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By P. Nyul, S. Caplan, M. F. Lamorte, T. Gonda

Therrnal resistance is measured on GaAs laser diodes in the temperature range 77" to 300°K. These data show that typically the thermal resistance increases fifteen times from 77 to 300°K. The increase is attributed to the decrease in thermal conductivity of Gds. Nornzalized thermal-resistance experimental and calculated from published thermal-conductivity data) values are compared and good agreement shown. In many practical applications, it is desirable to obtain high average power output from laser diodes. Average power output is determined in large measure by the external efficiency and thermal resistance of the diode.'-3 The average input power with which a laser diode may be pumped is dependent on the thermal resistance. Thermal resistance has been studied over the temperature range from 77" to 300°K which is usually of interest in practical applications. This correspondence presents data on thermal resistance for GaAs laser diodes and compares them to values calculated from thermal-conductivity data. Junction heating arises from three distinct components: 1) joule heating, 2) nonradiative recombinations, and 3) reabsorption of radiation. In high-threshold lasers, joule heating predominates.4 Typically, the nonradiative recombination is not negligible and contributes significantly to junction heating. The loss caused by reabsorption may be of the order of the joule-heating loss.' The fabrication and the geometry of laser diodes have been described in other publications.5 The data presented were obtained from diodes which were fabricated from the same region of a wafer to minimize differences. Fig. 1 shows four types of heat sinks employed in this study. In types 1 and 2, the laser cavities are alloyed; pressure contacts are employed in types 3 and 4, and indium is plated on the inside faces to improve the intimacy of contact between the diode and the heat sink. The thermal resistance R is defined by the following relationship: where AT is the junction-temperature rise above the heat-sink temperature for the diode power dissipation Pd. For measurement of thermal resistance, a direct current is passed through the junction, in the range from 1 to 50 pct of threshold. The diode is placed in the laser mode by superimposing a current pulse of low-duty cycle on the direct current.3 Junction-temperature rise is obtained from the time-resolved laser spectrum at the leading edge of the current pulse.' Typically, the laser line shift is 2.5A per OK. The resolution employed in these experiments is 0.5A; therefore, the accuracy in the temperature measurement is 0.2K. Typically, the temperature rise is 2" to 20°K. The power dissipation is the difference between the dc power input, and the radiation power exiting the diode. The measurement accuracy is less than 1

Jan 1, 1968

By N. L. Britton

About two years ago Dr. Newberry referred to me for study a considerable collection of fossil plants sent him by Dr. Arthur F. Wendt, engineer of the silver mines " El Cerro Rico de Potosi" in Bolivia. As I had been interested in working up the extensive accumulations of existing plants made by Dr. H. H. Rusby in the Bolivian Andes further north, and in assisting Dr. Rusby in the study of those now being collected by Mr. Miguel Bang in other parts of that country, I was glad of an opportunity of ascertaining something of the Tertiary flora of the region. I was unable to take up the subject at that time, but have since been able to conclude the investigation, and the results are here presented. At a time when the mineral resources of the Southern States are attracting such widespread interest and attention, I have thought it appropriate to give a short general description of the iron-ore deposits of a territory concerning which little is as yet known and nothing published, so far as I am aware. The data used here are due to the preliminary examinations of the North Carolina Geological Survey, on which work I was engaged during the past summer, and my acknowledgments are due to Prof. J. A. Holmes, State Geologist, and Messrs. Harris, Ashe, and Lewis, of the survey, for their co-operation in the work; also to Messrs. A. S. McCreath and C. B. White for analyses which they Kindly furnished. Other analyses were made by Mr. Charles Baskerville, assistant chemist to the survey, and this may be understood where the name of the chemist is not mentioned. All samples for analysis were dried at 212' F. The accompanying map has been prepared from the revised sheets of the United States Geological Survey by Mr. H. L. Harris, and will be referred to throughout this paper. Ashe county lies in the extreme northwestern part of North Carolina, bordering on Tennessee and Virginia; it is drained principally by the north and south forks of New river and their tributaries, and is therefore on the eastern edge of the great Mississippi drainagebasin. The country is exceedingly rugged and mountainous, having an average elevation of about 2900 feet above sea-level. Jefferson, the county seat, near the center of the county, is 45 miles nearly due south from the Norfolk and Western R.R. at Marion, Va., and 30 miles northwest from the Richmond and Danville R.R. at Wilkesboro, N. C. Geologically the ore-deposits described in this paper are situated in the area of the crystalline rocks, consisting chiefly of gneiss, hornblende-schist, and micaceous schists.

Jan 1, 1893

Edward Dyer Peters, the only child of Henry Hunter Peters and Susan Barker Thaxter, was born in Dorchester, Mass., June 1, 1849. From his father he was a descendant of the Peters family of Ipswich and Andover, Mass., whose earliest ancestor settled in Essex County in 1659; while upon his mother's side he descended from several old Hingham families, as well as from the Quineys and from Governor Bradford. Between the ages of fourteen and sixteen he was a student at the Episcopal School for boys in Cheshire, Conn. Near the school was an old tin mine, and he used to spend his Saturday afternoons exploring it. When Edward was sixteen, his father sold his property in South-borough, and for the next three years lived in Europe. Sept. 26, 1865, Edward entered the Royal School of Mines at Freiberg, Saxony. In the summer of 1867 he joined his family on Lake Geneva, and spent a part of the season in that vicinity, going to Chamounix and taking other trips. Extract from a letter to his father: Elbingerode, Harz, Aug. 30, 1868: I left Freiberg with my friend Lilienthal, on Wednesday the 19th of August, reached Leipzig in the evening and spent the night in that city: the next morning we took the cars and in the afternoon reached Eisleben, in Prussia, which was to be our first stopping-place; there are immense copper-mines and smelting-works at this place, and the method of working the mines is very peculiar ... The next morning we got up at five and spent the whole day in the smelting-works where I obtained a number of drawings of the furnaces they use here and a good many valuable data. Saturday morning we got up at four o'clock, and descended a mine about three miles from the town; the Director of this mine was one of the most intelligent and agreeable men that I ever met; he accompanied us in the mine and explained everything that was new to us. The system of mining at Eisleben is peculiar to this town, and is not used at any other place in the world; the copper ore comes in narrow, flat veins eighteen inches high, at the utmost, consequently the men work lying flat on their left side and using the pick with both hands: the ore is carried out of the side passages into the main ones, in very low waggons about twelve inches high, and four by two feet; the boys who pull these waggons have a board buckled to their left thigh and their left arm; they pass their bare foot through a strap in the waggon and wriggle along on their side dragging the waggon after them, with their foot, almost as fast as a man can walk above ground. In the afternoon we walked over to Hittstadt, about twelve miles, and remained there Sunday and Monday. Monday night, at ten o'clock we went out to one of the smelting-works, to see the refining of the copper; this is only done at night, so we worked there from ten in the evening till eleven the next morning, and came home all blackened up and with blistered hands, for our skin was not quite so tough as that of the workmen: at noon the same day we took the stage to Ascherls-leben, and then the train to Stassfurt, where there are immense salt-mines, as well as factories for the manufacture of bromium, which latter process is, however, kept a profound secret, so we had very little hope of seeing anything but the salt mines; we were talking with our landlord about our disappointment, that evening, when he told us that the director of the Bromium works was sitting in the next room with no company but his glass of beer, so we went over to him, introduced ourselves as Americans, and actually succeeded in persuading him that it could do his business no earthly hurt if he showed us his works; at last he consented, after making us give our word of honor

Jan 1, 1919

By J. G. Thompson

Determinations of the hydrogen content of irons and steels invariably are subject to two serious difficulties: (I) the determination of amounts of 0.001 per cent or less of any constituent requires an analytical procedure of unusual precision and accuracy, and (2) the hydrogen content of many samples is dccidedly not stable; i.e., there is no assurance that the content at the time the analysis is made is the same as it was when the sample was taken or at some previous time in the history of the piece. In respect to both the precision and speed of the determination, the vacuum-extraction procedure for the determination of hydrogen possesses advantages over the vacuum-fusion procedure, which has been the recognized standard for the detcrmination of other gaseous elements in sted-— oxygen and nitrogen for example. The basic facts upon which the vacuum-extraction procedure is based—i.e., the evolution of gas from solid steel when it is heated in vacuum, and the fact that the evolved gas is rich in hydrogen—were observed by Graham1 many years ago. Subsequent investigations have shown that hydrogen exists in steel chiefly as interstitial solid solution (i.e., in atomic dispersion) and perhaps to some extent as hydridcs that are unstable and decompose to form atomic hydrogen. In either case practically all of the hydrogen in steel at elevated temperatures exists in the atomic condition and consequently is able to diffuse readily through the metal. In contrast to this, other gaseous elements, such as oxygen and nitrogen, normally are present in steel chiefly in the form of relatively stable compounds such as oxides or silicates and nitrates; i.e., the oxygen and nitrogen atoms are fixed in stable combinations and are not free to migrate. The only oxygen or nitrogen that can diffuse in steel is the small amount in solution (atomically dispersed) and the rate of diffusion of these atoms is much less than that of hydrogen because of their greater atomic volume and lower mobility. Consequently, it is possible to extract most or all of the hydrogen from solid steel in a reasonable time at moderately elevated temperatures, but the procedure is not applicable to the determination of oxygen or nitrogen. It is only within the last decade that these observations have been developed into an analytical procedure for the determination of hydrogen. Apparatus and Procedure The apparatus used at the National Bureau of Standards,6 for the determination of hydrogen by the vacuum-extraction procedure, is shown schematically in Fig. I. The specimen, freshly cleaned and dried,* is suspended on a fine wire within the quartz furnace tube that is connected to the reservoir system and analytical train.

Jan 1, 1945

By H. C. Fiedler

The development of cube-on-edge secondary re crystallization texture in Si-Fe strip depends upon the ability of inclusions, such as manganese sulfide, to restrain nomal grain gvowth. The ability of inclusions to perform this function is shown to depend upon their size and distribution. The desired uniform dispersion of many small inclusions is obtained by controlling the cooling rate from above the solution tempmature of the inclusions or, alternatively, by drastic 'quenching from above the solution temperature followed by heat treating at a lower temperature. The development of the cube-on-edge secondary recrystallization texture in Si-Fe strip depends upon both establishing the proper primary recrystallization texture and having inclusions to restrain normal grain growth. It has been suggested that the first requirement is met with a texture which, though weak, is near (110)[001]. A mechanism for secondary recrystallization originally proposed by ielsen' is consistent with the presence of this primary texture. It is visualized that a secondary grain appears where two adjacent grains happen to be sufficiently similar in orientation to be capable of behaving as a single large grain. This pair of grains will grow at the expense of its smaller neighbors as a consequence of its having lower grain boundary free energy. Other explanations of the origin of the secondary recrystallization texture have been offered,' and it can be concluded that the mechanism is not fully understood. Nevertheless, it is apparent that operationally the necessary primary recrystallization texture is obtained simply by interposing an anneal during the cold reduction to final gage. The role of inclusions in the development of the secondary recrystallization texture has been demonstrated by May and Turnbull4 in a comparison of a high-purity heat and a heat containing manganese sulfide. They showed that the driving force for secondary recrystallization is inversely proportional to the diameter of the matrix grains and that the function of the inclusions is to maintain a small matrix grain size. Other inclusions, such as various sul- fides,')' silicon nitride,8 and vanadium nitride,' titanium carbide,'' and vanadium carbide," have been shown to be effective in promoting secondary recrystallization to the cube-on-edge texture. There is also evidence that silica inclusions in Si-Fe strip made by powder-metallurgy techniques perform this function.' This report is concerned with the second of the two requirements for secondary recrystallization, namely the importance of the metallurgical control of the size and therefore number of inclusions. While the concepts involved are simple, they are fundamental to the making of this material. EXPERIMENTAL PROCEDURE A heat containing 3.27 pct Si, 0.026 pct S, 0.06 pct Mn, and 0.004 pct C was made in an air induction furnace from electrolytic iron, 98 pct ferro-silicon, electrolytic manganese, and iron sulfide. The heat was divided between graphite and baked-sand molds with a cavity 2-5/8 by 5 in. and with walls 2-3/4 in. thick. Slabs, 1 in. thick and 2-5/8 by 5 in., were cut from the ingots and hot-rolled either in the as-cast condition or after one of the heat treatments described later. After pickling, the 80- to 100-mil-thick hot-rolled band was, unless otherwise noted, heat-treated for 5 min at 900°C before being cold-rolled to 25 mils. After a heat treatment of 1 to 3 min at 860°C, the strip was cold-rolled to 12 mils, the final thickness. The percent cube-on-edge texture was determined by dividing the maximum torque as averaged from four samples by the maximum torque of a 3-1/4 pct Si-Fe single crystal having the (110) plane in the plane of the sample. The torque measurements were made in a field of 1000 oe on 1-in.-diam disks. RESULTS AND DISCUSSION The importance of the thermal history of the ingot is evident in Fig. 1 from the appearance of strips heat-treated in a temperature gradient. The sample

Jan 1, 1964

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent investigations1. a data on relative grain boundary energies in silicon iron have been obtained. The present investigation is a continuation of this work along similar lines for the purpose of obtaining additional information on boundary energies. One aim has been to extend the data for a (110) series, which was formerly studied,' to small differences in orientation, since a recent theory3,4 based on a dislocation model of grain boundaries predicts a E. ? (A-ln ? )* form of energy curve for small differences in orientation. Another aim has been to provide data for a (100) series—all grains having (100) planes parallel with the surface of sheet speci-mens—and to compare the results with the predicted form of energy curve. Finally, information on the nature of approach to equilibrium conditions was to be obtained through observations on the movements of grain boundaries. Recently published papers2,3,5 have treated the mathematical problem of expressing equilibrium conditions for grain boundaries for the general case when boundary energy depends upon boundary orientation. The equilibrium equations, which relate equilibrium angles and grain boundary -free energies, contain additional terms that express the variation of energy with boundary rotation. It has been necessary in the present investigation, however, to neglect these additional terms since no data for their evaluation were available. Dropping the additional terms leads to the following approximate equations which were used: E12/sin ?3 = E18/sin?2 =E28/sin?1 or those of the form: E28 + E13 cos ?3 + E12 cos ?2 = 0 Experimental Procedure Except for sample F1, all specimens were made from two lots of silicon iron called C and L respectively. The compositions of these are listed in table I. In the preparation of 12 three-grain specimens for the present investigation, a controlled grain growth technique, which has been described previously,' was used. After preparation, the specimens were notched at the boundaries to shorten them as a means of providing more rapid approach to equilibrium in the anneals. Initial grain boundary angles were determined from micrographs taken at X500. Seven anneals, totaling about two days at 1300°C and two to four days at 1400°C, were run in an atmosphere of pure dry argon as described in a previous paper.' Boundary changes generally could be followed without metallographic surface preparation, because thermal etching occurred during the anneals. These observations indicated angle changes of as much as 35" in some instances, with the major changes occurring during the first anneal. Annealing was discontinued when the angles reached stationary values. Fig. 1 gives a schematic diagram for purposes of defining crystallographic and boundary directions for three grains with common plane parallel with the sheet. Differences in orientations (expressed by A) are the angles between [00l] directions. They can be calculated with the aid of the ?'s. The grain boundary angles can be calculated from the w'S. Results Results are given in table 11. Types of crystal-lographic planes refer to those parallel with the sheet. Orientations are given in terms of [00l] direc-tions as shown in fig. 1. Except for grain 3 of specimen H6, which was unintentionally tilted 7" out of a (100) plane, all grains generally were within 1" or 2" of the plane specified. The directions of boundaries were measured generally to within 1" on both upper and lower surfaces, and the average direc- tions were determined for use in calculating the grain boundary angles. Variations in grain boundary directions refer to deviations from average directions. Boundaries near the junction point for all specimens generally were very close to perpendicu-

Jan 1, 1951

By D. H. Davis, I. Fatt

Oil bearing rocks, usually found at depths of 2,000 to 10,000 it, are elastically deformed by overburden pressure. Although the change in porosity with pressure in a number of example rock.: has been shown to be small, it was thought that overburden pressure might have a significant effect on permeability. This note presents results of an investigation to determine the magnitude of the change in permeabilty with pressure. In routine core analysis permeabilities are measured on rock samples which are not under overburden pressure. If permeablity measured in this way differs from permeabilities measured under overburden pressure, a systematic error is introduced into well productivity calculations. The experiments described in this report were made to determine the magnitude of the change and thus to give an estimate of the error introduced into the calculations. The error introduced by the neglect of the change in permeability when overburden pressure is removed may account for part of the difference between well productivity calculated from core analysis and the actual well productivity. The results obtained in this investigation have only quali-tative significance because of the difficulty in reproducing in the laboratory the stress conditions on the rock buried in the earth. The assumption which is usually made is that the rocks in the earth are under a uniform pressure equal to the weight per unit area of the vertical overburden column from the rock in question to the surface of the earth less the pressure of the liquid in the pores of the rock. For an overburden consisting of sandstones and shales (of assumed average specific gravity of 2.3) and for a liquid pressure equal to the pressure in a salt water column (of specific gravity 1.0) reaching from the rock to the surface, the resulting net pressure on the rock is approximately 0.56 psi per ft of depth. EXPERIMENTAL METHOD Clean, dry sandstone core plugs one in. in diameter and about three in. long were mounted in a copper foil jacket as shown in Fig. 3 or molded in a Lucite jacket as shown in Fig. 4. All cores except those labeled "2" in Fig. 1 and "8" in Fig. 2 were measured in the copper foil jacket. Cores "2" and "8" were measured in the Lucite jacket. The jacketed core was placed in a high pressure hydraulic bomb in which the liquid pressure outside the jacket could be raised to 15,000 psi. Flow lines from the core were brought out of the bomb through special fittings in the bomh head and connected to a laboratory type gas permeameter. Measurements were made with nitrogen gas; the maximum mean gas pressure in the core was 16.1 psia. RESULTS The specific permeability of sandstone decreases with in. crease in overburden pressure. Most of the decrease takes place over the range of zero to 3,000 psi overburden pressure. If the net pressure on the rock is assumed to be 0.56 psi per ft of depth as discussed above, 3,000 psi of overburden pressure is equivalent to about 5,000 ft of overburden. At 3,000 psi overburden pressure, the permeability of the eight sandstone core samples tested ranged from 59 to 89 per cent of the permeability without overburden pressure. Figs. 1 and 2 show the permeability reduction as a function of overburden pressure. The permeability of the eight cores without overburden pressure ranged from 4.35 md to 632 md; these permeabilities are listed in Figs. 1 and 2. REFERENCES 1. Carpenter and Spencer: "Measurements of Compressibility of Consolidated Oil Bearing Sands," U. S. Bureau of Mines, R.I. 3450, (1940). * * *

Jan 1, 1952

By Peter Hood

Data on worldwide geophysical activity in mining exploration programs is collected annually by the Geophysical Activity Committee of the Society of Exploration Geophysicists as part of a continuing service to the industry. The data is obtained by sending out questionnaires to all organizations (which are) known to be carrying out mining geophysical work; the organizations canvassed include mining companies, contractors, government departments and universities. The questionnaire is divided into three sections, namely ground methods, airborne methods and research. In 1968, 515 questionnaires were circulated throughout the non-Communist world and 283 replies were received which is a 55% return. A 67% return was received from the U. S. organizations surveyed so the statistics quoted in this report for the United States are reasonably reliable. This report is published in condensed form, but with emphasis on the United States statistics, with the permission of the Society of Exploration Geophysicists. It was presented at the 39th Annual International Meeting of the SEG in Calgary, Alberta, on September 15, 1969. Worldwide utilization of mining geophysical methods reached a new high in 1968 with total expenditures of United States $41.4 million, compared lo $32.3 million in 1967, representing a 28%, increase. The expenditure distribution by area and type of activity is shown in the graph on page 64. In terms of money spent, ground geophysical surveys accounted for 49% of the total, airborne survey's 36% and research 15%. The percentage of the money spent on ground geophysical surveys fell by approximately 7% from 1967, that for airborne surveys, increased by 5%, and for research the amount increased by 2%. Industry accounted for 79°1% of the total monies spent on mining geophysical activity in the world in 1968 and governments and universities 21 o%.

Jan 1, 1970

By R. Kossowsky

USING etch-pit techniques, Johnston and Gilman' have shown that the stress dependence of dislocation velocity can be represented by the expression where r, is the dislocation velocity, a is the applied stress, and oa, is the stress to produce a unit velocity. Noble and Hul12 showed that the exponent m is strain-dependent and increases rapidly in the work-hardening region. This was explained by arguing that in the work-hardened material the applied stress required for any given velocity will be greater than in the annealed material by an amount equal to a back stress due to work hardening. schadler3 has stressed the importance of substructure as a possible source of error in dislocation velocity measurements, and took care to make velocity measurements in which dislocations moved such short distances that interactions with boundaries were avoided. schadler3 also pointed out that, if standard testing equipment is used, measurements of m from flow stress data could be seriously in error in materials with a high initial work-hardening rate. Noble and Hu112 have further argued that, due to the strain dependence of m , the extrapolation to zero strain4 to obtain the true value of m can be justified only in the preyield region. Microstrain experiments in high-purity iron5,6 have led to the conclusion that aiA (Ref. 5) (defined as the stress to first produce a permanent set of 10-6 in. per in.) and oflow are not controlled by the same deformation mechanism. It has been proposed5,6 that aA is governed by the lattice resistance to the motion of screw dislocations in a given slip plane and that oflow is controlled by the lattice resistance to a full-scale cross slip. The purpose of this note is to extend Noble and Hull's argument further and to show that measurements of m from flow stress data can be in error due to the rapid increase in stress in the microstrain region6 when stress is increased beyond aA. Double z-one-refined single crystals of molybdenum (with the (101)[ 111] slip system operating and a Schmidt factor of 0.475) were used in an experimen-

Jan 1, 1968

By C. W. Parmalee

The ideal fuel for burning ceramic wares is the one that, among other characteristics, has little or no sulfur. For that reason wood was long considered the most desirable fuel but its high cost has practically eliminated its use except in regions where it is very abundant or other circumstances warrant its choice. The fuels commonly employed are natural and producer gas, oil, and coal. The last named is undoubtedly the most important, not only in this country but abroad. Occasionally anthracite is used but the larger part is bituminous. The quality of the coal used depends on the kind and the value of the products being manufactured. For some materials, such as common brick, hollow block, etc., the quality of the coal is of less importance than in the manufacture of polychrome terra cotta, pottery, porcelain, etc. It is obvious that in burning clays that contain notable amounts of pyrite, marcasite or gypsum, as is the case with many common clays, the sulfur content of the fuel is of much less importance. The permissible amount of sulfur in the coal used will depend on the kind of product being manufactured. "A good sample1 of coal commonly used in pottery ovens has something like this quantity of sulfur: total sulfur, 1.20 per cent.; sulfur in ash, 0.11 per cent.; volatile sulfur, 1.09 per cent." This is based on English pottery practice. Correspondence with a. number of leading manufacturers in this country has produced the following figures: Sanitary Ware.—(a) 1.0 per cent, maximum, (b) 0.5 per cent. Sewer Pipe.—(a) 1.2 per cent., (b) 1.1 per cent, present run, 3.0 per cent, has been used. Terra Cotta.—(a) 0.5 per cent, basis of contract, 1.0 per cent, approximate. Pottery.—1.0 per cent, contract, 1.5 per cent, probable content. Enameled Brick.—1.3 per cent, maximum, (a) and (6) designate different firms giving figures. Since a pottery kiln for sanitary ware will require about 14 tons of coal for a bum, the quantity of SO2 that will be generated from a 1-per

Jan 1, 1920

By Chester A. Fulton

APATITE, the most abundant crystalline phosphate mineral, is found in igneous rocks and probably is the primary origin of all other phosphates, whether mineral or organic. Its chemical formula may be expressed as Ca5(Cl,F) (PO4) 3. The chlorine may be replaced almost entirely by the fluorine. It is found in large or small hexagonal prisms, usually of a vitreous luster and a green or red color, but also violet, white, or yellow. It is found largely as an accessory mineral in granitoid rocks. Its hardness is 4.5 to 5 and its specific gravity is about 3.2. There are many other phosphate minerals-for instance, amblygonite, autonite, collophane, lazulite, monazite, pyromorphite, torbenite, triphylite, turquoise, vivanite, wavellite-with base elements of calcium, magnesium, iron, aluminum, manganese, lead, cerium, lanthanum, lithium, or several of these in combination and with various amounts of water of crystallization. However, these phosphate minerals have but little value save as specimens for mineral collections, the exception perhaps being turquoise. While large deposits of igneous apatite are mined today for the production of fertilizers and chemicals, more than 90 pct of the world phosphate production is derived from secondary apatites, called phosphorites. These calcium (and magnesium, aluminum, and iron) phosphates have been formed in the alteration of sediments by solutions containing phosphoric acid. Such solutions have come from the weathering or leaching of igneous rocks containing apatite, bone deposits of prehistoric animals and marine life, or guano deposits (excreta of birds). These phosphorites are mostly alterations of phosphatic limestones that took place slowly over many years. Whether it is apatite or phosphorite that is being produced, it is known in the trade as "phosphate rock." The sedimentary phosphate deposits are of marine origin. Some, as laid down, were rich in phosphate or have become so by subsequent subaqueous action and have not been further enriched since emergence from the sea. Some were originally phosphatic limestones or marls from which calcium carbonate was dissolved away by waters containing carbon dioxide, in which calcium carbonate is much more soluble than

Jan 1, 1949

By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By William L. Fink, Dana W. Smith

In parts I1 and II2 of this series, there were presented results of investigations on the age-hardening of an aluminum-copper and an aluminum-magnesium alloy. It was shown that the simple precipitation theory of hardening3 adequately explained the aging phenomena, including certain so-called "anomalous" behaviors which had caused other investigators to reject or modify the precipitation theory. However, these papers did not discuss the double aging peaks, which have been stressed in recent articles by Dr. M. Cohen4 and Dr. M. L. V. Gayler.6 The present paper is devoted to an explanation of this "anomaly." Fig. 1 is a generalized schematic representation of aging curves at different temperatures. Curve A corresponds to the aging at the lowest temperature, and D at the highest temperature. Certain previous investigators have explained curve A and the initial peaks

Jan 1, 1938

By William L. Fink, Dana W. Smith

In parts I1 and II2 of this series, there were presented results of investigations on the age-hardening of an aluminum-copper and an aluminum-magnesium alloy. It was shown that the simple precipitation theory of hardening3 adequately explained the aging phenomena, including certain so-called "anomalous" behaviors which had caused other investigators to reject or modify the precipitation theory. However, these papers did not discuss the double aging peaks, which have been stressed in recent articles by Dr. M. Cohen4 and Dr. M. L. V. Gayler.6 The present paper is devoted to an explanation of this "anomaly." Fig. 1 is a generalized schematic representation of aging curves at different temperatures. Curve A corresponds to the aging at the lowest temperature, and D at the highest temperature. Certain previous investigators have explained curve A and the initial peaks

Jan 1, 1938

By J. B. Austin, R. H. H. Pierce

IN developing a consistent picture of the thermal expansion of the commercial chromium steels, which cover a range of, carbon contents, it is desirable to know the expansion in the limiting case of the binary, carbon-free, iron-chromium alloys. We have, therefore, determined the thermal expansion of a series of five special alloys, ranging in chromium content from 3 to 10.5 per cent, with not more than 0.03 per cent carbon, over a temperature range extending beyond the transformation region; this low carbon content enables us to draw reasonably reliable conclusions as to the behavior of the carbon-free system. Moreover, the measurements serve to determine the beginning and the end of the alpha-gamma transformation; and they emphasize once more the fact that a transformation temperature determined by any method in which the specimen is .cooled at an appreciable rate is apt to be seriously in error, particularly if the metal contains a transformation-retarding element such as chromium or managanese. The lag, or undercooling, observed at the ?-a transformation is explained in terms of the influence of temperature on transformation velocity; the rather unusual shape of the ? loop is attributed to a change with temperature and with composition of the distribution of chromium between the alpha-iron and gamma-iron solid solutions. The exact composition of the alloys which were obtained through the courtesy of Dr. W. Rohn, of the Heraeus Vakuumschmelze A-G., is given in Table 1. Determinations of the linear thermal expansion and of transformation temperature were carried out in the vacuum dilatometer previously described,1 using a rate of heating and of cooling of 3.0° to 3.5° per minute unless otherwise stated. Magnetic susceptibility, which was measured in studying the rate of transformation, was determined with a magnetic balance, which also has. been described.2

Jan 1, 1935

By A. G. Metcalfe, Koeneman

A study of the structure of chemically deposited nickel by Goldenstein, Rostoker, Scpssberger, and Gutzeit has been reported recently. In this work it was shown that the nickel deposit produced by the catalytic nickel-reduction process was an amorphous solid. Crystallization occurred at elevated temperatures when the original powder pattern which showed only a diffuse ring with a d-spacing of 2.01A became sharp, revealing nickel and nickel-phosphide lines. The phosphide was indexed provision%lly on a tetragonal lattice of parameters a = 9.01A and c = 4.42A, which is in reasonable agreement with the structure of Ni3P proposed by No-wotny and Henglein.3 The transformation from the amorphous to the solid state occurs abruptly (e.g., after 7 min holding at 400°C) with the evolution of considerably more than 1000 cal per gm-mole. A more detailed analysis of these effects requires a knowledge of the solubility of phosphorus in nickel. Konstanti-now3 mapped out the phase diagram in 1908 but did not determine the solid solubility. The eutectic was placed at 11 pct P and 880°C. The purity of typical catalytic nickel deposits is very high.' Spectrographic analysis for heavier elements showed only trace amounts of aluminum, calcium, iron, magnesium, lead, and silicon. The term "strace" is a qualitative definition for less than 0.1 pct and probably less than 0.01 pct. Analysis for the interstitial elements yielded 0.04 pct C, 0.0023 pct 0, 0.0005 pct N, and 0.0016 pct H. Some of this material with 7.5 pct P was used in the present work. EXPERIMENTAL METHODS Alloys were prepared from carbonyl-nickel shot and a master composition containing 7.5 pct P. Cold-crucible, nonconsumable-arc melting was used.

Jan 1, 1959

By B. H. Bergstrom, A. P. Cohen, D. W. Fuerstenau

B.H. Bergstrorn (Research Div., Allis-Chalmers Mfg. Co., Milwaukee, Wis.) — Fuerstenau and Cohen have concluded from our study of single particle crushing, which had suggested that the size moduli of the crushed specimens were determined by the specific energy expended independent of feed size, that the same independence with respect to feed size exists for the specific energy-product size relationship for rod mills. They present data supporting this conclusion. Our single particle crushing experiments were on single spheres of soda-lime (type of glass was not given in our study) glass for which the feed size can truly be neglected. However, the feed size cannot be neglected in any case where the effective size modulus of the feed is not too much coarser than the size modulus of the product. This can be illustrated in the second experi- ment of Fuerstenau and Cohen where the feed is considered to be the original -6 +%mesh material. However, one can also consider the product from the 7.5-min grind to be the feed for the 10, 15, 20, 25-min grinds, and the 10-min product to be the feed for the 15, 20, 25-min grinds, etc. If the specific energy-product size moduli curves are drawn for these other feeds, as shown on Fig. 3, the new curves (and some curvature is apparent) are much steeper than the -6 +%mesh feed line. The slopes of these new curves are about -1.5, —1.8 and -3.0. This observation is in accord with the observation by Bond, who states that the net specific energy input to a grinding mill is equal to the specific energy represented by the product less the specific energy represented by the feed. Bond presents, on a diagram similar to Fig. 3, a series of curves which illustrate the effect of

Jan 1, 1963

By R. C. Gifkins, A. Gittins

A. Gittins and R. C. Gifkins (University of Mel-houvne)— Evidence from somewhat similar experiments to those described in this paper has led us to the conclusion that possibility 2) of the four listed on p. 319 is a description of what happens in grain boundary sliding. That is, sliding is limited by accommodation deformation, it being necessary to the Continuance of sliding that this accommodation should take place. An example of such accommodation, though probably not the most important, is fold formation at triple points. The evidence and arguments for this point of view are set out in Refs. 14 to 16. In particular, an experiment with a lead bicrys-tall5 seems to support point 2) rather than 3). In creep of this specimen it was found that at least 90 pct of the extension of a zone 0.3 mm wide at the boundary was supplied by sliding at the boundary. The sliding was localized in a region at the boundary very much smaller than 0.3 mm, in fact, in a region too narrow to resolve optically. In poly crystalline Specimens&apos; there appears to be a surface effect, as found by Rachinger," but it appears that this may not manifest itself at low strains. "Low strains" means <10 pct for a Pb-TI alloy, <2.5 pct for magnesium or "Magnox" A12 alloy, or <40 pct for a 0 brass. Up to this extension the sliding, measured by the mean vertical step at boundaries, is proportional to extension. We are able to say this with some confidence, since the error bars on our points are statistically derived. Our results would lead us to think that the error bars on other work, including that of Mullendore and Grant, are much too large at low strains to show this

Jan 1, 1963

By J. R. Jargon, H. K. van Poollen

Non-Newtonian fluids may be injected into a reservoir during secondary recovery operations. The non-Newtonian fluid used in this work is a power-law type of fluid that is, the viscosity of the fluid decreases as the flow rate or rate of shear increases. This paper presents equations for steady-state linear and radial flow of such fluids, transient behavior results from a finite difference model of a radial system, and transient behavior results from a field test. The equations that describe the flow of a non-Newtonian fluid are non-linear and are solved numerically. Finite difference solutions are presented as curves of dimensionless pressure drop at the wellbore us dimensionless time for a constant injection rate. Solutions were obtained for 5-percent, 10-percent and 100-percent PV of a non-Newtonian fluid for injection rates of 1, 10, 100 and 1000 cc/sec and for a 5 percent PV of non-Newtonian fluid located at T = Tw&apos; 3, 10, 20, 50 and 100 ft for a flow rate of 1 cc/sec. The buildup curves do not exhibit a stmight-line portion as is the case for Newtonian flow through porous media. Correlations also are shown for the productivity index vs rate for the computer model study and the field tests. INTRODUCTION During various secondary recovery operations non-Newtonian fluids are injected. Such fluids, in general, include thickened water and gelled fluids. The term "non-Newtonian" implies that the viscosity is not only dependent upon temperature and pressure, but also on the rate of shear that is applied to the fluid. For example, water, which is a Newtonian fluid, will have essentially the same viscosity no matter what rate of shear is applied. A pseudo-plastic fluid exhibits a decreasing viscosity when higher rates of shear are applied; a dilated fluid has an increasing viscosity with increasing rates of shear. The objective of studies performed and described in this report is to obtain relationships and mathematical and empirical descriptions of the flow of non-Newtonian fluids through porous media. Simple mathematical relationships, computer studies that include the unsteady-state behavior of such fluids, and field tests are used. PREVIOUS LABORATORY STUDIES Laboratory studies have been performed by several investigators. The fluids used in one investigationl were surfactant-stabilized dispersions of water in hydrocarbons. Its Fig. 6 is reproduced as our Fig. 1. This effective-viscosity vs frontal-velocity diagram shows that this fluid is of the power-law type over a fairly large range of frontal velocities. Gogartyl developed an equation for the effective viscosity as a function of shear rate that reduces to Eq. 2 for frontal velocities greater than about 2 ft/D. The fluid characteristics used in the present study are similar to those reported by Gogarty. Christopher and Middleman2 performed experiments with power-law fluids flowing through pipes packed with glass beads. They used a modified Blake-Koteny

Jan 1, 1970

By T. F. Witherbee

THE Fletcherville Furnace was built in 1864 and 1865, making its first blast from August until October of the latter year, when it was blown out to prevent its "bunging-up." Repairs were made in time to enable it to be blown in again December 12th, 1865, the blast ending October 7th, 1866. Total product 1921.15 tons iron, an average of 6.8.2.5 tons per day, from ores yielding 44.8 per cent. Consumption of charcoal 223.2 bushels per ton of iron. The furnace journal up to this time shows no record of furnace dimen¬sions, or temperature of the blast, but as near as can be ascertained, they were as follows, viz. Height of stack, 42 feet. Diameter of bosh, 11 feet. Angle of bosh, 7 1/2 inches to 12 inches rise, about 58°. Diameter of open tunnel head, 42 inches. Number of tuyeres 3; each 3 inches in diameter. Dam 15 inches high. Tuyeres 24 inches high. Tymp 22 1/2 inches high. Diameter of steam cylinder, 20 1/4 inches. Stroke 5 feet. Diameter of blast cylinder, 64 inches. The engine is direct-acting horizontal non-condensing. December 26th, 1.866, the furnace was again put in blast, having been considerably altered in the crucible; the height of stack, bosh, and tunnel head remaining as before. Six tuyeres were put in, three in each of the side arches. The hearth or crucible was rectangular in form, 3 feet wide x 32 feet long x 62 feet high. Inclination of bosh 58°. Height of tuyeres 26 inches ; nozzles 2 1/4 inches diameter. Temperature of blast estimated to be about 500°.

Jan 1, 1874