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By Robert H. Leach

SILVER the whitest of all metals, has been used for thousands of years. Students of antiquity agree that silver, gold, copper, and their alloys were the first metals discovered by man and they have all played an important part throughout the advance of civilization. Native silver has been found in different parts of the world in varying form and size, such as clusters of fine wires in rock cavities, thin sheets along cleavage planes in veins of rocks, and pieces of irregular shape that vary in size from extremely small particles to masses weighing many pounds. Nearly pure silver is found in, the native state but the native metal is more likely to contain copper or gold. Some of the natural alloys closely approximate the compositions of synthetic alloys that are used in the arts at the present time. As these native silver alloys usually are malleable and ductile, it is evident that prehistoric man was provided by nature with metals that he could work, with the crude tools at his command, into simple ornaments or other articles. The relative scarcity of silver combined with its resistance to attack under ordinary atmospheric conditions have been important factors in determining the purposes for which man has used it. Its scarcity and indestructible character have made its possession particularly desirable, and from the earliest times its principal use has been as a measure of wealth and a medium of exchange. The comparatively high value of silver in relation to other commodities makes it possible to transport a large amount of wealth in small bulk, and silver has traveled back and forth over all parts of the world. Even when made into ornamental pieces, such as bracelets,

Jan 1, 1953

By J. F. Myers, S. E. Sharp

The safety data presented in this paper are based upon replies to a Questionnaire sent out to representative mining companics. The authors feel that it is a fair cross section of the milling industry, in that the 17 companies, of the United States and Canada, reporting on 22 mills, are scattered from the Hudson Bay to the Mexican border and from coast to coast. These data concern the accident records of the various plants from 1939 to 1944, inclusive and the six years are divided into two periods. The first period (1939, 1940 and 1941) represents something of a normal operating condition. The second period (1942, 1943 and 1944) represents the period of time that was most affected by war conditions. During the second period there was a high labor turnover, inexperienced workers were numerous, women replaced men in many kinds of work, a labor shortage existed more or less throughout the industry, and supervision was pushed for peak production. All of the companies reporting compiled their accident experiences for these six years in accordance with the standards set up by the American Standards Association (New York, N. Y.), consequently the tabu lated data presented herein are comparable. The authors of this paper feel that the industry as a whole is greatly indebted to the personnel of the companies that furnished these data, which make this study possible for presentation. This survey covers a total exposure of 74,528,880 man-hours, with 105,471 man-days of lost time from 870 accidents. Safety Records In Table I, the safety record is shown of the various mills reporting. The severity rate is usually conceded to be the most vital statistical figure in safety parlance, therefore the participating companies are listed in order of their severity rate for the combined six-year period, under size of organizatiori. The table also shows the frequency rate as well as the frequency-severity ratio (F/S). As noted in Table I, most of the companies suffered an increase in both severity and frequency rates during the second period; only six of the 22 enjoyed an improvement. From correspondence with the various plants, it seems that a few had very little labor shortage or turnover, and these were not greatly affected. A few plants, anticipating the situation, strengthened their training facilities and actually were able to show a better experience during the second period. This gives great credence to the value of organized training in any safety program. The frequency-severity ratio (F/S) shown in the last column of Table I offers

Jan 1, 1947

By S. E. Sharp, J. F. Myers

The safety data presented in this paper are based upon replies to a Questionnaire sent out to representative mining companics. The authors feel that it is a fair cross section of the milling industry, in that the 17 companies, of the United States and Canada, reporting on 22 mills, are scattered from the Hudson Bay to the Mexican border and from coast to coast. These data concern the accident records of the various plants from 1939 to 1944, inclusive and the six years are divided into two periods. The first period (1939, 1940 and 1941) represents something of a normal operating condition. The second period (1942, 1943 and 1944) represents the period of time that was most affected by war conditions. During the second period there was a high labor turnover, inexperienced workers were numerous, women replaced men in many kinds of work, a labor shortage existed more or less throughout the industry, and supervision was pushed for peak production. All of the companies reporting compiled their accident experiences for these six years in accordance with the standards set up by the American Standards Association (New York, N. Y.), consequently the tabu lated data presented herein are comparable. The authors of this paper feel that the industry as a whole is greatly indebted to the personnel of the companies that furnished these data, which make this study possible for presentation. This survey covers a total exposure of 74,528,880 man-hours, with 105,471 man-days of lost time from 870 accidents. Safety Records In Table I, the safety record is shown of the various mills reporting. The severity rate is usually conceded to be the most vital statistical figure in safety parlance, therefore the participating companies are listed in order of their severity rate for the combined six-year period, under size of organizatiori. The table also shows the frequency rate as well as the frequency-severity ratio (F/S). As noted in Table I, most of the companies suffered an increase in both severity and frequency rates during the second period; only six of the 22 enjoyed an improvement. From correspondence with the various plants, it seems that a few had very little labor shortage or turnover, and these were not greatly affected. A few plants, anticipating the situation, strengthened their training facilities and actually were able to show a better experience during the second period. This gives great credence to the value of organized training in any safety program. The frequency-severity ratio (F/S) shown in the last column of Table I offers

Jan 1, 1947

By H. W. Miller, V. H. Wilhem

Although the year 1933 was a period of uncertainty, considerable new development was initiated, with a high percentage of favorable results, for owing to financial conditions only projects of merit were proposed and developed. Unfavorable marketing conditions caused severe financial losses to refinery and sales departments of nearly all companies during the first half of the year. In anticipation of stabilized Government control, earnings were generally favorable during the third quarter but failure of the Government to take legal action against violators of the proration orders, and lack of agreement on a definite plan of curtailment, resulted in considerable overproduction and demoralization of the market structure during most of the final quarter. However, toward the close of the year Government action against violators of the Oil Code had a tendency to decrease overproduction materially and give the market a firmer tone. As a whole, the price structure of crude oil was maintained at a high level during the year; in fact, at a much higher level than the price of refinery products warranted. At no time during the year was production within 10,000 bbl. daily of the state allotment, overproduction of crude reaching a peak of 70,000 bbl. on Sept. 7, average daily average for the year being about 27,000 barrels. Numerous plans for equitable curtailment were prepared and tested during the year, none of which fully solved the many and intricate problems faced by operators who were in most cases willing to curtail if they could feel that cooperation was being practiced by their neighbors. Outstanding events in California oildom during the period under discussion may be classified under the following headings: 1. New discoveries. (a) New development in proven areas. (b) Deeper zones in settled pools. 2. Unproductive wildcat operations. 3. Whipstocking practice and procedure. 4. Progress of unit and orderly plans of development.

Jan 1, 1934

By Fred J. Hurst

In 1934, Irvin Lavine (A), University of North Dakota, stated that the low-rank coals (lignite and subbituminous) of this country represent a vast tonnage of fuel of commercial value and predicted that some day they will play an important role in our economic welfare. Lavine also pointed out that one of the major problems with efficient utilization of the low-rank coals is their high moisture content. Following the discovery of uranium-bearing lignite in the Williston basin of North and South Dakota in 1948 by D. G. Wyant and E. P. Beroni, detailed investigations were conducted (primarily during 1950 to 1954) by members of the U. S. Geological Survey to evaluate the geologic factors and economic possibilities of the radioactive lignites as a source of uranium. The information gained in these studies and summarized in several papers indicated that a large potential reserve of uranium is contained in the subbituminous coal and lignite deposits of the Dakotas and Wyoming (2,3,4). Most investigators concluded that an epigenetic emplacement of uranium in the coal by means of circulating groundwater and the more extensive concentrations of uranium in coal are apparently related to the permeability of the rocks enclosing the coal beds. Breger (5) and others have shown that uranium is readily adsorbed by coal and is held irreversibly as a disseminated adsorbed constituent. Briefly, lignite beds containing 0.1 to 10% uranium have been discovered in the Dakotas and Wyoming. The distribution of uranium was found to be erratic and was usually concentrated in thin layers, which were characteristically 10 to 14 in. thick and occasionally 30 to 36 in. thick. Lignite beds more than 3 ft. thick generally contain more uranium at the top of the bed than at the bottom. Special strip mining techniques are required to mine these thin

Jan 1, 1983

Jan 1, 1888

By C. E. Lundin

The Ce-H system was investigated in the temperature range, 573° to 1023°K, and the pressure range, 10-3 to 630 Torr, as a function of 'composition up to 72 at. pct H. Families of isothermal arid isopleth curves were plotted from the pressure-terr~perature-composition relationships. From these curves the solubility relationships were determined for the system. The isopleths are analytically represented by equilibrium dissociation pressure equations. The relative partial molal enthalpzes and entropies of solution of hydvogen in the systerrz were calculated fronz the dissociation pressure equulions and are tabulated. The integral free energies, enthalpies, and entropies of mixing in the Ce-H system were determined from the relative partial quantities and are also tabulated. The standard free energy, enthelpy, and entvopy of reaction of the dihydride phase at kcal per kcal per mole H2, and ?S° = -34. 1 cal per deg mole H2, respectively. The equilibrium dissociation pressure equation in the two-phase region is: UNTIL recently very little was known of the detailed solubility and thermodynamic relationships of the Ce-H system. Two previous investigations1,2 are noteworthy. However, significant discrepancies and omissions exist on analyzing them. The work of Mulford and Holley1 on cerium did not clearly delineate the boundaries of the two-phase region, Cess - CeH2-x. The plateau partial pressures were not thoroughly defined and were considerably displaced in pressure compared to those from the work of Warf and Korst.2 These latter authors concentrated their studies primarily from 823° to 1023°K in the pressure range of 1 to 760 Torr. No data were determined to outline the regions of primary solid solubility and the hydride phase. Also the establishment of the plateau partial pressures was rather limited in scope. In neither work was a treatment conducted of the relative partial molal enthalpies and entropies of solution of hydrogen in the single-phase regions and the integral thermodynamic quantities of mixing throughout the system. Therefore, it was the objective of this research to determine the complete equilibrium solubility relationships and thermodynamic data for the system by pressure-temperature-composition studies. EXPERIMENTAL PROCEDURE The cerium metal for this study was donated by the Reno Metallurgy Research Center of the Bureau of Mines. Total impurity content was 0.13 pct with only 60 ppm O. The metal was checked metallographically and contained only minor amounts of second phase compared to cerium from other sources. Specimen preparation was done in a dry box flushed with argon gas. The surface of a small rectangular piece of cerium (about 0.2 g) was filed with a clean, mill file. Final weighing was done in a tared enclosed vial containing argon gas. The specimen was then loaded quickly into the reaction chamber which was purged several times with high-purity hydrogen gas and then allowed to pump to about 10-6 Torr. The furnace was heated to the reaction temperature and the run started. The equipment used to conduct the hydriding was a Sievert's-type apparatus. Basically it consisted of a source for pure hydrogen, a precision gas-measuring burette, a heated reaction chamber, a McLeod gage, and a mercury manometer. Pure hydrogen was supplied by the thermal decomposition of uranium hydride. The 100-ml precision gas burette was graduated to 0.1-ml divisions and was used to measure the quantity of gas and admit it to the chamber. The reaction chamber was a quartz tube. Prior to each run, the cerium specimen was wrapped in a tungsten foil capsule to prevent reaction of the cerium with the quartz. Control of the temperature was achieved within ±1°K. Pressures in the manometer range were measured to ±0.5 Torr and in the McLeod range (10-3 to 5 Torr) to ±3 pct. The compositions of hydrogen in cerium were calculated in terms of hydrogen to cerium atomic ratio. These compositions were estimated to be ±0.01 H/Ce ratio. The technique used to study the equilibrium pressure-temperature-composition relationships of the Ce-H system was to develop experimentally a family of isothermal curves of composition vs pressure. The range of pressure through which each isotherm was developed was from 10-9 to about 630 Torr in the temperature interval, 573° to 1023°K. RESULTS AND DISCUSSION The hydriding characteristics of cerium are iso-morphous with those of the elements of the light-rare-earth group (lanthanum, cerium, praseodymium, and neodymium) wherein the region from the dihydride to trihydride is continuously single phase.' The structure of this phase is fcc.3 The heavy rare earths form a trihydride,2 which is hcp, separated by a two-phase region from the fcc dihydride phase. The Ce-H system is represented by the family of experimental isotherms in Fig. 1. Due to the small scale required to draw the curves, the experimental points are omitted; however, a total of 240 experimental data points were taken to prepare these curves. The solubility relationships can be deduced therefrom. Three distinct regions of partial pressure and composition can be seen. The region of cerium solid solution is represented by the rapidly rising isotherms in the dilute composition range. In accordance with Gibbs Phase Rule only one solid phase, the cerium solid so-

Jan 1, 1967

By R. J. Hafsten, E. S. Davenport, R. A. Grange

THE influence of austenite grain size upon the hardenability of steel is now fairly well understood; for a given austenite, increasing the grain size increases the depth of hardening, and, since the latter is related to the fundamental transformation behavior of austenite, it follows that austenite decomposition must, in general, be retarded by increasing grain size. To date, very little quantitative information bearing directly on the effect of austenite grain size upon the progress and result of isothermal transformation has been published. Davenport and Bain,1 and Zimmerman, Aborn and Bain2 have shown that the transformation is definitely retarded in hypereutectoid plain carbon steels at temperatures near and above the upper region of rapid transformation (Ar') when the austenite grains are increased in size. More recently, Griffiths, Pfeil and Allen3 investigated the effect of a series of different heating (austenitizing) temperatures upon the progress of isothermal transformation at 1245°F. (675°C.) and 745°F. (395°C.) in a medium carbon, low-alloy steel; while they reported no measurements of the austenite grain size, their results suggest that increase in grain size retards austenite transformation at 1245°F. (675°C.), but has no appreciable effect at 745°F (395°C.). The present paper deals with the results of a study of the isothermal transformation of austenite in a single commercial alloy steel in which a fine-grained or a coarse-grained state was induced by appropriate selection of austenitizing temperature. The data are presented in the form of isothermal transformation diagrams, which clearly show that coarsening the grains lessens the rate of transformation of austenite to proeutectoid ferrite and pearlite-that is, at temperature levels above about 1000°F. (540°C.)-but is without significant effect at lower temperatures where the transformation product is bainite or martensite. It is to be presumed that the foregoing statement would be valid, at least in principle, for many other grades of steel; it confirms again that the mechanism of transformation to a pearlitic structure is fundamentally different from that to an acicular structure. A number of related observations were made, which seem to throw some light on the transformation process as it takes place in alloy steels, particularly at temperature levels in the vicinity of 1000°F. (540°C.), where the transition from lamellar to acicular structures occurs. These data are discussed briefly in the belief that they may lead to a clearer understanding of this aspect of the subject. MATERIAL AND EXPERIMENTAL PROCEDURE The material investigated was a commercial grade of S.A.E. 4140 steel, the composition of which was as follows: 0.37 per cent C, 0.77 per cent Mn, 0.98 per cent Cr and 0.21 per cent M0. It was hot-rolled to a 1 1/8-in. round bar and normalized by air-cooling from 1800°F. (980°C.).

Jan 1, 1941

By Richard H. Hopkins, R. W. Kraft

A new technique facilitating the rapid determination of the three-dimensional morphology of phases suspended in an opaque matrix is described. The vapidity of the technique is based upon continuous cinephotomicrographic recording of specimen microstructure as the specimen surface is removed under controlled conditions in an electrolytic cell. The advantages of the technique for determining spatial morphologies in opaque materials are illustrated by application of this method to the study of the configuration of faults in a specimen of directionally solidified CuAl2-Al eutectic alloy. A spatial model of the eutectic fault network deduced in this manner has substantiated the facts that faults in this alloy tend to lie parallel to one another in a direction close to that of the specimen growth axis and that the majority of faults tend to bridge lamellae rather than run parallel to them as growth proceeds. For the specimen studied fault density decreased as growth proceeded. ALTHOUGH metallographic observation is a powerful tool for investigating the correlation between structure and properties in metallic alloys, ordinary metallographic methods suffer the fundamental limitation that any conclusions concerning the three-dimensional structure of these opaque materials must rely upon inference from two-dimensional microsections. For this reason it is frequently impossible to make valid judgments regarding the true spatial distribution of the micro-constituents in specimens under investigation. Several techniques have been devised to circumvent the basic limitation of planar microsec-tioning and employed with varying success. These include construction of three-dimensional models of alloy microstructure from sequences of photomicrographs,1-3 quantitative deduction of spatial features based upon statistical studies of data from random and/or selected plane microsections,4-6 and selective dissolution of one phase in a two-phase alloy to reveal the topography of the phase remaining.' However these techniques also have certain obvious disadvantages. Construction of three-dimensional models is a very time-con- suming procedure due to the tedious polish-etch-photograph cycle needed to obtain the necessary photomicrographs to portray the spatial microstructure. Statistical methods by their very nature give only average values of the quantities being studied and cannot therefore give a detailed physical picture of the microstructure to be observed. Finally, the technique of selective dissolution is only applicable in systems where the phases are of vastly different chemical reactivity; it is of little use in the study of single-phase alloys. Since the determination of the three-dimensional structure of opaque materials is hindered by two facts—the materials are opaque to radiation in the visible spectrum and construction of spatial models of microstructure is quite laborious—two solutions to the problem suggest themselves: 1) use radiation of energy great enough to render the alloy transparent, i.e., some microradio-graphic method, or, 2) devise a rapid means to section and record alloy microstructure. Stereomicroradiography has indeed been used to study internal arrangements of phases in several materials8,9 but the method, in general, is limited to very thin specimens (due to X-ray absorption) and simple microstructures. It would seem then that development of a rapid, simple, and generally applicable technique for studying the details of alloy microstructures in three dimensions can best be undertaken by following the second approach above. Using this idea a new technique for rapid evaluation of spatial microstructures was developed based upon cinephotomicrographic recording of the micro-structure of a specimen undergoing controlled electrolytic dissolution. It was further felt that application of this technique to the careful study of the spatial configuration of faults in a CuAl2-Al eutectic alloy would yield information that could be correlated with the extensive data3,6,10-12 already compiled concerning the solidification and crystallography of this eutectic. The practicality and usefulness of similar methods for studying three-dimensional features in alloys has recently been illustrated by the study of dislocation loops in zinc13 and spheroidized structure in steel.14

Jan 1, 1965

By K. Thirumalai

Although the term "spalling" has long been known, Norton l first referred to its usage for the fracture or disintegration of materials subjected to rapid temperature changes. Spalling of ceramic materials at high temperatures has received attention in the past.2-4 Removal of the char formed during ablation in reentry of space vehicles has been referred to as mechanical spalling.5 The first experiments to evaluate the process of rock fragmentation by thermal spalling were conducted by Stoces6 using a series of gasoline burners on the quartz veins of the Zinnwald deep mines in Germany. After the development of rocket-jet burners, the principles of thermal spalling combined with high fluid momentum found wide practical application in rocks. The well-known jet piercing process for drilling blastholes in taconite and for jet channeling in the quarrying of granite are among the more notable of these application.7 For the purposes of this study, thermal spalling or spallation of rocks is defined as progressive failure caused by thermal stresses induced by a sudden application of heat from a high temperature heat source. Gray observes that the size of the spall is dependent on the pattern of induced thermal stresses before failure. The spallability or the relative susceptibility of rocks to failure by thermal spalling is a complex but potentially useful parameter for qualitative comparisons. Fundamental differences exist in the degree of spallability among different types of rocks. Accurate prediction of spallability of any particular rock has so far not been possible. Measurement of the state of stress and temperature in the rock during the rapid thermal spalling process poses difficult problems that must be solved. Identifying the parameters that influence the thermal spalling proc-

Jan 1, 1970

By C. K. Ferguson, J. A. Klotz

This paper describes experimental investigations conducted at the California Research Corporation's model oil well. The first part describes filter loss from several drilling muds through bore hole walls during mud circulation and drill string rotation. The effect of mud properties and drill string rotation with mud circulation is described. Filtration from a bore hole full of drilling mud, not circulating, but under pressure for extended time periods, is also discussed. The second part describes filter loss to permeable formations from beneath a drilling bit where filter cuke has no opportunity to develop appreciable thickness. If potential flow theory is applied to predict filtrate invasion from this hole bottom, targe invasions arc calculated. But model well experimentation shows that filtrate invasion from the hole bottom is controlled by mud particles that penetrate the formation ahead of the bit. This experimentation provides data to estimate the effect of mud particle penetration on fluid loss to formation. The third part presents an estimate of mud filtration during drilling of a well. INTRODUCTION As oil wells are drilled by the rotary method, drilling mud circulates up the annulus between drill pine and well wall. Drillers adjust mud density so that the pressure at the bottom of the mud column is several hundred psi greater than the pressure of reservoir fluid. As a result of this pressure difference, the liquid part of the mud filters into the rock around the bore and mud solids deposit as a filter cake on the well wall. For many reasons the petrogleum industry, within the past 20 years, has spent much money and energy to determine the volume of mud filtrate that enters rock around the well bore and dedicated much research effort to reduce this volume. Among the reasons for attempts to determine the volume of mud filtrate and to reduce this volume are the following: 1. If filtrate damages the permeability of oil sand, the resultant damage to oil well productivity will depend on the distance that the filtrate invades the oil sand; reduction of filtrate volume may, therefore, increase well productivity. 2. Filtrate that penetrates shale sections may cause the shale to swell and to slough into the well bore. Uncontrolled sloughing may stick drill pipe. Reduction in filtrate volume may reduce drilling trouble. 3. Electric log resistivity curves are changed by invasion of a mud filtrate; the change depends on the depth to which filtrate invades. Knowledge of this depth is necessary before resistivity logs can be interpreted accurately. For these reasons, specifications the place an upper limit to drilling mud filter loss are now written into almost all drilling programs. These specifications are based on APT Recommended practice 29, Standard Field Procedure for Testing Drilling Fluids,' which describes a static filtration test operated at 100 psi filtration pressure and at ambient temperature. Although this test is adequate for mud control, it cannot be used to compare filtration properties of different muds. Schremp and Johnson' showed, for example, that mud with a low API filter loss does not necessarily have low filter loss at bottom hole temperature and pressure. Also, no information has been available about the effect of bottom hole mechanics (mild circulation, drill string rotation, and bit action) on mud filtration. This paper discusses filtration data measured in the California Research Corporation's model oil well, which models closely oil well bottom hole geometry and hydrodynamic conditions. The filtration processes that

Jan 1, 1955

By Lawson P. Entwistle

SUMMARY ONE of the important reserves of manganiferous iron ore is at Boston Hill, near Silver City, New Mexico. The area consists of a faulted block of gently dipping Lower Paleozoic shale, dolomite, limestone and sandstone, which have been intruded by a roughly circular mass of quartz-bearing monzonite porphyry and subordinate dikes. From a noselike protuberance of the intrusion radiate many premineral faults, which have localized much of the hypogene mineralization. Three important stages of hypogene mineralization can be recognized: (1) mesitite, a manganiferous iron magnesite, (2) quartz sulphides, and (3) barite-galena. The carbonate stage is widespread but stronger near the intrusion. The quartz may have been derived from hydrothermal alteration of the igneous rocks. Barite-galena is most important in the Chloride Flat mining district, about one mile north, where argentiferous galena provided silver for the supergene ore. The hypogene carbonate, lean in iron and manganese, has been oxidized and consequently enriched by meteoric waters containing an excess of oxygen and carbon dioxide to form ore bodies of intimately mixed hematite and pyrolusite. The ore bodies, at one place attaining a length of 1600 ft., a width of 300 ft., and a thickness of 25 ft., are largely confined to areas of brecciation and to spreads from faults in Silurian dolomite beneath soft Devonian shale.

Jan 1, 1944

By George S. Rice

STUDIES of ground movement and subsidence caused by mining necessarily chiefly deal with causes and effects of making extensive excavations underground with spans beyond the strength of the un- supported or temporarily timbered roof or hanging wall. Perhaps no other phase of engineering is so de- pendent for results upon the assemblage of what may be called "experience data." That this is the case is cot surprising when one considers the number of variables involved in any at- tempted mathematical formula to determine the angle of draw or the angle of permanent slope of the rocks in any particular case. It is not like dealing with construction materials in which, through testing of. small specimens, in conjunction with the tests of large built- up specimens, relative stresses and strains may be deter- mined and formulas closely approximated for still larger constructions.

Jan 1, 1931

By I. A. Lange, A. M. Richardson

Although methods for determining shaft lining thickness are well documented, little attention has been given to the design of station breakouts and other related shaft ground support structures. This paper discusses design of selected shaft structures for the Cathedral Bluffs project, a planned 54-kt/d (60,000-stpd) oil shale mine in western Colorado. Design philosophy and construction sequences used in the three completed 520-m (1700 ft) deep, 4.6-m (15 ft) to 10.4-m (34-ft) diameter shafts are described.

Jan 1, 1984

By JOHN D. SUMMER

THE Premium Price Plan for copper, lead, and represent, the approach of the Office of Price Administration to the urgent of wartime problem of securing increased output of nonferrous metals. Some of the problems encountered in too operation of the Plan and the considerations which led to it?s adopt it will here he reviewed. The Plan provides for extra payment by the Metals Reserve Co., to mine operators who exceed established quotas of production. Producers are thus directly, compensated for the higher costs of working ores that are not commercial at the ceiling price, although the metal obtained from these ores is directed into regular channels of distribution at the established prices for copper, lead, and zinc. Higher-cost metal is thus available to fabricators and to the government agencies at the regular ceiling price and the dual objective of increased production and table pries is achieved.

Jan 1, 1943

By E. A. Holbrook

IT may be taken for granted that a mine official knows his duties, as outlined by the bituminous mining laws of the State, he knows how coal should be mined and transported, and he has judgment on any possibly unsafe condition in his mine. Certainly, if he is weak on any of these points, there are definite ways in which he can acquire the needed knowledge. If with this knowledge the mine official has the necessary practical experience to bring self-confidence, he stands before the world as a man who knows his job. There is, however, another side to his work, one not found in hooks, a side even that may not be learned at the face even though one spends a lifetime there. The actual duties a mine official knows and performs are the tangible and definite things about his work. There are other things which may be termed intangible, because they are hard to pin down and see, and. which appear to be of equal importance in successfully handling a job and which in time determine the very success of the company itself.

Jan 1, 1930

By O. D. Gonzalez, R. A. Oriani

A thermo-osmosis technique has been used to measure the heat of transport, Q* , of hydrogen and of deuterium dissolved in a iron and in nickel, and of hydrogen in Feo.6Nio.4 in the tempevature range 400° to 600°C. For all these systems, Q* is negative and has a large temperature coefficient; an isotope effect can be established for the solutes only in nickel. The magnitude of Q* is considerably larger than the activation energy, E , for migration in the case of these isotopes in a iron, so that all variants of the Wirtz model must be rejected. The phenomenological definition of Q* is developed to show that Q* is related to the mechanisms by which the activation energy is dissipated back into the lattice, and that Q*/E is a function of the ratios of the mean free paths of electrons and of phonons to the distance of jump of the diffusing atom. A correlation is shown to exist between the sign of Q* in thermal diffusion and that of the effective charge in electro migration, and may be understood as due to the large ratio of the mean free path of electrons to that of phonons. THE study of nonisothermal diffusion in the solid state is of interest because certain aspects of the mechanism of diffusion are made manifest which remain concealed though still present in the isothermal case. The thermodynamics of irreversible processes characterizes nonisothermal diffusion, known as thermal diffusion or as the Ludwig-Soret effect, by a quantity, Q*, called the heat of transport, which essentially measures the sign and the magnitude of the steady-state concentration gradient produced by the imposed temperature gradient. The problem then is to understand the quantity Q* at the atomistic level. There does not exist a theory for the atomistic interpretation of the heat of transport. There are, however, two classes of simple models which seem to afford some physical insight into Q*. Wirtz's model1, z and its subsequent generalizations partition the activation energy, E, for the migration of the atom spatially about the region of the migrating atom, so that Q* is the difference between the portion of the activation energy centered about the original site of the jumping atom and that portion about the arrival site. Clearly, the magnitude of Q* cannot on this model be larger than the activation energy for migration. The model of Oriani3 also considers the spatial distribution of E not only before but also after the atomic jump, and Q* is related to the variation of the spatial distribution of E that is produced by the jump. The simplest kind of system with which to compare the consequences of these ideas is the interstitial solid solution, since one may easily choose a temperature at which only the interstitial component moves, the solvent lattice serving as a completely satisfactory frame of reference. Thus, one avoids complications arising when both species in a binary system move. In addition, one avoids the necessity of knowing the energy for the formation of a vacancy, something which is needed for the analysis of thermal-diffusion data on metals which diffuse by the vacancy-exchange mechanism. However, the number of well-measured interstitial systems is extremely small, and, in particular, there are almost no data in the published literature for the temperature dependence of the heat of transport. If one works with solutes which are gases in the pure state at ordinary temperatures, one may use the technique of thermo-osmosis4 which permits thermal diffusion to be measured over a small temperature difference so that the temperature dependence of Q* can be more easily determined. The choice of dissolved hydrogen in iron and nickel was based on these considerations as well as on the desire to look for an isotope effect associated with localized

Jan 1, 1965

By W. G. Oldham

By monitoring the capacitance of abrupt p-n junctions it is possible to follow the motion of substitu-tional impurities. A p-n junction is formed by growth of silicon from an Al-Si alloy on an n-type silicon sutstrate at a temperature in the range 650" to 750°C. The diodes are etched and sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed to various temperatltres for 10 mm and the capacitance remeasnred. For very heavily doped diodes (-1019 per cm3) observable capacitance changes occur at neutron fluences of >1015 per cm 3. The results may be interpreted in seceral ways, the simplest of which is to assume simple vacancy diffiision with small impurity -racancy interaction (at the diffiision, i.e. annealing temperature of 700°C). In this interpretation it is found that a typical vacancy makes about 1024 jumps and travels about 10-5 cm before disappearing. The required effective annihilation center density is about 1016per cm3 . Estimates of the vacancy-impurity interaction can be made and the above numbers correctecl, but for arty reasonable assumptions the number of vacancy sinks connot be much reduced. ThE complete annealing of radiation induced defects requires that the vacancies and interstitials either recombine, travel to the surface of the crystal, or travel to an annihilation center, e.g., a dislocation or a precipitate. If the interstitial is ignored except as a possible vacancy annihilation center at low temperatures,* the motion of vacancies may be followed by monitoring the corresponding motion of substitutional impurities. pfister2 has measured the enhanced diffusion of impurities in an asymmetric shallow diffused silicon structure by optically monitoring the junction movement. In these experiments we monitor instead the capacitance of a heavily-doped deep symmetric p-n junction. The sensitivity for this method is several orders of magnitude higher than in Pfister's technique, mainly for two reasons: 1) the junction capacitance of a heavily-doped junction is sensitive to impurity movements in the Angstrom range* com- and 2) the junction may be far from the surface which is a major annihilation center for vacancies. THE EXPERIMENT A p-n junction is formed by the epitaxial growth of silicon from an A1-Si alloy on a silicon substrate at a temperature in the range 650° to 750°C. The technique used is the transport of an aluminum melt through a temperature gradient.4 A 10-mil thick aluminum disc is sandwiched between two silicon wafers and the assembly raised to about 650° C with a temperature gradient normal to the sandwich. After about 8 hr the upper (hotter) wafer has been entirely transported and deposited epitaxially on the substrate wafer. The substrate and overgrowth resistivity are measured with a 4-point probe. The as-grown structure is lapped until the wafer is about 1/2 mm thick with the junction in the center. Contacts consisting of electroless nickel covered by electroplated rhodium are applied to both the p and n sides. The wafer is diced into square dice 1/2 to 1 mm on a side and the dice are etched sufficiently to remove approximately 1 mil of silicon. The following results are all for aluminum (p-side) and antimony (n-side) doped specimens with NA =3x 1018 per cm3, ND = 2-8 x 101A per cm3. The diodes are sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed and the capacitance remeasured. A special capacitance measurement method is used to insure a low sensitivity to shunt resistance. The diode is voltage driven and the current monitored by a phase lock amplifier. It is possible to adjust the detector phase to a point where shunt resistances as low as 100 O have no effect on the reading. The diodes in this study have a capacitance in the range 1000 to 5000 picofarads and a shunt resistance in the range 100 to l06 O depending on the stage of the anneal. THEORY The theoretical problem is twofold: 1) The computation of the amount of impurity diffusion and hence the impurity profile resulting from a given amount of vacancy motion, and 2) the computation of the capacitance from the impurity profile. A comparison of the theoretical and experimental capacitance (in particular the changes) yields the amount of vacancy motion. Vacancy Motion. A convenient parameter to measure the total amount of vacancy motion is Jv the total number of vacancy jumps per unit volume. Although this parameter varies with position in the crystal, owing to vacancy annihilation at the surfaces, it is approximately independent of position far from the surfaces, i.e. in the junction region. In terms of the number of vacancies per unit volume Nv and the vacancy diffusivity given by

Jan 1, 1970

By Ralph Hultgren

IN solid solutions atoms of differing sizes occupy the same crystalline lattice, requiring that some of them be compressed and others expanded. The energy involved has been called misfit strain energy and is an important concept of crystal chemistry. If the atomic sizes and elastic constants of interatomic bonds are known, the misfit energy may be calculated,' provided certain simplifying assumptions are allowable. Usually, isotropic crystals are assumed and interatomic distances are taken to be the statistical average determined from X-ray diffraction. Such calculations yield values of the misfit energy of the order of 1 or 2 kcal per atom in alloys such as Au-Cu at compositions of 50 atomic pct. However, evidence has accumulated in recent times that atoms change their sizes with composition of alloys, implying electronic rearrangement of the bonds. The size changes have been found particularly by application of the X-ray method developed by Warren, Averbach, and Roberts.' Thus, Averbach, Flinn, and Cohen3 determined radii in Au-Cu alloys. Oriani4 showed that these new radii led to a calculated misfit energy in disordered AuCu, which was decreased from the values calculated by the usual theory more than twenty-fold, to only 80 cal per g atom. Thermodynamic calculations from the phase diagram5 also show misfit energy to be no more than a few hundred calories per g atom in this alloy. The question of what electronic rearrangements are possible therefore becomes compelling in estimating misfit energy. In the following pages the results of certain calculations on the AuCu tetragonal superlattice are submitted. Conclusions drawn from these should be applicable in large degree to disordered solid solutions. As in all ordered states, bonding distances in the superlattice are individually known, rather than being merely average distances as found from lattice constants of disordered states. Moreover, only the Au-Au and Cu-Cu distances are strained; the elastic constants of these are known in the elementary state. In the usual calculation it is necessary to assume elastic constants for Au-Cu bonds. Misfit energy has thus been calculable without the need of many simplifying assumptions usually made. It is still assumed that equilibrium bond lengths and elastic properties of the bonds are the same in the alloy as in the pure metals. As previously discussed, this is probably not correct. Also assumed is that the bonds are not affected by strain of neighboring bonds. A calculation of Young's modulus from compressibility data shows this to be far from true; extensive electronic rearrangements take place. It would seem that misfit energy cannot be calculated from elasticity data for the elements. The usual methods may, however, give an upper limit which is often much higher than the true value. The question of electronic rearrangement is, of course, a complex one. Pauling's theory gives a simple, approximate treatment of the relation between type of bond and bond distance. This has been applied with some success to the Au-Cu system, as will be shown in a later section. Misfit Energy in Au-Cu Alloys Hume-Rothery and Raynor6 discuss the Au-CU system as a type example of strain energy. The gold atom is 12.8 pct larger in diameter than the copper atom, near the size factor limit beyond which solid solubility is severely restricted. They therefore consider the misfit energy to be large, a conclusion for which they believe they find evidence in the phase diagram. Gold and copper are completely miscible in the solid state, but the alloy has a minimum melting point at an intermediate composition. From this Hume-Rothery and Raynor conclude that the strain energy is nearly large enough to prevent miscibility; the phase diagram tends toward a eutec-tic type. In Ag-Cu, which has almost identical size relationships, solid miscibility is quite limited; whereas in Au-Ag, where atomic sizes are nearly the same, there is complete miscibility without a minimum in the melting point. From their arguments the heat of formation of Au-Cu would be expected to be endothermic or only slightly exothermic, that of Ag-Cu to be endothermic, and that of Au-Ag to be exothermic. Deviations, from Ve-gard's law of additivity of atomic radii support these conclusions, since Au-Cu and Ag-Cu both have pronounced positive deviations, and Au-Ag has a negative deviation. Nevertheless, Au-Cu alloys form exothermically; indeed, considerably more exothermically than Au-Ag, Table I. Hence, strain energy must be much less important in this case than Hume-Rothery and Raynor have supposed.

Jan 1, 1958

By S. Y. Ezz

The quality and extent of fluidization of fine iron ore beds with gases were investigated. Factors affecting the rate of reduction with H, and the sintering of the partially reduced material were studied. Trials to retard sintering by covering the particles' surface with nonsintering materials were successful. THE gaseous reduction of iron ores is a gas-solid reaction. Hence the fluidization technique seems ideally suited to it. However, a serious drawback

Jan 1, 1961