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By R. M. Goldhoff, H. J. Beattie

The high-temperature properties of a 1 Cr-Mo-V forging steel are described. A series of controlled heat treatments was designed to delineate the effects of austenitizing and tempering treatments, temile strength, and grain size on such properties. Studies indicate that the mechanical properties and their varlations under creep can be described by the initial metallurgical structures and their changes droPirzg exposure, particulavly the carbide reactions. Such structures are described and correlated with the mechanical properties. FOR many years the large steam turbine industry has relied on the 1 Cr-Mo-V type forging steel for critical applications. Because of its adequate heat resistance and relative economy, it is currently in use in the temperature range up to about 1050" to 1075°F. Attempts to understand the large property variations attainable in this steel involve the structural modifications due to the wide latitude in its heat treatment. The heat treatment essentially involves a two-step process which includes solution-ing of carbides in the austenite range followed by a suitable tempering treatment below the critical to adjust the level of properties. The latter step is referred to as "secondary hardening" and is basically an ordinary aging reaction involving carbides. In the commercial heat treatment of large components of such steel, homogenizing and stress-relief anneals may be included and have some importance in determining subsequent properties. Several studies of the engineering properties of this steel as a function of transformation micro-structure have been reported.1 3 However, in this steel the carbide reactions, which are a function of composition and heat treatment, appear to be the property-controlling factor rather than the micro-structure defined as a transformation product. Thus, the tempering resistance of this type of alloy steel is mainly a function of the size and distribution of alloy carbides.4 However, it is also necessary to consider the stability of the microstructure and the effect of dynamic carbide reactions on subsequent properties. It is the purpose of this paper to show the interdependence of properties and corresponding structures, particularly carbide reactions, developed for a limited set of controlled heat-treatment conditions applied to 1 Cr-Mo-V steel. MATERIALS AND PROCEDURE The material for this work came from a large production forging whose chemical composition is shown in Table I. The property data accumulated on this steel as a function of heat treatment were room-temperature tensile and smooth- and notch-bar creep rupture at 1050°F (notch geometry: shank diameter = 0.357 in., depth = 50 pct, radius = 0.005 in.). To achieve controlled structural variations the temperature and time of both austenitizing and tempering were varied in a manner to produce a series of eight steels each at one of two grain sizes and one of two hardness levels in proper combination for valid comparisons. This will be clear upon examination of Table I. Structural studies involved the use of optical and electron microscopy as well as X-ray and selected-area electron diffraction. To reveal the nature of carbide precipitations, electrolytic extraction techniques were used with subsequent analysis of the residue by X-ray diffraction. Weight losses of the steel specimens during electrolysis were measured and successive chemical fractionations of the residues were applied and checked by X-ray examination. The details of fine structural distributions, morphologies, and crystallography of the precipitates as well as dislocation distributions were investigated by examining in the electron microscope three common types of preparation. a) Relief Replicas. Mechanically polished sections were etched in 2 pct nital, replicated with a nitrocellulose film, which was shadowed by chromium vapor deposited at a glancing angle of 20 deg. b) Extraction Replicas. A thin film of carbon was vapor-deposited on the polished and etched surface. The carbon films were then etched off and gathered on electron-microscope supporting grids. The carbides left imbedded in the carbon replica in their original distribution were then examined crystallo-graphically by selected-area electron diffraction. c) Thin Films. Specimens were mechanically ground and polished down to a thickness of 0.001 to 0.003 in. Final thinning was done electrolytically in a "chrome-acetic" electrolyte. When holes began to appear in the foil, the voltage was interrupted and applied in several 1-sec bursts. Sections of the foil between holes were thin enough to pass a 100-kv electron beam that carries an image.

Jan 1, 1965

By K. G. Davis, P. Fryzuk

WEINBERG,' in an investigation of solute distributions along unidirectionally solidified rods of dilute silver in tin alloys, concluded that, for rods of 2 mm diameter or larger, a very high degree of convective mixing takes place in the melt ahead of the advancing interface. Suggested causes for this mixing were (1) thermal convection, (2) convective currents set up by changes in fluid density associated with concentration gradients, and (3) currents set up by changes in volume during freezing. Evidence was presented that causes (2) and (3) were not primarily responsible for solute mixing. Further, convective mixing took place in horizontal rods with temperature gradients as low as 6°C per cm, putting doubt on the importance of thermal convection. In the present work, convective mixing is examined in melts with known initial solute distributions. The absence of a moving solid-liquid interface eliminates convection caused by volume changes on solidification. In the first experiment, three silica tubes 2 mm in diameter and approximately 20 cm long were filled with an alloy of 100 ppm Ag in tin (99.999 pct purity), placed adjacent to one another in a horizontal furnace, and solidified from one end at 1 cm per hr. A110, a Y emitter, was used as tracer. A few centimeters at the start of the rod were left un-melted, to determine the initial concentration Go. After solidification was complete, one sample was removed. The hot furnace was then brought back to

Jan 1, 1965

By Klaus Detert, Joseph Ziebs

The progress of primary recrystallization has been studied in alloys of nickel with 0.01, 0.1, and 1.0 at. pct Ta. It can be shown that in one particular alloy containing 0.1 Ta and 0.02 02 a large grain structure (0.5 mm diameter) could he developed by primary recrystallization in thin sheetswhich were cold-worked to 97.5 pct reduction in thickness. Electron transmission microscopy demmstrates that this phenonmena was linked to the occurrence of fine precipitates at subboundaries. A discussion of how fine precipitates can exert under certain circumstances a rather distinct retarding effect on nucleation rate is included. IN a former investigation, the recrystallization and texture formation in a series of binary nickel alloys including pure nickel were studied.' Nickel alloys with some tantalum added displayed peculiarities during primary recrystallization which have been studied in more detail by the present investigation. The alloys were prepared by powder-metallurgy techniques similar to the previous investigations.' Pure metal powders were thoroughly mixed to obtain alloys with 0.01, 0.1, and 1.0 at. pct Ta, referred to as alloy A, B, or C, respectively. The metallic impurities were kept below 0.005 at. pct except iron and cobalt with slightly higher values, by using highly purified nickel and tantalum powders.' The mixtures were pressed into bars and sintered at a temperature of 1300°C. The sintering atmosphere was either high vacuum, dry hydrogen, or wet hydrogen. The sintered rectangular bars were rolled 60 pct to a thickness of 3 mm, then annealed under dry hydrogen at 1000°C and again cold-rolled to about 97.5 pct reduction of thickness. After this heavy deformation, the sheet thickness was 0.07 5 mm. In order to study primary recrystallization which occurred in measurable times between 400" and 600°C, samples of the rolled sheets were annealed in a salt bath at various temperatures for various times in order to study the progress of recrystallization by hardness measurements and microscopic examination. For optical observation, the samples were polished and etched in a solution of 65 cu cm HNO3, and 18 cu cm acetic acid in 20 to 100 cu cm H2O, depending of the particular sample and annealing treatment. For transmission electron microscopic observations, thin foils were prepared by the combined window and Bollmann techniques.273 The electrolyte consisted of 23 pct perchloric acid and 77 pct acetic acid held at 15°C. Polishing was performed at a current density of 0.4 amp per sq cm. The examination of the thin films was accomplished by a Siemens Elmiscope-type electron microscope operating with an accelerating voltage of 100 kv. RESULTS The progress of primary recrystallization was very accurately followed in these alloys in order to establish the time when recrystallization started and ended during an isothermal anneal. Table I gives some of the data obtained by these studies. The time for beginning is a mean value, where somewhat less than 5 pct of the matrix has recrys-tallized. The end of recrystallization is the time when at least 95 pct of the matrix has recrystal-lized. Listed are three different B alloys, with 0.1 Ta distinguished by different sintering atmospheres which influence the rate of primary recrystallization. By the above method, the state of the grain structure when primary recrystallization was completed, but grain coarsening had not started, could be clearly defined. The average grain diameter of the recrystallized matrix is also given in Table I. The grain size did not depend on the temperature of the isothermal anneal. With one exception the grain size of the primary recrystallized matrix was found to be rather fine

Jan 1, 1965

By Joseph A. Cavallaro

This report describes the timed release analysis technique that was developed to serve as a tool for assessing the froth flotation cleaning potentials of fine-size coals. Using this developed technique, 16 coals from 10 different coalbeds were tested. All of the coals included in this study were quite amenable to froth flotation with float coal yields ranging from 80.7 to 99.5 percentage points. Float-and-sink analyses of the coals tested are shown to be of limited value in predicting froth flotation cleaning potential. Generally the float-and-sink analyses indicated a better product could be obtained than froth flotation could provide; although, in four of the coals tested froth flotation results were superior to those expected from the gravimetric analysis. The fixed carbon content of the samples collected was found to correlate with the floatability of the coals. The higher rank coals were the most readily floatable coals while the lower rank coals did not respond quite as well to flotation.

Jan 1, 1965

By J. M. Stuve

Calorimetric data for the dissolution of scandium sesquioxide and scandium trichloride in 4.360 molal hydrochloric acid were used to evaluate the standard heat of formation of ScCl3(c). The heat of reaction for Sc(c) + 1.5Cl2(g) = ScCl3(c) at 298.15° K was computed as -225,440 ±340 cal/mole.

Jan 1, 1965

By W. M. Wojcik, R. F. Kowal

Oxygen and sulfur distributions in commercial, 5-ton ingots of killed, medium carbon steel are described. Oxygen distribution is found to vary with deoxidation practice. Irregular distribution of oxygen within ingots makes necessary special precautions in sampling of rolled products for analysis of oxygen. Oxygen distribution is discussed in terms of recently published solidification concepts which had been successfully applied to simpler cases of segregation. These concepts have been found inadequate to explain observed oxygen distributions. Convective movements of the liquid metal, as determined by tracer elements, are shown to be capable of accounting for the observed distributions of oxygen. IN an effort to explore the origin of surface and subsurface imperfections in pierced steel products, a study of oxygen and sulfur segregation was made on ingots cast in open-top and hot-top molds. The results of our previous investigations1"3 have indicated the importance of the location and amount of oxide inclusions in an ingot. Inclusions close to the surface of the ingot have been found to contribute greatly to the formation of imperfections in the surface of finished products. This study of the effects of deoxidation and casting practice on segregation and the resulting oxygen distribution in ingots was initiated to determine the parameters controlling the location of inclusions in an ingot. Segregation of solute elements during solidification of low-melting binary alloys has been studied in the past.1, 5 Formation and growth of inclusions in iron melts have been studied under specific conditions."- In spite of these and other recent studies,10-12 segregation during solidification of commercial, killed steel ingots is not well understood. Consideration of solidification rates, of segregation during solidification of the chill, dendritic, and central zones, and of material balances for the segregated elements has indicated that a simplified theoretical solidification model is not adequate. However, the observed high oxygen contents in localized volumes of the dendritic zone can be rationalized if additional effects of convection currents in the ingots, precipitation, and rapid growth of new phases are considered. EXPERIMENTAL PROCEDURE Steelmaking and Processing. A group of nine killed. medium carbon steel heats having compositions listed in Table I have been studied. The deoxidation and mold practices used were varied to give a wide range of steel oxygen contents. The amounts of aluminum added to the ladle and the ingot casting practices (hot top and open top) were the main variables. The steel was made by a duplex practice in 160-ton tilting basic open-hearth furnaces. All nine heats were top-cast into 24 by 24 in. big end down, fluted molds, to a height between 60 and 76 in., using both open tops and exothermic hot tops. The deoxidation practice and the tapping and teeming details for each heat and ingot studied are given in Tables II and III, respectively. Hot-top practice is indicated by the letter H following the heat designation. Furnace and ladle temperatures were measured by standard disposable-tip, Pt/10 pet PtRh thermocouples. Teeming-stream temperatures were obtained as described by Samways et al.,13 by immersing a Pt/10 pet PtRh thermocouple, covered by a silica sheath, into the teeming stream under the nozzle. The output of this thermocouple was recorded with Leeds & Northrup Speedomax potentiometer. Calibration of the latter thermocouples was based on the freezing point of a pure iron/oxygen alloy (2795°F). The accumulated errors of measurements were within ±10°F. The thermocouple measurements were supplemented in this investigation by continuous recording of a ratioing, two-color pyrometer (Shawmeter), protected from smoke by a blast of clean air within the sighting tube, and calibrated to read with better than ±10°F accuracy. Following teeming of three heats, P, R, and T, tracer elements were added to the steel in the molds to obtain a record of the progress of solidification. As soon as the teeming stream was shut off, a 0.010-in.-thick steel can containing a mixture of crushed standard ferro-titanium and ferro-vanadium (0.05 pet of each alloy element) was plunged into the middle of the steel pool to a depth of 6 in. In about 30 sec no indication of the can or its contents remained. The surface of the open-top ingots solidified in 20 to 30 sec. A study of liquid metal movement and the precipitation of oxides was facilitated materially by use of the tracer technique as titanium has a low distribution coefficient between solid and liquid steel while vanadium has a high distribution coefficient.

Jan 1, 1965

By Frank A. Jerabek

Problems of mine backfilling and fill material deposited underground, the characteristics and relationship between the deposited fill material and overlying ground, and the practical applications and limitations of hydraulic backfilling as ground support are discussed. A great variety of materials ranging from coal washery refuse to concentrator tailings is used as hydraulic fill. Some materials will solidify and cement; others will resemble quicksand, Hydraulic fill as ground support is more efficient in inclined mine openings than in horizontal mine openings, where it cannot be placed tightly to the back. This and other deficiencies of hydraulic backfilling led to the development of pneumatic stowing. Research work in hydraulic backfilling at the Pennsylvania State University is also discussed. This research work includes the investigation of segregation in the discharged fill slurry, the quantity of solids escaping in the drain liquid, the relationship of escaping solids to slurry concentration and discharge rate, and the compressibility of fine fill material.

Jan 1, 1965

By B. B. Letson

The heats of formation of lithium chloride and lithium oxalate were determined with the aid of a Bureau-developed, glass Dewar-type solution calorimeter which uses thermistors as its temperature sensing element. Values obtained at 298.15° K were -98.38 ± 0.54 kcal/mole for lithium chloride and -329.02 ± 0.79 kcal/mole for lithium oxalate, using graphite as the standard state for carbon.

Jan 1, 1965

The principal activities of the Bureau of Mines Explosives Research Center from July 1, 1962, to June 30, 1963, are described briefly in part 1. Part 2 gives short abstracts of publications that appeared during fiscal year 1963; in general, the research reported in these publications antedates the report period.

Jan 1, 1965

By G. W. Tuffnell, S. Floreen

Three Fe-18 pet Ni-base ternary alloys cortaining carbon, molybdenum, or cobalt were aged to pgroduce hardening by carbides, Ni3Mo, or ordering, respectively. Each alloy was tested in rotating-beam fatigue tests after hardening to 195 ksi ultim.ate tensile strength. The fatigue properties of three alloys soere essentially identical. The results suggest that tlze fatigae strength of an igron-base alloy should depend primarily upon the tensile strength, and not iipon the hardening mecaanisrn. THE fatigue strengths of many steels have been found to be directly related to their ultimate tensile strengths. For ultimate strengths below 200 ksi, the fatigue endurance limit at 107 to 10' cycles is approximately half the ultimate strength. Essen- tially all of the steels that have been tested, however, have been hardened by carbon. Thus it is not certain whether the relationship between fatigue and ultimate strengths is a general one that applies for other types of hardening in steels, or whether it applies only for the particular method of hardening by carbon. The recent developments of the martensitic precipitation-hardened stainless steels and the marag-ing steels have shown that it is possible to achieve high strengths in iron-base alloys by other hardening mechanisms than that due to carbon. Therefore, it is now possible to compare the fatigue properties of several iron alloys having the same ultimate strengths but hardened by different mechanisms. For the present study a binary Fe-18 pct Ni martensite was selected as a base material. This particular matrix composition has been found to have deformation characteristics very similar to pure iron.' Three ternary alloys were prepared by adding either 0.23 wt pct C, 5 wt pct Mo, or 20 wt pct Co to this base composition. After suitable heat

Jan 1, 1965

By I. R. Kramer

In his technical note entitled "Specimen Temperature During Electropolishing of Aluminum Crystals" Dr. Nakada 1 reported that the temperature of his aluminum specimen increased 65°C when it was polished electrolytically; he therefore concluded that the temperature of the specimens used in our work (Nakada's Refs. 4 and 5) similarly increased by this amount. From this he further concluded that the change in plastic-flow characteristics associated with the removal of the surface by electropolishing during deformation were due solely to a temperature effect. We believe that these conclusions are not justified. It is, of course, realized that the amount of the temperature increase is associated with the total heat transfer of the entire system, including the efficiency of the stirring action, heat flow through the grip on the specimen, and so forth. Of great importance is the type of electrolyte used for polishing. For example, in Dr. Nakada's experiment a methanol-perchloric acid solution was used. This solution has a relatively low conductivity and for the current densities of 0.3 amp per sq cm the electrical input appears to be 30 to 40 w. In our research a methanol-nitric acid solution was employed and for the size of specimen employed by Dr. Nakada the power never exceeded 7 w. There are major differences in his test apparatus which also appear to affect the temperature rise. In our case a steel specimen holder was used in order to provide a good heat sink and conduction path. The cathode was a coiled aluminum tube through which a coolant was passed to provide additional cooling capacity near the specimen. The stirrer was placed in a position to obtain maximum cooling efficiency. On the other hand Dr. Nakada used a teflon grip to support the specimen at one end only and a flat copper cathode, thus providing a much less efficient heat sink as compared with the metal grips used in our studies. The relationship between current density and the temperature increase for two sizes of aluminum crystals tested in our tensile apparatus is shown in Fig. 1. The temperature measurements were determined from a thermocouple spot-welded to the surface of the specimen. The thermocouple was protected from the acid by means of a thin film of stop-off lacquer which covered just the outer surface of the thermocouple junction. Whereas Dr. Nakada reported a time delay of 8 min to obtain thermal equilibrium, our temperature change occurred in less than 15 sec. This emphasizes the importance of the heat transfer in the entire system. However, readings were taken over a period in excess of 5 min to assure thermal equilibrium. The data given in Fig. 1 were also confirmed by determining the thermal expansion of the specimen in a sensitive creep apparatus. As may be seen, for the smaller specimen the increase in temperature is 8°C for a current density of 1.5 amp per sq in. The majority of our data on the effects of surface removal on the plastic behavior of aluminum were obtained at current-density values at or below this value. Above 1.5 amp per sq in. the temperature rise is uncertain; for under certain conditions, especially in the vicinity of 2 amp per sq in., the anode can become polarized and the current flow is erratic. This condition is easily recognized because wide fluctuations in the creep and stress-strain data make it virtually impossible to obtain reliable results, a condition which was always avoided in our work. The temperature increase for the larger specimen is less than that of the smaller specimens below a current density of 1.5 amp per sq in. At a current density of 2 amp per sq in. the temperature increased 13°C. The above temperature data are in accord with observations made during creep experiments. Using a transducer capable of detecting strain in the order of 10 -6, temperature changes in excess of 8°C were not detected when the current density was increased to as high a value as 1.5 amp per sq in. Finally we wish to point out that our experimental data cannot be explained solely in terms of a heat effect. For example in Fig. 1 of Ref. 2, the change in slope of Stage II as a function of the rate of re-

Jan 1, 1965

By R. H. Martinson, E. Teghtsoonian

The effects of magnesium-rich surface layers of varying thickness on the mechanical properties of LiF have been studied. The yield stress, critical tensile stress, and work-hardening slope increase linearly with layer thickness, while the strain to fracture decreases yapidly with increasing layev thickness. The results of tension tests, supplemente!d by metallogvaphic evidence, indicate that the yield stress and the critical tensile stress of LiF are not determined by surface-source operation. DESPITE many studies, which have recently been reviewed,' certain fundamental aspects of the plasticity of LiF remain obscure. For instance, one question still awaiting a satisfactory resolution is: does the nucleation and/or multiplication of dislocations in LiF occur preferentially near the crystal surface? It is now well-known that mobile dislocation half-loops are readily introduced into LiF by surface damage and that the mechanical properties of LiF are affected by such surface damage. However, it is not known whether, in the absence of large numbers of artificially introduced surface sources, dislocations arise more easily near the crystal surface than in the crystal interior. It is also not known to what extent existing mobile dislocations multiply preferentially near the crystal surface. The present work is an experimental study of these matters. A short investigation of the effect of magnesium -alloyed surface layers on the deformation of LiF single crystals has been published by Westwood.~ Some relevant conclusions drawn from this research are restated here for purposes of comparison with the present work. 1) Tests on as-cleaved, chemically polished, coated and uncoated specimens show that a coating can restrict the operation of artificially introduced surface sources, thereby raising the yield stress. A coating also decreases the initial rate of work hardening of as-cleaved LiF crystals by reducing the number of active dislocation sources, so that mutual dislocation interference effects are lessened. 2) A catastrophic breakthrough of groups of edge dislocations piled up against the coating can cause stress drops in the stress-strain curve. 3) A surface coating can act as a stable barrier to the egress of dislocations, causing pile-up,

Jan 1, 1965

By S. J. Aresco, A. A. Orning

This paper presents a scheme for determination of precision for the various steps in coal sampling, sample preparation, and analysis. It also gives resulting data on 100 American coals from various coal fields covering all ranks from lignite to low-volatile bituminous. The variances of the various steps of the process are studied as a function of the coal preparation, the top size of coal as sampled, and the ash content. To understand the variables that control the overall precision of coal sampling, sample reduction and analysis, there is need for measurement of the variances due to successive steps of the process. The purpose of the present paper is to study these variances as a function of the coal preparation, the top size of the coal as sampled, and the ash content. The sampling data included are from 100 individual preparation plants from various coal fields in the United States and cover all ranks of coal from lignite to low-volatile bituminous; various types of preparation; deep, strip and auger mines; and, in many instances, mixtures from two or more coal beds or types of mines. The collection of data is continuing, but sufficient work has been done to draw some important conclusions. Since the work was done in conjunction with the Bureau of Mines sampling of coal, the time that could be spent at any one preparation plant was limited. This, in turn, limited the number of samples that could be taken for each coal. For this reason, the results from various plants were pooled in blocks. Two major blocking categories were "raw" and "washed!' The raw coals had no preparation other than crushing and/or screening. The washed coals were prepared further by some combination of wet or dry mechanical cleaning. The categories were further divided ac-

Jan 1, 1965

By T. S. Lovering

The use of geothermal energy is expanding very rapidly. This type of energy has proven commercially profitable for generation of electricity, for space heating, process heating, auxiliary heating of water in conventional steam power plants and for recovery of chemicals contained in natural hot water and steam. Two types of geothermal energy sources are recognized: 1) hot springs in regions of nearly normal heat flow that tap a deep reservoir through which water moves slowly to a hot springs conduit and then rapidly to the surface; 2) hyperthermal areas in which the water is heated by a relatively concentrated heat source related to volcanicity. If there is a geologic trap that provides a geologic analog to a steam boiler, as at Larderello, Italy, the hyperthermal area will have a convecting system that develops superheated water at relatively shallow depth and may provide natural steam in large quantities. If a hyperthermal area is to be productive for a long time, the underflow into the reservoir should be slow enough to allow the heat source and convective system to heat the underflow to the working temperature, and the production rate must not exceed this rate of underflow. A model based on a typical aquifer suggests that the rate of movement of water through the reservoir be such that a few years are spent in transit between isotherms that are spaced about 2°F apart. The possibility of finding blind geothermal areas is illustrated by discussion of the techniques developed in evaluating the subsurface temperatures in the East Tintic district of Utah where a map of isotherms at water level (2000 to 2000 ft below the surface) shows that a hyperthermal area may exist a short distance southeast of the mining district. Very nearly all of the energy that man currently uses comes ultimately from the sun's radiation. This includes water power, fuels such as wood, peat, coal and petroleum, the wind and all our animal power. In the paper summarizing a conference on solar energyl6 the average amount of solar energy received daily on the earth is taken at about 1 cal per m2 per min or slightly less than 2 pcal per cm2 per sec; this is almost exactly the amount of energy on the average that the earth liberates in regions of normal geothermal gradient due to its own internal heating. In many places, however, the energy released is many times the average and in some of these hyperthermal areas, geothermal steam is used for generation of electricity, and hot springs are used for heating buildings and private dwellings, process heating, auxiliary heating of water in conventional steam power plants, and chemicals may be recoverable from both hot water and steam. The use of hot springs waters for heating houses goes back hundreds of years but until recently was confined to a few dwellings close to the hot springs. In Korea, some houses had hot spring water channeled through conduits in the floor centuries ago and thus the Koreans can be credited with pioneer development of radiant heating. In Iceland at present nearly a third of the population uses natural thermal water for domestic heating." The Reykjavik system pipes hot spring water at about 94°C throughout the city and has devised insulated double pipes that allow the water to be piped for some 25 km with a drop of only 1°C for every 5 km. The actual cost to the Icelandic consumer is only one-third the cost of heating by imported coal and yet the industry is one of the most profitable in Iceland. The most profitable use of geothermal energy has been its conversion into electricity which can be transmitted economically much greater distances than hot water. The largest installation at the present time is that at Larderello, Italy, where the Count of Larderello began to experiment in the production of electricity from geothermal steam 60 years ago — in 1904. He installed his first steam turbine, with a capacity of only 250 kw, in 1912 as the result of a local quarrel with the power company which furnished the current required in the Larderello chemical industry - an industry that then dated back nearly a century. As experience was gained in drilling deep holes to tap geothermal steam and in converting it to electric power, the capacity of the installation of Larderello gradually increased, but was all destroyed by the Germans during their retreat from Italy in the closing

Jan 1, 1965

By A. A. Sonnek

A simple, portable helium analyzer was developed primarily for field use. Its utility lies in making preliminary surveys before exact analyses are required. The analyzer is based upon chromatographic principles; that is, separation of gas mixtures resulting from variable retention times of the components with respect to a separation medium (column-packing material). It uses thermistors for sensing detectors, a dry battery as source of power, and a micro-ammeter for indicating helium concentration. The absolute accuracy of the instrument depends upon the recency and care with which the instrument is calibrated with a standard gas. The unknown gas should be analyzed immediately after calibration, and another calibration should be made before another unknown sample is analyzed. The instrument is simple to operate, requiring approximately 15 minutes, after calibration, to determine the helium content of a natural gas sample. Although developed primarily for helium determination, the analyzer possibly can be used for other analyses that can be performed at ambient temperatures.

Jan 1, 1965

By S. J. Aresco

The Bureau of Mines has been active in promoting the purchase of coal for Government use under specifications that define the requirements in terms of heating value of the coal, expressed in British thermal units, and the composition as shown by proximate analyses. To these, when required, are added the ash-softening temperature, the free-swelling index, and the Hardgrove grind-ability index. Under most of these specification contracts the bidders guarantee the quality of the coal, and that guaranteed by the successful bidder becomes the standard of his contract. The deliveries are sampled in accordance with instructions4 issued by the Bureau of Mines; the samples are analyzed in the Bureau laboratory to determine whether the coal is of the quality guaranteed by the contractor; if it is not, a price adjustment is made. Analyses of the delivered coal and tipple samples (samples collected at mine tipples as coal is being loaded into railroad cars or trucks) provide valuable data for use in evaluating future bids. In addition, the continuous sampling of coal as delivered is a check on the practical results obtained in burning the coal.

Jan 1, 1965

By Wallace W. Key

The California pesticide industry in 1962 consumed about 30,000 tons of clay, talc, limestone, diatomite, sulfur, and other minerals as fillers (carriers and diluents) in pesticide formulation. This was 10 percent of the U.S. filler requirement for pesticides. About two-thirds of the California total was supplied by a few local mineral producers; the remainder came mainly from Florida, Georgia, and Wyoming. The objectives of this report are to provide data on quantities, sources, specifications, and market conditions for minerals used as fillers by California pesticide formulators. The study disclosed that specifications for mineral fillers have become more rigid and formulators have become more numerous in recent years. During 1962 over 1,200 firms registered 16,000 pesticide products with the Bureau of Chemistry in California. Factors which will tend to diminish future need for mineral fillers include the trend toward greater use of organic sprays rather than dusts and further development of biological controls, such as the development of sterile insect strains.

Jan 1, 1965

By R. P. Agarwala, M. S. Anand, S. P. Murarka

Using the residual radioactivity technique, grain boundary diffusion of chromium in the a phase and lattice diffusion in the a and the ß phases of zirconiuttz have heen studied. The diffusivities (in units of square centiwzeters per second) have heen expressed as THE rate of diffusion of atoms along surfaces and grain boundaries is much greater than that through the bulk of metals. These processes dominate over volume diffusion at lower temperatures and can be isolated from it by virtue of the fact they yield high diffusion coefficients and low activation energies. In zirconium, however, it has been difficult to identify the volume-diffusion parameters separately. The values of diffusivities in a and ß phases yield activation energies which are much lower than those for volume diffusion calculated from semiempirical or empirical relations.1-3 Diffusion frequencies (Do) are also low, especially in the a phase, and they yield negative entropies of activation.4 Similar results have been obtained for the diffusion studies in titanium.5 It is yet to be investigated whether in these cases diffusion is controlled by some extraneous factor like high reactivity of these metals, or some different mechanism is operative as suggested by Pound et a1.6 However, Federer and Lundy,7 in a recent study of the diffusion of zir-conium-95 and columbium-95 in zirconium, and Gibbs et al.,8 in the study of impurity diffusion in titanium, found a temperature dependence of D, Do, and Q. Their study yielded low values of Do and Q at low temperatures, as has been found by other workers, and fairly high values at high tempera-

Jan 1, 1965

By A. Bar-Or, G. Hirsch, P. Wynblatt

The rates of nucleation and growth at various temperatures in U-0.45, 1.1, and 1.35 at. pet Cr alloys were determined, providing a qliantitative proo-f that the transformation under study is controlled by nucleation and diffusional growth. The linear relationship, log NV US 1/T2, suggests that the nucleation of the alloys is probably controlled by the classical law of nuclei formation. The established linear relationship, log G us 1/T, in the three alloys suggests that growth in each alloy is controlled by bidimensional nuclei formation. It was established that both the rate of growth and the rale of nucleation are retarded by chromium. Using classical formulae, sApN and sApG (the ß/a apparent interphase energies) were calculated from the nucleation and growth results, respectively. It was found that their values are of the same order of magnitude. However, why sApN is unaffected by the addition of chromium, while sApG increases with it, needs further clarification. In the last few years, an appreciable amount of research has been conducted into the mechanism of the ß —a transformation in uranium and uranium alloys. Recently, Burke1 reviewed the published work concerned with this transformation. He concluded that in dilute uranium alloys it is firmly established that, at high temperatures in the a range, ß decomposes by a diffusional process. However, he based his conclusion either on experiments dealing with the over-all transformation,2 or on qualitative results.3 It was felt that a better insight into the mechanism of transformation could be gained from the quantitative measurements of growth and nucleation rates, which we aimed to carry out in the present work. In a previous work,4 we have shown that a rim of a grains is formed during isothermal transformation at the high a range. The thickening of this rim with time was used for measuring the rate of growth in U-0.45 at. pet Cr.5 This method was also used in the present work for two more alloys. For meas- uring the rate of nucleation, a method of quenching and macroetching was developed to allow differentiation between a grains formed during isothermal transformation at the upper a range and those formed after quenching, Fig. 1. EXPERIMENTAL WORK AND RESULTS The Rate of Nucleation. The measurement of the rate of nucleation was effected by counting the num-

Jan 1, 1965

By P. M. Blair

This paper presents numerical solutions of the equations describing the imbibition of water and the countercurrent flow of oil in porous rocks. The imbibition process is of practical importance in recovering oil from heterogeneous formations and has been studied principally by experimental means. Calculations were made for imbibition of water into both linear and radial systems. Imbibition in the linear systems was allowed to take place through one open, or permeable, face of the porous medium studied. ln the radial system, water was imbibed inward from the outer radius. The effects on rate of imbibition of varying the capillary pressure and relative permeability curves, oil viscosity and the initial water saturation were computed. For each case studied, the rate of water imbibition and the saturation and pressure profiles were calculated as functions of time. The results of these calculations indicate that, for the porous medium studied, the time required to imbibe a fixed volume of water of a certain viscosity is approximately proportional to the square root of the viscosity of the reservoir oil whenever the oil viscosity is greater than the water viscosity. Results are also presented illustrating the effects on rate of imbibition of the other variables studied. INTRODUCTION The process of imbibition, or spontaneous flow of fluids in porous media under the influence of capillary pressure gradients, occurs wherever there exist in permeable rock capillary pressure gradients which are not exactly balanced by opposing pressure gradients (such as those resulting from the influence of gravity). The importance of such capillary movement in the displacement of oil by water or gas was recognized in early investigations and described by Leverett, Lewis and True in 1942.1 Methods advanced by these authors for studying the process using dynamically scaled models were rendered more general and flexible by the research of later workers.2"4 The influence of capillary forces in laboratory water floods has also been discussed by several authors.6 While imbibition plays a very important role in the recovery of oil from normal reservoirs, Brownscombe and Dyes7 pointed out that imbibition might be the dominant displacement process in water flooding reservoirs characterized by drastic variations in permeability, such as in fractured-matrix reservoirs. In water-wet, fractured-matrix reservoirs, water will be imbibed from fractures into the matrix with a countercurrent expulsion of oil into the fractures. If the imbibition occurs at a sufficiently rapid rate, a very successful water flood can result; if the imbibition proceeds slowly the project might not be economically attractive. Scaled-model studies have demonstrated the vital importance of imbibition in secondary recovery in fractured reservoirs. It is therefore important in the evaluation of waterflooding prospects to develop a thorough understanding of the quantitative relationships of the factors which control the rapidity of capillary imbibition. The imbibition process serves reservoir engineers in still another important way by providing a technique for studying the wettability of reservoir core samples. Such experiments are usually conducted by observing the rate of expulsion of oil or water from core samples submerged in the appropriate fluid. Several papers have been 'published on the experimental techniques involved?? Although Handy has recently published a method for calculating capillary pressures from experiments with gas-saturated cores, it has not yet been possible to deduce quantitative information regarding water-oil relative permeability and capillary pressure characteristics of the rock from the experimental results. Thus a technique is needed for studying the quantitative dependence of imbibition rate on oil and water viscosity, initial water saturation, relative permeability-saturation, and capillary pressure-saturation relations. The development of such information, including saturation and pressure profiles by laboratory experiments, would be very difficult. However, recent advances in the applica-

Jan 1, 1965