressure exerted by high-head edge water. The well first chosen for repressuring is about halfway up the flank of the structure and had been on the beam making about 250 bbl. of fluid daily, cutting about 60 per cent. emulsion. The fluid lcvel was 230 ft. from the surface and the top of the sand was 4393 ft. Tubing was run to 4000 ft. with a packer and the space above the packer was filled with water to balance the high pressures. Gas was started in slowly to allow the fluid to be pushed back into the sand, and required three days at a pressure of 1500 Ib. per sq. in. before starting into formation. The pressure was once built up to 1800 Ib. and the compressor was shut down for a few hours. When again started, the well took gas at 1500 Ib., and after about three weeks the pressure was dropped to 1450 Ib. The present pressures required range between 1400 and 1450 lb. Volumes as high as 1,500,000 cu. ft. per 24 hr. were put into the well. Increases as high as 50 per cent. in production were obtained in wells up-structure with very little increase in wells down-structure. Also, the water cut on one edge well materially decreased. After about 40 days the repressuring was moved to two wells farther down-structure and the well originally repressured was put on production. The result of this was a great increase in the production of wells one location farther down-structure, a rapid increase in one well one location up-structure, and a decrease in production of the wells farthest up-structure. Later the gas started to short-cut to the nearest well down-structure, nullifying to a certain extent the effects of the repressuring work. The increased production that could be definitely attributed to the repressuring work

Jan 1, 1928

By S. Fisher Morris

The New River coal-field embraces that portion of the Appalachian coal formation which lies on the waters of the New River, principally in Fayette and Raleigh counties, West Virginia, covering a strip of territory about forty miles in length along the line of the Chesapeake and Ohio Railroad from Quinnimont to Kanawha Falls, where the New River empties into the Kanawha, the railroad following the banks of the river the whole distance. (See map.) Between Kanawha Falls and the Valley of the Ohio lies the great Kanawha region, and these two coal-fields possess a greater variety of coal than can be found in any other portion of the country, enabling them to furnish the best fuels for any of the various demands of manufacture or domestic use, the Kanawha region possessing many varieties of gas, hard splint, and cannel coal, and the New River region bituminous and semi-bitnminous, steam and coking coal. The New River, in its westward course towards the Kanawha, has cut its way entirely through the Sera1 conglomerate or No. XII of the Pennsylvania Reports, the Umbral red shales of No. XI appearing at the foot of the mountains at the eastern end of the region at Quinnimont, one of the upper ledges of the Conglomerate forming the summits; while at the western end, at Kanawha Falls, the top of the Conglomerate is nearly down to the level of the river, a portion of the " Lower Productive Measures" forming the greater portion of the mountains. These mountains rise abruptly from the banks of the river to a height of from 800 to 1200 feet, leaving only here and there narrow strips of bottom land, a few acres in extent; and as the measures consist principally of hard sandstones, shales, and conglomerates lying ill a nearly horizontal position, the mountain-sides are very precipitous, with many long and high cliffs, which, with the great height of the mountains, give the country a very rugged appearance. Along the sides of these mountains fronting on the New River and its many tributaries there are exposed the outcroppings of several veins of bituminous and. semi-bituminous coal, varying in thickness from a few inches to over four feet, five of them being workable, or

Jan 1, 1880

By F. E. Jaumot, R. L. Smith

Self-diffusion in zinc at temperatures below 200°C has been studied using both single crystal and polycrystal samples. Anomalous results were obtained for single crystal samples, the data indicating that in some cases grain boundary diffusion predominated. These anomalous results are presumed to be due to low angle lineage boundaries in the single crystals. When volume diffusion occurred in either single or polycrystal samples, the values for the diffusion coefficient were as much as several orders of magnitude larger than would be expected from high temperature data. ONSIDERABLE work has been done on self-^-*diffusion at temperatures in the neighborhood of two thirds of the melting temperature (in OK) and higher, but very little has been done at lower temperatures. This is particularly true of self-diffusion in single crystals. This paper reports work on self-diffusion in zinc at temperatures below 200 °C where both polycrystalline and single crystal samples have been used. The measurements were made using both the sectioning and absorption techniques. The experiments on diffusion at low temperatures were initiated primarily for three reasons: to obtain data from single crystal diffusion covering a wide range of temperatures, to obtain values of the activation energy for grain boundary diffusion, and to obtain, if possible, a lower limit to the temperatures at which the absorption technique may be used. It is possible to determine whether volume or grain boundary diffusion predominates at low temperatures by analyzing the manner in which the concentration of the diffusing atoms varies with the depth of penetration. The analysis is possible only for the sectioning technique. For volume diffusion and for the boundary conditions of the present experiment, the curve of the logarithm of the concentration, C, vs the square of the penetration depth, x, is a straight line with the slope proportional to — 1/D. If grain boundary diffusion predominates, Fisher' has shown that a curve of In C vs the first power of the penetration depth should be a straight line. This linear dependence of concentration on depth has been observed experimentally by several investigators. (See, for example, refs. 3 and 4.) Following Fisher's analysis, the grain boundary diffusion coefficient can be written as where 8 is the grain boundary width, D, is the volume diffusion coefficient at the temperature involved, t is the time of diffusion, C is the concentration of diffusing material, and x is the depth of penetration. A more general analysis employing the same model as Fisher's but with fewer assumptions has been given by Whipple.' In contrast to Fisher's analysis the more general analysis of Whipple does not always yield a straight line relation between In C and x. Recently Turnbull and Hoffman have discussed both analyses and have applied the Fisher-Whipple model to a more refined dislocation model of the grain boundary. They have also discussed the possibility of a large effect of grain boundary direction on diffusion. In the case of the absorption technique, for which results are also given, one simply gets a value for the diffusion coefficient with no indication of the predominating mechanism. Experimental Techniques Single crystals of 99.99+ pct Zn were grown using a modified Bridgman method. Polycrystal samples were prepared in three grain sizes (small, about 4 mm2; medium, about 9 mm'; and large, about 25 mmz) by quenching, air cooling, and furnace cooling. The grains of the polycrystalline samples tended to be columnar, with some preferred texture such that the c-axis was inclined at about 20" to 25" from the normal to the diffusion face, particularly in the medium and large grain size samples. The samples were cut from the rod, polished, and heavily etched, and faces cut accurately parallel using a jeweler's lathe. They were again etched to remove the lathe smear and annealed for 3 hr at 250" to 300°C. After annealing, they were etched, examined, and the orientation determined by Laue back reflection photographs. They were then electroplated with Zn. The plated surfaces were examined for uniformity; nonuniform coatings were removed by etching and the samples replated without additional preparation. For the diffusion anneals, the samples were placed in pairs, with active faces together, in evacuated Pyrex tubes. Constant temperature baths were used, and the variation in temperature did not exceed ±l°C, Diffusion runs were made at l00°,

Jan 1, 1957

By W. T. Weller

In Part I, a study of pressure build-up curves calculated for conditions under which both oil and gas flow led to the conclusion that the presence of a dispersed free gas phase in an oil reservoir must be taken into consideration to estimate accurately average reservoir pressure and permeability from build-up curves. Familiar methods based on the assumption of no free gas can be extended to the two-phase case by using total compressibility and mobility in place of single-fluid compressibility and mobility. These methods give correct values for average pressure and permeability when gas saturation is small. Errors become larger as the gas saturation increases. However, for the use to which the results will be put, the methods are satisfactory for reservoir engineering purposes. An improved method of calculating the performance of depletion-type reservoirs is presented in Part 2. Because the mathematical relationships describing simultaneous flow of oil and gas are quite involved. simplifying assumptions are made to provide means of obtaining approximate solutions of reasonable accuracy. One such approximate method now in use is the constant-GOR solution. It involves the assumption that at any instant, the ratio of total gas flow rate (both free and disolved) to oil flow rate is the same at all points in the reservoir. The approach is not applicable unless the free gar saturation in the reservoir is everywhere greater than the critical gas saturation. This paper presents a modification which, by avoiding the constant-GOR assumption, makes the method applicable to all reservoir conditions, and so far appears to be more accurate than the constant-GOR solution and to he comparable in required compuctation time. PART I— BUILD-UP CURVE ANALYSIS INTRODUCTION Pressure build-up characteristics of shut-in wells have been used for many years by engineers to evaluate average reservoir pressure, effective permeability thickness of the pay section, effectiveness of well completion (skin effect) and reservoir size. A number of methods of analysis have appeared from time to time."" Without exception, these methods are based on the assumption that the reservoir contains but one fluid of constant small compressibility and constant mobility. It has been suggesteda" hat these single-fluid methods may be applied to data from reservoirs containing both oil and gas by substitution of some effective total properties of the multiphase system in place of the corresponding single-phase properties. The present investigation was undertaken primarily to evaluate this approach. METHOD A number of theoretical build-up curves were calculated for conditions of two-phase flow, under the assumption of certain reservoir and fluid properties, and were analyzed by single-fluid methods with appropriate total compressibility and total mobility values for the corresponding single-fluid properties. Results of the analyses were compared with the assumed conditions. The theoretical build-up curves were completed by procedures similar to those of West, Garvin and Sheldon." Since these calculations require a considerable amount of computer time, an attempt was made to derive an approximate calculation method. The attempt was unsuccessful for calculating build-up curves, but the effort did result in a new approximate method of calculating the performance of solution gas drive reservoirs, which appears to be an improvement over the constant-GOR method" used previously (see Part 2). The West, Garvin and Sheldon calculations involved the following assumptions: (1) the reservoir is circular and completely bounded, with a completely penetrating well at its center; (2) the porous medium is uniform and iso-tropic, with a constant water saturation at all points; (3) gravity effects can be neglected; (4) compressibility of rock and water can be neglected; (5) the composition and equilibrium are constant for oil and gas; (6) the same pressure exists in both the oil phase and the gas phase; and (7) no afterproduction occurs, i.e., the well is shut in at the sand face for build-up. These assumptions make it possible to describe two-phase flow of oil and gas by the partial differential equations:

Jan 1, 1967

By H. S. Thomsen, W. C. Duesterhoeft, R. E. Hartline

The attenuation and phase shift which formations produce in the electromagnetic field of an induction-type electrical well-logging instrument are great enough to substantially affect the response of the tool to formation conductivity under normal logging conditions. The application of the general equations for the propagation of an electromagnetic field in a conductive medium to the transmitter-receiver coil pair of an induction-logging-tool coil system gives an expression for the response which properly takes the propagation effects into account. A comparison of a calculation of this type with the response computed from the commonly used geometric factor concept, which does not include the propagation effect, leads to a factor Go representing the ratio of the responses computed by the two methods. The value of Go decreases not only with increasing formation conductivity, but also with increasing transmitter-to-detector coil spacing. For a single coil pair with a 40-in. spacing, the value of Go is 0.972 in a 20-millimho/m formation. The value is reduced to 0.915 and 0.812 for conductivities of 200 and 1,000 millimhos/m. As a result, the basic signal generated by the induction-logging coil system is not linearly related to formation conductivity as expected from the geometric factor concept. A uniform conductivity scale can be obtained only by adding a suitable nonlinear element to the recording system. The addition of auxiliary coils, having spacings less than the main-coil span, to achieve focusing results in an even greater departure of the basic signal from linearity with conductivity. The solution of the field equations near the interface between two formations of different conductivity gives the curve shape on an induction logging tool in crossing the interface. The addition of auxiliary coils to achieve focusing can add anomalous character to the curve shape in crossing the interface, which might be mistaken for lithological detail. Preliminary calculations which include the propagation effects in the determination of the conductivity correction for thin beds lead to correction factors which are substantially smaller than those obtained from geometric factor considerations. It is apparent that thin-bed corrections derived from geometric factor calculations are of doubtful validity. INTRODUCTION Although the electromagnetic induction type of electrical well log has been used for a number of years and has gained general acceptance in quantitative well-log interpretation, no technically complete investigation of the mechanism and of its operation has been published. The studies which have been presented are based upon the premise that neither the shape nor the intensity of the induction field of the logging tool is in any way affected by the electrical characteristics of the formation. From the inception of induction logging it has been recognized that under some formation conditions the performance of the instrument could be expected to be substantially different from that predicted by the simplified analysis. This anomalous performance has been called "skin effect" since it is the result of the same phenomenon which causes high-frequency alternating currents to flow only near the surface of metallic conductors. In the range of conductivities encountered in the sediments, the formation actually does not exhibit the sharply defined conducting "skin" shown by metals. The gradual modification of the distribution of the currents in the formation, produced by the induction field of the logging tool, is the direct result of phenomena associated with the propagation of the electromagnetic field through the formation. Therefore, it can be much more appropriately described as the "propagation effect". One purpose of this paper is to review the results of a solution of the equations for the performance of a single transmitter-receiver coil pair induction-logging system which takes into account the propagation effect, showing the manner in which the tool performance established by this analysis differs from that derived from the less comprehensive analyses currently in use. PRINCIPLE OF OPERATION OF THE INDUCTION LOGGING INSTRUMENT The high-frequency alternating current which is maintained at a constant value in the transmitter coil

By W. O. Philbrook, H. W. Hosking, N. B. Melcher

A simple and inexpensive mercury-tracer method has been develohed to study rates and Patterns of gas flow in blast furnaces. A Pulse of mercury is injected into the hot blast, and its arrival at the sampling Point is recorded by an electronic circuit that measures resonant absorbtion of ultraviolet light by mercury vapor in the gas aspirated .through the detecting. cell. A rapidly developing interest in blast-furnace technology in recent years has created a strong demand for precise knowledge of the rates and patterns of gas movement through the stock column. Classical fluid-flow theory cannot supply the desired information because the complexity of the blast-furnace situation precludes the accurate determination of many of the parameters required for solution of the equations. In fact some of the terms employed in fluid-flow treatments become almost meaningless under blast-furnace conditions. The void fraction of the stock column, for example, varies widely from place to place and is affected by the segregation of charge materials, attrition of lumps during descent, and channeling. Gas density varies with changes in local pressure, temperature, and composition, while viscosity varies with temperature and composition. Even if mean values for these functions were acceptable, they would be either impossible or extremely difficult to determine with a high degree of accuracy since the value of the mean for all gas properties would depend upon the flow distribution itself. Attempts to study gas movement by the pitot-tube determination of kinetic pressures have met with little acceptance. Reproducibility of results is extremely difficult to achieve in a situation where alignment of the tube orifice with respect to the flow direction in tortuous channels cannot be guaranteed. Because of these difficulties it would appear that progress can be achieved only with a direct method of measuring gas velocities and determining the shape of flow paths through the stock. The establishment of such a method is described in this paper. SELECTION OF METHOD Direct measurement suggests the use of a tracer by means of which the progress of a "parcel" of gas can be followed through the furnace. Several requirements must be met before any selected material can be considered a suitable tracer. First of all, it must be a substance not normally present in blastfurnace gas or dust; otherwise its presence in a gas sample will have little significance. It should be volatile at temperatures normally existing within the furnace, to ensure that it will travel with the gas, as a gas. It should possess special properties enabling its presence in the gas to be detected readily, and it should not undergo exchange reactions with any material normally present within the furnace, including refractories and coke as well as all components of the metal and slag. Radioactive materials naturally are considered because their radioactivity renders them susceptible to detection. However, of the many radioactive materials available, almost all are eliminated from final consideration by their unsuitability in terms of other properties. Radioactive silicon, carbon, calcium, phosphorus, and many others have been considered and discarded, either because they are not volatile over the whole range of significant temperatures, or because they could be expected to undergo exchange reactions with burden or refractory materials. Others which might be suitable in terms of these properties are eliminated because of a low activity, short half life, or the necessity for fragile counting apparatus. Of the many elements available in radioactive form, perhaps radon is the only one suitable for blast-furnace gas-flow studies. This has been used in several investigations1-4 with considerable success. The use of radiotracers has certain inherent disadvantages. One is the cost. An appreciable sum must be allowed for materials each time a test is made. Also, special methods of handling must be employed, and very often the progress of an investigation must be governed by the availability of isotopes and the delivery arrangements that can be made for them. An advantage is immediately gained if the tracer material can be a substance which can

Jan 1, 1960

By H. C. H. Darley

The influence of particle size and concentration on the development of chip hold-down pressure (CHDP) was studied in an apparatus designed to measure the change of filtration rate during the first second of the filtration process. CHDP is controlled by the "bridging" particles (i.e., particles in the 50 to 0.2 micron range), whereas filter loss is controlled by the colloid fraction. The results indicated that a fast drilling fluid with a low filter loss could be obtained if the concentration of bridging solids and the viscosity were kept very low. A novel group of drilling fluids, which we have named colloid emulsions, was developed to meet the above requirements. These colloid emulsions are made by dispersing art oleophilic colloid in oil and emulsifying about 5 per cent of this dispersion in water or a dense brine. Good results have been obtained in field trials with emulsions which use asphalt as the oleophilic colloid. INTRODUCTION In recent years it has been found that fast rates of penetration can be maintained in hard formations by using "clear" water as a drilling fluid. In some cases, however, water cannot be used because the very high down-hole filter loss creates various difficulties in drilling, in logging, or in producing the well. It then becomes necessary to "mud up", which results in a decrease in drilling rate. The reason that mud decreases drilling rates is a complex subject which has been well covered by such authors as Garnier and van Lingen, Cunningham and Eenink,' and van Lingen.3 One of the principal factors involved is the tendency of the drilling fluid to develop a filter cake on the bottom of the hole. The pressure differential which develops across this filter cake opposes the action of the bit in dislodging chips from the rock. This pressure differential is referred to by Garnier and van Lingen' as the chip hold-down pressure, which is denoted by the initials CHDP in this paper. The work described in this paper was undertaken to develop a drilling fluid which would minimize CHDP but which would still have a low filter loss—in other words, a fluid which would deposit a filter cake on the sides but would lay little or no filter cake on the bottom of the hole. EVALUATION OF CHDP EXPERIMENTAL Conditions governing the growth of filter cake on the sides of the hole are obviously different from those on the bottom of the hole. On the sides of the hole, cake will form continuously but at a decreasing rate, until eventually the rate of growth will equal the rate of cake erosion by the mud stream.' On the bottom of the hole, each time a bit tooth dislodges a chip the cake is removed, a fresh rock surface is exposed, and the filtration process must start over again. Thus the CHDP is determined by the amount of cake which can form in the interval between successive tooth strikes at a particular spot, normally a fraction of a second. Our first step therefore was to study filtration rates over the first second or so of the filtration process. These tests were conducted in the simple type of dynamic filter cell shown in Figs. 1 and 2. In this cell the mud was filtered through a train of rock cores while rotating blades kept the mud flowing over the surface of the core. The procedure was to evacuate the cores to 0.05 mm of mercury, saturate with brine, and assemble in the holder under brine. The permeability of the core train was then determined. A plastic seal was placed on the face of the core train, and a rip cord was attached from the seal to one of the blades. At the start of the test, 500 psi was applied to the mud, and the meniscus in the capillary measuring tube was adjusted to zero. When the blades were started, t,he seal was ripped from the face of the core, and filtration began. The filtration rate was at first measured by photographing the advance of the meniscus in the capillary tube. Using

Jan 1, 1966

By John D. Price

COAL blending, in the preparation of coal before coke making, is so commonly practiced as to be almost universal. But the reasons underlying this practice, the benefits resulting from it, and the materials used in blending vary widely. This paper will outline the various phases of the subject and present information which may be correlated with work that has been done elsewhere. It will deal entirely with work done on the high-volatile coking coals of the western part of the United States, special emphasis being given to the coals of Colorado and Utah. A surveyL of the 86 coke plants in active operation in the United States during 1949 indicates that only 9 plants, or 10.5 pct of the total, charged one single rank of coal into their ovens, while the remaining 89.5 pcl made use of blending in some form. This report indicated that of these total plants 5 used straight high-volatile coal, 4 used straight medium-volatile coal, 47 used blends of high and low-vola-tile coals, 25 used blends of high, medium, and low-volatile coals, 2 used blends of high and medium-volatile coals, 3 used blends of medium and low-volatile coals. The fact that certain plants operated on a single kind of coal should not be interpreted to mean that no blending was practiced there, for invariably such plants secure their coal from more than one source and in the interest of uniformity do blend the coals as received. The general term coal blending covers two fields, the first of which is the mechanical mixing of a number of coals to secure uniformity. Often it is found necessary to secure coal for coke production from a number of different mines; these coals, though of the same general type or rank, may differ in their chemical composition or in the physical qualities they impart to coke made from them. Again, it is not unusual to find that coal from different sections of the same mine may show variations in quality. Under such conditions it may be necessary, in the interest of a uniform final product, to introduce a system of blending bins, a bedding yard, or other mechanical methods of securing a uniform mixture. Unfortunately this form of blending has received very little attention up to the present time; it has not received the consideration its value merits. The second type of blending, while also for the purpose of coke improvement, deals more particularly with the use of a blending agent differing in character from the base coal: it is this form of blending that will be discussed here. To consider only the western coals, for blending may be found necessary for other reasons with other coals, blending has been practiced experimentally or commercially under the following conditions: 1—When a single coal or mixture of coals of the same rank does not produce a satisfactory coke. For example, a high-volatile coal when used alone is likely to contract when coked so that a comparatively weak coke is formed. Or, if of very low rank, the coal may be deficient in the necessary bitumens required for good coke production. 2—When a product of some special quality is required, for example, when a plant ordinarily producing blast furnace coke must operate at slow coking rate to produce a high-grade foundry coke. Under this condition the reduced daily production of all products which accompanies slow coking time may be undesirable, and the use of some blending agent to increase the size of coke made at faster coking rates may be necessary. 3—When greater yield of coke or its coproducts is needed. Depending upon economic values of the products it may be found desirable to increase the yield of one or the other. 4—When supply of a particular coal must be used, either to protect reserves of high quality coking coal or to utilize a surplus or inferior product not otherwise usable. Many materials have been used for blending purposes, the exact agent to be used depending both upon the condition to be corrected and the nature of the base coal. No universal blending agent that can

Jan 1, 1954

By G. F. Bolling

STUDIES of grain boundary migration in zone-refined metals have all shown that the rate of migration is greatly reduced by small added solute concentrations. However, it is apparent that a difference exists between boundary migration during normal grain growth and single boundaries migrating in a bicrystal to consume a substructure. To effect the same reduction in velocity in the two cases, much more solute is required for grain growth than for the single boundary experiments. One case is available for direct comparison; both Bolling and winegardl and Aust and utter' added silver and gold to zone-refined lead to study grain growth and single boundary migration, respectively. For comparable reductions in migration rates, about 500 times more solute was required to retard grain growth than to retard the single boundaries. A reason for this difference is suggested here. The rate of grain boundary migration is dependent on solute concentration and must therefore also depend on the solute distribution; i.e., regions of higher solute concentration encountered by a moving boundary must produce greater retardation and thus could determine any observed rate. A dislocation substructure can be the source of a nonuniform solute distribution since it can attract an excess concentration of certain solutes. In fact, it is probable that the solutes which impede grain boundary migration most would segregate most severely to a substructure for the same reasons. Thus a dislocation substructure present in a crystal being consumed could locally magnify the concentration of solute confronting an advancing grain boundary. In the single boundary experiments a low-angle substructure, within single crystals obtained by growth from the melt, was used to provide the driving force to move a grain boundary; in grain growth, no substructure of this magnitude was present. The increased solute concentration at subboundaries should be given approximately by C, = G e c,/kT, where t, is a binding energy and CO the bulk concentration. To account for the difference between the two experiments in the Pb-Ag and Pb-Au cases, C, must be the concentration impeding the single boundary migration, and a value of t, = 0.25 ev is necessary. This is reasonable, even though calculation on a purely elastic basis gives t, = 0.12 ev. because electronic effects must enter for silver and gold in lead. The compound AuPbz forms3 and the metastable compound AgrPb has been reported to nucleate at dislocations prior to the formation of the stable, silver-rich phase.4 Other observations support the hypothesis that a magnified solute concentration impedes the single boundary migration. For example, some crystals were grown by Aust and Rutter at concentrations of ~ 0.1 wt pct Sn and 2 x X at. pct Ag or Au which exhibited a cellular substructure, and in these crystals no boundary migration was observed. It is therefore evident that the higher concentrations at cell boundaries drastically inhibited migration. Inclusions would not have been responsible for this inhibition since according to recent work on cellular segregation,5 no second phase should have occurred in the segregated regions at the cell boundaries for the conditions of growth used, at least in the Pb-Sn system. In the purest lead, only the "special" boundaries observed by Aust and Rutter gave rise to the same activation energy as that obtained in grain growth. It is reasonable to suppose that the structure of special boundaries does not favor segregation at low concentrations and thus solute, or an inhomogeneity in its distribution, would have no effect. Random boundaries, on the other hand, are affected by solute and the substructure would enhance residual concentrations in the zone-refined lead, leading to a higher activation energy. It is clear, even without a detailed theory, that the apparent activation energies and exact solute dependence in the two experiments must be different as long as the non-uniform solute distribution produced by the substructure is important. Recrystallization experiments should also be susceptible to the same kind of local segregation at subboundaries or disloca tion cell walls; a suggestion similar to this has been made by Leslie et al.' Following the arguments presented here, the effects of a given solute concentration would be like those observed by Aust and Rutter if segregation occurred, and like those of grain growth otherwise. This work was partially supported by the Air Force Office of Scientific Research; Contract AF-49(638)-1029.

Jan 1, 1962

By G. A. Vissac, R. G. Minet, N. E. Sylvander

R. G. Minet—The authors' description of the remarkable progress made in the last few years in applying the fluidized solids technique to the problem of lignite drying and carbonization clearly demonstrates that engineering techniques available today may make many processes practical and profitable which a few years ago were considered otherwise. As pointed out in the article, the future of the carbonization step hinges on the value and utilization of low temperature tar. On paper, at any rate, this tar looks like a valuable raw material for the chemical industry to use. Some 50 to 60 pct may be converted to pitch for electrodes, roofing, road tars, and other valuable products; the 25 to 30 pct tar acids could conceivably form a basis for a new low cost resin or plastic of the phenolformalde-hyde type. Yet these materials are so new and dissimilar from available sources that much work must be undertaken by the chemical industry before they will be accepted. Now that the work of Dr. Perry and his colleagues has made a large supply of low temperature tar a real possibility, I would expect the chemical industry to accelerate its work in this field. On the basis of certain data available in the literature it appears possible to produce a more aromatic tar, although in smaller yield, by operating at temperatures in the range of 1300" to 1500°F. Operating a fluidized bed process for lignite at these conditions should be technically possible, at least, and could produce a tar having more familiar characteristics. I wonder if Dr. Parry would care to comment on such a possibility. Incidentally, in our own work on carbonizing coking coals in fluidized beds, using Ohio, Pennsylvania, and West Virginia high volatile bituminous coals, we have obtained yields which agree with the correlation given for tar yields vs moisture and ash-free volatile Btu. Our data are slightly under the line, but certainly in the range of the correlation. We have also obtained evidence in support of the authors' statement as to the effect of air on the process. In our pilot plant all the heat required for carbonizing is released by internal combustion of char in the fluidized bed in normal operation. We are also equipped to obtain all carbonization heat by external electric heaters on the shell of the carbonizer while introducing only an inert gas to the process. We note no difference in tar yield or characteristics between the two operations. In the case of the gas, however, it appears that some hydrogen is consumed by the air combustion. We would be interested in hearing in a little more detail about the hot dust and char handling problems at Sandow. Have the authors found char subject to spontaneous combustion? Have they ever tried a coking coal in their pilot plant? V. F. Parry (author's reply)—Production of a more aromatic tar by operation of the carbonizer at 1300" to 1500°F does not appear to be economical. 1) The capacity of a reactor operating at 1500°F would be 30 to 50 pct less than the capacity at 932 °F and the cost of processing would increase materially. 2) The cracking of tar vapors in a reactor requires appreciable time to complete the reactions and it is doubtful that considering the very short time of residence of tar vapors within the reactor (4 to 10 sec after evolution) the basic character of the tar would be changed significantly. This is indicated from the data reported in Table XIV. 3) General studies have shown that it is advisable to operate at the minimum temperature to produce the maximum tar and minimum gas. 4) Operating problems and the maintenance of vessels and reactors, and the hazards of handling hot char, increase with the temperature of carbonization. It is technically possible to operate at temperatures as high as 1500°F, but in my opinion it is not economical or desirable. We believe that the primary tar must be won in the simplest way and then processed alone to change its character for production of desired products. It is interesting to have confirmation of our observations on the reaction of air with the products of carbonization. The major reaction is with the char, fol-

Jan 1, 1957

By U. N. Bhrany, J. H. Brown

The specifications of particle size and the size analyses of fine particulate materials are commonly presented without reference to the method of analysis. A review of the various sizing methods showed that not only numerous sources of error but also different definitions of size are inherent in the different methods of analysis. To demonstrate the magnitude of the differences, the size distribution of finely crushed quartz was determined by several methods and a critical comparison of the data was made. The experimental results show that appreciably different sizes may be indicated for one material depending on the method of analysis used. However, because the shape of the size-distribution curves determined by almost all methods was constant, a simple method of correlating the data can be adopted. Conversion factors, by which size measurements obtained by the various methods can be expressed in terms of screen sizes, are presented as one method of correlating the results. The size analysis and size specification for lump rock and particulate materials are commonly determined with sieves. With this technique, a readily reproducible measure of size can be obtained merely by duplicating the sieve and the method of sizing. For coarse materials, such as lumps of rock, this technique is simple and effective; and the effects of properties of the material such as shape can be readily understood. When very small particles are measured, however, problems arise. Small sieves are difficult to construct and maintain, and size separations become sensitive to the analytical procedure. For these difficult sieve sizes and for still smaller particles, other sizing techniques employing, for example, sedimentation, light extinction, and microscopy are available. Because these various techniques employ different size-dependent responses to establish size, it is appropriate to examine them and the results they yield to determine their relationships and their limitations. The 'size' of a lump of rock is not an absolute quantity, but rather a defined one. With sieves, for example, the size is defined by the screen aperture and no reference is made to the actual shape of the particle, yet only in the case of a regular body, such as a sphere, can the sieve size be related to the shape. With sieves only two dimensions of a particle can be suggested, for the sieve makes no allowance for the length of the particle passing through an aperture. Similarly, the size of a particle as measured by a microscopic technique need bear no relationship to the size as measured by sieves, although the two measurements may be related statistically. In fact, all size measurements are not only defined quantities, but the measurement actually used is an average that is controlled by the technique employed and, hopefully, reflects the property in question of the material of interest. Many papers have been presented that illustrate the accuracy of the various sizing methods, present the advantages of certain methods for certain applications, and describe the principles and technical backgrounds of the various methods. No attempt will be made in the present paper to review this work in detail. The purpose of the present paper is to examine the limitations of the various sizing methods, and to demonstrate experimentally the relationships between the sizes as determined by the various methods of analysis. It is hoped that by recognition of these limitations and relationships, errors in size specification and size interpretation will be avoided. REVIEW OF SIZING METHODS In specifying the size of a material, not only the data but also the method of measurement must be stated. For example, the size of the lump might be specified as its total volume, as its weight, as its maximum dimension, or as its minimum cross section; any one definition might be completely satisfactory for one problem, but not for another. In practice, size analyses follow four basic approaches and fortunately, the conditions that restrict each approach are known. These major methods include: 1) screen analysis, 2) direct measurement of particle dimensions, 3) determination of equivalent spherical size in response to fluid flow, and 4) specific surface determination. Each of these techniques has several variations and some new techniques are also available, but the limitations of the basic techniques are sufficient to permit at least a preliminary

Jan 1, 1962

By V. C. Allen

THE Tri-State Zinc, Inc., Galena, Ill., was confronted with the problem of securing ore from a deposit because the hoisting shaft was several thousand feet from the mill. The orebody is several thousand feet long, averaging 200 ft in width and 60 ft in height and opened up by vertical shafts some 300 ft deep. Mining is by the room-and-pillar method. During the initial operation the ore was loaded by conventional electric 1/2-yd boom-and-dipper shovels and hauled to the shaft by 8-ton diesel trucks. This underground ore loading and hauling was well adapted to the conditions and productive of low costs per ton. However, with the mill situated as mentioned, a triple handling of all broken rock was necessary: l—from the stope to the shaft by truck, 2—up the shaft by skip br can into the surface hopper, and 3—by truck from the surface hopper to the crushing plant at the mill. In addition to the repeated handling, serious troubles were encountered during the winter because of freezing in the shaft hopper. Consideration was given to either moving the mill to the new orebody or to the construction of a second mill. The presence of other orebodies to be mined at a later date made the first alternative impractical while the capital outlay for a second mill, when the present plant of approximately 850 tons per day was deemed sufficiently large for the total reserves, made the second alternative also unwise. It was decided to retain the mill in the originals location and continue to move the ore to it. The idea of driving an inclined adit from the surface to the bottom of the orebody suitable for truck haulage and big enough to allow the passage of all mechanical equipment was conceived. Among the apparent advantages of such an incline were: 1— Direct haulage from the stope to the mill without rehandling. 2—Elimination of virtually all grizzlies. Trucking from underground to the mill would do away with all hoppers, chutes, gates, and skips and make the maximum rock size dependent solely on the size of the shovel dipper at the mine and the crusher opening at the mill. 3—Less secondary blasting would be needed. 4—Ease of transporting equipment and supplies underground. Shovels and trucks could be taken through the incline intact. 5—Equipment could be brought to the surface for repairs and servicing without loss of time. The same advantages of ease in moving would be present in the handling of men, steel, powder, and supplies. 6—There would be far less difficulty in increasing the amount of tonnage that could be moved by truck up an incline than would be found in attempting to increase the capacity of a shaft. 7—All the broken ore in the stopes would serve as bin capacity, as it would take the breakdown of all of the loading and hauling equipment to have the same effect as a delay in shaft hoisting. 8—All danger of men being trapped in the mine as a result of shaft fire or power stoppage would be eliminated. 9— Virtually all trouble from severe winter conditions would be eliminated by the direct haul underground to the mill. The decision was made to proceed with the driving of an inclined adit. The topography of the surface between the orebody and the mill was such that it was possible to locate the portal at a point 170 ft above the mine floor and 1800 ft horizontally from the central point of the orebody to the south and 2500 ft from the mill to the north. A grade of 10 pct was found to be optimum for continuous truck haulage when the various factors of speed, safety, and truck maintenance were all considered. The incline as driven was consequently 1700 ft long on 10 pct grade and 12 ft high by 17 ft wide in cross section. The tunnel-driving equipment was chosen so that it could be used in mining after the completion of the tunnel. Drilling was done with a jumbo with two Joy jibs mounting 3-in. drills, loading with an Allis-Chalmers diesel-powered, front-end loader of approximately 11/4-yd capacity, and hauling by Koehring Dumptor trucks of 8-ton capacity, diesel-powered. The width of the tunnel allowed the end loader and Dumptor to be placed abreast. Since the Dumptors can be driven either forward or backward with equal facility, loading was accomplished without turning around either machine throughout the loading operation. The crew in addition to the tunnel foreman was comprised of three men per shift at the start and in the later work, four men. Each crew could perform any part of the working cycle. If the drilling was completed and the round blasted in the middle of a shift, the same men would proceed with the loading and hauling. Since the mine already had been drained to the bottom levels, no water was encountered. At the halfway point the tunnel was widened for approximately 100 ft to permit trucks to pass. The total cost of the tunnel excluding the capital outlay for equipment, which was all continued in use in the subsequent mine operation, was $60,363.00 or $35.50 per ft. The tunnel was completed at the end of June, 1949 and has been in continuous use since that time. In the five months from July to November inclusive, 106,049 tons have been transported to the mill or an average of 835 tons per day. No unforeseen disadvantages have been encountered and the advantages which had been predicated before the adit's construction have been more than realized. As previously mentioned, the deposit is worked by the room-and-pillar system with occasional faces up to 125 ft high. Except in driving development drifts when diesel-powered, front-end loaders such as were used in the tunnel are employed, all shoveling is done by Yz-yd boom-dipper type shovels electrically driven. These units need a width of 25 ft and a height of 14 ft in which to operate. All hauling is by diesel trucks, mainly Koehring Dump-tors. Roads are maintained with caterpillar tractors and a road grader. The tonnage output from the

Jan 1, 1952

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969

By E. A. Steigerwald, G. L. Hanna

The influence of work-hardening exponent on the variation of fracture toughness with material thickness was studied for high-strength steel, aluminum, and titanium alloys. The results indicate that, when materials are compared at similar fracture toughness to yield strength ratios, the material with the lower work-hardening exponent undergoes the transition from flat to slant fracture at a larger thickness than material with a high work-hardening exponent. In the thickness range where complete slant fracture is obtained the reverse is true and a lower work-hardening exponent results in a lower fracture toughness. The influence of work-hardening exponent on fracture toughness is, therefore, dependent on the particular fracture mode. In the transition region a low work-hardening exponent is beneficial for fracture toughness while in the 100 pct slant region it is detrimental. THROUGH the use of fracture mechanics analyses, the influence of geometric variables on the crack propagation resistance of structures can be interpreted with reasonable consistency. However, in order to gain a more complete understanding of the fracture process, the influence of material parameters on crack propagation must be defined and coupled to the macroscopic fracture mechanics approach. The work-hardening exponent, which characterizes specific material behavior, may serve as an effective parameter to allow some degree of coupling to be accomplished. In the extension of a crack in a specimen of suitable dimensions the propagation process occurs in a stable manner when the crack extension force is balanced by the resistance to crack extension, which exists in the material at the crack tip. As the applied stress, and therefore the crack extension force, on the specimen increases, the resistance also increases primarily because the effective plastic zone at the crack tip, which is the main energy absorption process, becomes larger. Since the work-hardening rate of a material influences the stress-strain relationship, it will also influence the energy absorption process in the plastic enclave at the crack tip and hence should have an effect on crack propagation. A number of studies have been made correlating the strain-hardening exponent or the strain to tensile instability with the ability of a material to resist fracture. Gensamer1 concluded that a low-strain-hardening exponent would result in a steep strain gradient at the base of a notch. He reasoned that a large work-hardening coefficient would result in high-energy ab- sorption due to the increased area under the stress-strain curve. Larson and Nunes2 experimentally observed in Charpy tests on steels heat-treated to below 200,000 psi yield strength that the energy to failure in the fibrous mode, i.e., above the brittle-to-ductile transition temperature, was logarithmically related to the strain-hardening exponent. In order to avoid the complicating effects present in studying materials which undergo a brittle-to-ductile transition, Ripling evaluated the notch sensitivity of a variety of fcc metals with varying work-hardening exponents.3 The results indicated that the relative notch sensitivity, as determined from tests on specimens with a sharp notch, decreased with increasing values of strain hardening. Although the energy required for ductile or fibrous fracture increases with increasing work hardening, high-strength steels often exhibit improved crack propagation resistance when heat-treated to obtain low values of strain hardening.4,5 An analysis of whether low strain hardening is beneficial or detrimental to crack propagation resistance must depend on the particular fracture criterion involved. At temperatures where the material is relatively ductile and the development of a critical strain is required for fracture, high strain hardening increases the energy required to produce failure. In the transition region and below, however, a critical stress law appears to be valid6 and a low rate of work hardening may produce superior resistance to semibrittle crack propagation. The experimental program is aimed at studying these possibilities and determining the specific influence of strain hardening on the crack propagation resistance of several high-strength materials. MATERIALS AND PROCEDURE The alloys, chosen as representative of various classes of high-strength materials, are summarized in Table I. The heat treatments evaluated along with the smooth tensile properties are presented in Table 11. Pin-loaded sheet tensile specimens were employed to determine the smooth tensile properties. A strain gage extensometer (measuring range 0.200 in.) was used at a strain rate of 0.02 in. per in. per min. The work-hardening exponents were determined from the stress-strain curves generated in the smooth tensile tests and the assumption that the portion of the stress-strain curve beyond the yield point can be described by the power relationship: where a is the true stress, P is the true plastic strain,

Jan 1, 1969

By Jei Y. Choi, P. G. Shewmon

The surfrrce-diffusion coefficients (DJ for Aulg8 on (100) and (111) surfaces of copper have been determined between 1050" and 780°C using a new avuzlysis imd experimental procedure. The results are: D, has also been determined fm cua4 at 870°C, and the values found are 4.5 times larger than those measured by the grain boundary grooving technique for the same surface orientations. This difference is felt to result from the approximate nature of the mathematical solution used in the present work. Attempts to measure D, for silver on copper and silver surfaces indicated a means of matter transport different from surface diffision was dominant in moving tracer from the source out over the surface. Cnlculations and experiment both indicate that this is the flow of silver through the vapor phase which completely masks the much smaller flow due to surface diffusion. The previous self-difhsion studies of D, for silver and copper are discussed in terms of our own analysis and found to yield values of D, factors of lo5 or more greater than those found by the grain boundary grooving tech -nique. UNTIL about 5 years ago it was widely believed that the activation energy for surface diffusion, AH, , was less than that for grain boundary diffusion, AHb,, which in turn was less than that for diffusion through the lattice, AHz.' This was concluded from various evidence that D,> Db>Dl, and one tracer study of D, for silver on silver from which AH, was inferred.2 In 1959 Mullins and Shewmon demonstrated that D, could be determined from the kinetics of the growth of grain-boundary grooves.3 Using this procedure, Gjostein measured D, on copper between 800" and 1050°C and found that the activation energy was roughly equal to AHl .4 Subsequent work on copper,5" silver,',' and goldg between the melting temperature T, and 0.87 T, confirmed that AH, as determined using the grain boundary grooving or scratch-relaxation technique was equal to or greater than AHz. During the same period, Drew and Pye again determined AH, for silver on silver using a tracer techniquelo and a mathematical solution similar to that of Nicker son and arker.' Though the values of D, Drew and Pye measured at any given temperature were about 200 times smaller than those reported by Nickerson and Parker, they again found a low activation energy of about 10 kcal, or about one fifth that found at the higher temperatures with the mass transport technique. A distinguishing characteristic of these two previous tracer studies is that they have worked at low temperatures (-1/2 T,) where they felt volume diffusion was negligible and then analyzed these data as if all tracer atoms leaving the source flowed out into and remained in a homogeneous high-diffusivity surface layer of undefined thickness. This is totally different from the model used in the mass-transport studies or the studies of grain boundary diffusion, which assume the high-diffusivity surface layer to be only a few angstroms thick. If this latter model is applied to the earlier tracer studies, it is shown that the tracer has really pe!etrated into the lattice a mean distance of 1000A. Thus the tracer distribution observed after an anneal is thought to be due to the combined effects of surface and volume diffusion. Independent of the relative validity of the two models, it seems evident to us that any comparison of the values of D, as determined in these two ways is meaningless and misleading, since the values of D, and AH, obtained in these two ways would be totally different for the same physical distributions of tracer. Once the fundamental difference in the approaches of the two techniques is established, we are faced with the question of which model better approximates physical reality. Here all the evidence seems to be on the side of the ''thin surface layer" analysis. In fact, the authors of Refs. 2 and 9 do not argue for the "thick-layer model" we have described; they simply invoke it through the equation they use to calculate D, . The primary evidence for the thin-film approach is: a) grain boundary grooves and scratches widen in proportion to tU4 and Mullins' rigorous analysis shows that this is only valid for a surface layer which is quite thin relative to the width of the groove;11 b) all accepted or seriously discussed models of solid-vapor interfaces and high-angle grain boundaries assume that the disturbed region of the interface is at most a few a0 thick. With the above in mind, it was desirable to determine D, using a radioactive tracer and a "thin-

Jan 1, 1964