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By C. F. Cockrell, H. E. Shafer, J. W. Leonard

A significant technological development is discussed for the processing of certain power plant flyashes that are a problem because they contain a high water-soluble mineral content and yield inferior flyash-based brick. This development is based on the addition of hydrochloric acid to the flyash-bottom ash-sodium silicate blends used for the production of flyash-based structures. Favorable changes are evi-dent in sodium silicate consumption, where about half the amount used for making brick from normal flyash is required, processing costs, and strength and appearance of the resulting freshly formed green and fired structural products. In some high cost in-stances (above the $30 or less per thousand brick estimated for normal flyash), hydrochloric acid additions can replace or reduce other costly additives normally required for problem flyashes. This results in savings of as much as $9 per thousand brick. These developments offer promising possibilities for utilizing problem flyashes as well as flyashes which may come into contact with water soluble sulfur as a result of the eventual application of certain experimental air pollution control processes. Much of the research datal-6 accrued through work by the Coal Research Bureau of West Virginia University for the Department of Interior's Office of Coal Research on converting waste power coal ash to valuable brick and other structural products, can be categorized as follows: (1) general ash-to-brick tech- nology; (2) specific ash-to-brick optimization; (3) pilot plant progress; (4) production cost estimates. A summary of the progress on bench-scale experiments indicates that coal ash can yield two types of brick. An acceptable brick is obtained by mixing 73.6% fly-ash, 23.5% bottom ash and 2.9% sodium silicate solution (dry basis). Depending on the flyash and bottom ash used, optimum brick can be manufactured by mixing 72-77% flyash, 20-25% bottom ash and 2.3-3.0% sodium silicate (dry basis) with Na2O : SiO2 ratio varied according to the composition of the flyash used. These blends are thoroughly mixed and mechanically formed into green brick shapes at pressures ranging from 1000 to the more usual 3000 lb per sq in. The green shapes then are dried and fired at temperatures ranging from 1975-2150°F using clay brick cycles that are shorter than standard. Other findings reported to date indicate that when making optimum brick, it is necessary to carefully control the top size of the moisture-releasing bottom ash so that it falls between 8 and 30 mesh, depending on the flyash used. Moreover, the chemical composition of bottom ash and flyash have been found to be of little significance with the exception of a few problem flyashes which are the subject of this paper. Finally, the pilot plant, which was previously reported under construction, is now in operation. This will indicate, among other things, the cost of brick production, which was earlier estimated for non-problem flyashes at $30 or less per thousand brick. The foregoing bench-scale technology is applicable to all the initially tested ashes as well as to the majority of ashes examined during the course of research. However, a few of the ashes yield green and fired products that may be structurally inferior or unacceptable, necessitating excessive and diverse reagent addition, and/or may be coated with unsightly surface deposits. These problem ashes generally originate in certain areas of Illinois, western Ken-

Jan 1, 1969

By J. Chipman, T. P. Floridis

The equilibrium of gaseous H2O-H2, mixtures with liquid iron is used to establish the activity coefficient of dissolved oxygen as log f o = — 0.20 [%O]. Discrepancies in earlier work are explained or eliminated. Additions of cobalt, molybdenum, tungsten, and platinum increase the activity coefficient of oxygen whereas copper and gold decrease it. THE importance of dissolved oxygen as a refining agent in liquid steel has led to a number of studies of its thermodynamic properties. It is the purpose of this paper to examine the effects of a number of alloying elements on the activity of oxygen in the steel bath. As a preliminary to the study of the effects of alloying elements, it seemed desirable to examine certain minor discrepancies in the published data on the properties of oxygen in simple iron-oxygen solutions. The activity and free energy of oxygen in liquid iron were studied by chipman1 in 1933 by means of the reaction h2(g)+-o = H2O (g);K; = PH2O/PH2[% O] [1] The data were in fairly good agreement with calculations from results on the similar reaction CO (g) + O- = CO2 (g); K2 =P CO2/P CO [% O] [2] which had been obtained by Vacher and Hamilton2 as an incidental part of their study of the reaction of carbon with oxygen dissolved in the melt. It was found that the equilibrium ratio k1 was not a true constant but varied with the oxygen concentration in the manner shown in Fig. 1, which is copied from the original paper. This early observation has been refuted in subsequent work but is confirmed in the present paper, and an explanation of the discrepancy can now be presented. In Fig. 1, the two points on the extreme right were disregarded in drawing the

Jan 1, 1959

By John C. Draper

The principal object of an underground coal mine transportation system is to move coal from the face where it is produced to the outside of the mine where it is prepared for market. In addition to the movement of coal, a transportation system must also move supply materials to the inside ; it must move men in and out of the mine ; and it must move rock and other debris out of the mine for disposal. Usually, mine haulage is divided into three categories named for the various areas of the mine served : 1) Pace Haulage. This is used at face from the mining machine to the intermediate transport system. 2) Intermediate or Secondary Haulage. Generally this is used between face haulage and main haulage. Sometimes this is merely an extension of the main haulage. 3) Main Haulage. This extends from the secondary haulage to the outside and is usually either a track or conveyor system, sometimes a combination of both. Transportation modes of coal in the various areas pose different problems, but the whole system must be synchronized. For instance, at the face the coal should be removed quickly from the various places to facilitate the movement of machines, whereas the intermediate system just passes the same coal on to the main transportation system. Selection of the transportation system must be based on the seam height, mining methods used to extract the coal, capacity required, ease of coal handling, and haulage efficiency. When driving rooms, mine cars can be used. They often simplify supply haulage and rock handling because they can also handle these items. Conveyors could be used and would have a greater haulage capacity but they cannot handle supplies easily or segregate the rock. When using a different mining method, such as longwall, mine cars cannot be used because there is not sufficient space to move the cars at the face nor can the cars haul the coal without delays which would cause excessive losses in production. As for ease of handling

Jan 1, 1981

By Roy A. Lindgren

SINCE the year 1643, when the first blast furnace in America for treating iron ore was built at Saugus, Mass., out of mica schist quarried in the neighboring district, the procurement of a suitable refractory for furnace lining has been a problem of concern to the operators of furnaces. The stacks built of mica schist continued to smelt iron ore until about 1836, when, according to F. H. Norton, the first firebrick were produced', at Queens Run, Pa. Other writers speak of brick having been molded and burned in Massachusetts about the year 1834. In 1841, Andrew Russell began to produce medium refractory plastic clay brick near East Liverpool, Ohio, that were used for lining blast furnaces'. The well-known Kentucky clay-producing district was not opened up until the year 1871, but since then it has produced a large percentage of the linings for iron blast furnaces. While some strides have been made by the refractories industry during the 100 years that have passed since the first firebrick were produced, it has been only during the last two decades that any real progress has been made towards bettering the product, even though the method of production had improved. Perhaps the fault lies with the user of the brick rather than with the producer, for not sooner demanding a supe¬rior product. During the past 15 years the tonnage produced per lining has increased from 500,000 gross tons to 1,000,000 gross tons, and now some furnaces are producing 1,600,000 gross tons and better on a single lining. It is true that enlarged capacity of furnaces and improved practice have accounted for some of this increase in tonnage, nevertheless better quality in firebrick must be given credit for its share. However, we are not yet ready to say that we have reached a maximum life of furnace lining. We believe that a better product can be produced and that the refractories industries of America will, through their extensive research depart-

Jan 1, 1937

Jan 1, 1922

Jan 1, 1922

By D. G. Westlake

The electrical resistance of a series of V-H alloys (0 to 3.5 at. pct H) has been measured over the temperature range G° to 360°. Interstitial impurities made contributions to the residual resistivity, but not the ideal resistivity. The contribution of hydrogen in solid solution is expressed by Ap = 1.12 microhm-cm per at. pct H; but the contribution of precipitated hydride was negligible. A portion of the so1vu.s for the V-H phase diagram is presented. The solubility limit is given by In N (at. pct H) = (5.828 i 0.009) - (2933 i 44)/RT. Comparison of critical temperatures joy hydride precipitation and published critical temperatures for hydrogen embrittlement suggests the two are related. ThiS study was initiated as part of an investigation of the mechanism by which small concentrations of hydrogen embrittle the hydride-forming metals at low temperatures. It has already been shown that, in the case of hcp zirconium, a reduction in ductility accompanies the strengthening resulting from precipitation of a finely dispersed hydride phase.''' Our attempts to detect a similar precipitation of a second phase at low temperatures in V-H alloys by transmission electron microscopy have been thwarted because we have been unable to prepare thin foils that are representative of the bulk material with respect to hydrogen concentrati~n.~'~ The present investigation establishes the solvus of the V-H system at subambient temperatures. Subsequently, we hope to be able to determine whether the embrittlement temperature is related to the critical temperature for precipitation of the hydride in a given V-H alloy. veleckis5 has proposed a partial phase diagram for the V-H system based on extrapolations of the pressure-composition relations he measured at higher temperatures. Kofstad and wallace' conducted a similar study of single-phase alloys but did not attempt to establish the phase diagram. Zanowick and wallace' and ~aeland' have studied a portion of the phase diagram by X-ray diffraction, but they investigated no alloys in the hydrogen concentration range 0 to 3 at. pct, the range of interest to us. EXPERIMENTAL PROCEDURE The vanadium was obtained from the Bureau of Mines, Boulder City, Nev., in the form of electrolytic crystals. The analyses supplied with them listed 230 ppm by weight metallic impurities, 20 ppm C, 100 ppm N, and 290 ppm 0. The crystals were electron-beam-melted into an ingot that was rolled to 0.64 mm. Strips, 60 mm long and 4.2 mm wide, were cut from the sheet, and both rolled surfaces were ground on wet 600-grit Sic paper to produce specimens 0.4 mm thick. They were wrapped in molybdenum foil, vacuum-encapsulated in quartz, and annealed 4 hr at 1273°K. The specimens were annealed in a dynamic vacuum of 2X lo-' Torr for 30 min at 1073°K for dehydrogenation, and charged with the desired quantity of hydrogen by allowing reaction with hydrogen gas at 1073°K for 2 hr and cooling at 100°K per hr. Purified hydrogen was obtained by thermal decomposition of UH3. Sixteen specimens were studied: two contained no hydrogen and the others had hydrogen concentrations between 0.5 and 3.5 at. pct (hydrogen analyses were done by vacuum extraction at 1073°K). Electrical resistances were measured by the four-terminal-resistor method on an apparatus similar to the one described by Horak.~ The specimen holder was designed so that both current and potential leads made spring-loaded mechanical contact with the specimen. The potential leads were 30 mm apart, and the current leads were 55 mm apart. The current was 0.10000 amp. We used the following baths for the indicated temperature ranges: liquid nitrogen, 77°K; Freon 12, 120" to 230°K; Freon 11, 230" to 290°K; and ethanol, 290" to 340°K. Temperatures lower than 77°K were achieved by allowing the specimen to warm up after removal from liquid helium. Temperatures above 77°K were measured by a calibrated copper-constantan thermocouple (soldered to the specimen holder) and below 77°K by a calibrated carbon resistor. The temperature of the bath changed less than 0.l0K between duplicate measurements of the resistance. RESULTS AND DISCUSSION Typical plots of resistivity p vs temperature T are shown in Fig. 1. In the interest of clarity, only five curves are presented and the data points have been

Jan 1, 1968

By I. E. Rosenzweig

GEOPHYSICAL prospecting by earth-resistivity methods is frequently applied to investigation of structural problems in geology. Fig. 1 indicates a scheme of the general arrangement used in these methods of measurements. The battery (or generator) E is connected with two "current electrodes" II and 12. The current of intensity J, supplied by this battery, passes through the earth between these elec- FIG. 1.-GENERAL ARRANGEMENT OF APPARATUS. trodes. A potential difference U will be measured between two other electrodes V1 and V2, called "potential electrodes." According to the configuration of electrodes (Fig. 1), the resistivity of a homogeneous soil results from the formula p = 2pcaU/J [1] where c=1/a/b11 - a/b12 ? (a/b21-a/b22) [2]

Jan 1, 1938

By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph',' to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox' make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952

By K. E. Brown, A. R. Hagedorn

A 1,500-ft experimental well was used to study the pressure gradients occurring during continuous, vertical, two-phase flow through 1-in., 1 1/4-in. and 1 1/3-in. nominal size tubing. The test well was equipped with two gas-lijt valves and four Mathak electronic pressure transmitters as well as with instruments to measure the liquid production rate, air injection rate, temperatures and surface pressures. Tests were conducted for widely varying liquid flow, rates, gas-liquid ratios and liquid viscosities. From these data, an accucrate pressure-depth traverse was construcred for each test in each of the three tubing sizes. From the results of these tests, correlations have beer] developed which allow the accurate prediction of flowing pressure gradients for a wide variety of tubing sizes, flow conditions, and liquid properties. Also. the correlations and equations which are developed satisfy the necessary condition that they reduce to the relationships approprate to single-phase flow when the flow rate of either the gas or the liqutid phase becomes zero. All the correlations involve only dimensionless groups. which is a condition usually Sought for in similarity analysis but not always achieved. The correlations developed in this study have been used to calculate pressure gradients for pipes of larger diameter than those upon which the correlations are based. Comparisons of these calcuclaed gradients with experimetally determined gradients for the same flow conditions obtained from the literature indicate that extrapolation to these larger pipe sizes is possible with a degree of accuracy sufficient for engineering calculations. The extent of this extrapolation can only he determined with additional data from larger pipe diameters. INTRODUCTION The accurate prediction of the pressure drop expected to occur during the multiphase flow of fluids in the flow string of a well is a wideiy recognized problem in the petroleum industry. The problem has been brought even more into prominence with the advent of tubingless or slim-hole completions which use small-diameter tubing. Many of the correlations which give reasonably accurale results in the lager tubing sizes are greatly in error when applied to small-diameter conduits. Small-diameter conduits are defined as 1 1/2-in. nominal size tubing or smaller. The study of the pressure gradients which occur during multiphase flow of fluids in pipes is exceedingly complex because of the large number of variables involved. Further difficulties relate to the possibility of numerous flow regimes of widely varying geometry and mechanism and the instabilities of the fluid interfaces involved. Consequently, a solution to the problem by the approach normally used in classical fluid dynamics based on the formulation and solution of the Navier-Stokes equation has not been forthcoming. This is primarily the result of the nonlincarities involved and the difficulty of adequately describing the boundary conditions. As a result of the foregoing, most investigators have chosen semi-empirical or purely empirical approaches in an efford to obtain a practical solution to the problem. Much of the previous work in this area was done in short-tube models in the laboratory. A number of problems arise, however, when attempts are made to extrapolate these laboratory results to oilfield conditions where a much longer tube is encountered. In those few studies where data taken in long tubes were utilized, the data covered only a limited range of the variables, and as a result inaccuracies are introduced when the correlations are extended outside the range of the original data. Also, as a consequence of the limited amount of data available for these studies, the effects of several important variables were overlooked. The problem of predicting the pressure drop which occurs in multiphase flow differs from that of single-phase flow in that another source of pressure loss is introduced, namely, those pressure losses arising from slippage between the phases. This slippage is a result of the difference between the integrated average linear velocities of the two phases, which in turn is due to the physical properties of the fluids involved. In contrast to single-phase flow. the pressure losses in multiphase flow do not always increase with a decrease in the size of the conduit or an increase in production rate. This is attributed to the presence of the gas phase which tends to slip by the liquid phase without actually contributing to its lift. Many investigators have attempted to correlate both the slippage losses and the friction losses by means of a single energy-loss factor analogous to the one used in the single-phase flow problem. In an approach of this type, hourever, many of the important variables, such as

Jan 1, 1966

By F. C. Holden, R. D. Buchheit

In the course of studies made on the Ti-Cu alloy system,' particles identified visually as TiH were encountered unexpectedly in a specimen of high-purity Ti-0.8Cu alloy. The particles did not appear immediately after preparation, but following-storage in a dessicator for several days. Since the alloy had been vacuum annealed to a low hydrogen concentration (19 ppm by vacuum-fusion analysis), the appearance of the TiH particles was suspected as a surface contamination effect. A specimen of a Ti-0.8Cu alloy had been annealed 2 hr at 790°C and water quenched, to produce the single-phase equiaxed a structure. The metallo-graphic sample was ground through 600X paper, rough-polished on a high-speed wheel with a mixture of alumina and chromic acid, awLhish-polished on a slow-speed wheel. Disturbed metal layers were removed from the final surface by alternately etching with a 1 1/2 HF-3 1/2 HNO3-95 H2O solution and polishing on the slow-speed wheel with fine alumina. The final surface was swab-etched with a 1 1/2 HF-3 1/2 HNO3-95 H2O solution, rinsed in tap water, and dried in a stream of filtered air. The micro-structure, shown in Fig. 1, was composed of equiaxed a grains without any trace of second phase. After storage in a dessicator for 3 days, the appearance of small particles in the structure became evident (see Fig. 2). After 7 days of storage, the particles were more distinct, and in some grains, began to appear as elongated particles. The specimen then was etched a second time (without repolishing) to produce the structure shown in Fig. 4. On the basis of micro- structural observation, the line markings were identified as TiH; attempts to obtain diffraction patterns from the surface for positive identification were not successful. That the structure is a surface effect was demonstrated by grinding with 240X paper to remove the surface layer. The surface then was ground, polished, and etched using the procedures described previously. The same observations were made: the freshly prepared surface was devoid of any second phase, whereas the particles again appeared after several days storage. The same effect has been observed in other a-stabilized titanium alloys, including a high-purity Ti-0.20 alloy containing only 16 ppm H by analysis. The effect has not yet been observed in unalloyed titanium, nor does its appearance appear to be consistent with any particular alloy system. From these observations, it is concluded that certain a-titanium alloys are susceptible to the formation of titanium hydride at the surface of metallo-graphic specimens. The hydrogen probably is diffused into the surface from a residual film of etchant decomposition products. Estimates of the hydrogen

Jan 1, 1961

By Charles S. Barrett

THIS paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstructures. About 12m exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,1 and a number of these have been selected to illustrate the results obtained. Prints are also included showing the common types of falsities-to borrow a term from the biological field, the "artifacts." In brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. n addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains. Since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. SPECIMEN PREPARATION AND PHOTOGRAPHS Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for repeated polishing and etching (each successive polish becoming less severe and each etch lighter), since the final etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and IC, the replicas used were of silica, deposited up0n polystyrene and floated from the polystyrene in ethyl bromide according to polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1943

By C. S. Matthews, H. M. Girner, C. D. Williams, M. J. Edwardson, H. R. Parkison

Quantitative interpretation of electric logs requires knowledge of formation temperature. In this paper, methods are developed for computing changes in formation temperature caused by circulation of mud during drilling operations. The basis of the method is the mathematical solution of the differential equation of heat conduction. The solution of this equation is presented in a series of graphs. These graphs are used to determine formation temperature disturbance at various radii for arbitrary mud circulation histories. Example comparisons with field results show reasonable agreement. It is concluded that, in general, the temperature disturbances caused by circulating mud are small beyond 10 ft from the wellbore but are quite significant near the wellbore. INTRODUCTION Quantitative interpretation of electric logs requires knowledge of the formation temperature in order to establish the resistivity of the formation water with accuracy. To determine the formation temperature, the temperature disturbances produced by circulating drilling mud must be evaluated. -The objective of this investigation was to develop a method for the numerical determination of these temperature disturbances at any distance from the wellbore as a function of time. The first step was to solve the differential equation describing the temperature behavior in the formation during and after mud circulation. This solution was used to calculate a series of curves relating temperature disturbance to shut-in time for various circulating periods. An "exact" method for computing formation temperatures with the use of these temperature-disturbance plots is described, and the results of an application of this method to a well in Montana are presented. Procedures for approximating formation temperatures are also discussed. BASIC EQUATIONS AND ASSUMPTIONS With the assumptions that (1) cylindrical symmetry exists, with the borehole as the axis, (2) heat flow is 1. The formation can be treated as though it is radially infinite and homogeneous in extent, as regards heat flow. 2. The presence of mud cake can be disregarded. 3. The effect of heat generated by bit action is negligible. 4. After mud circulation ceases, the rate of radial heat flow at the wellbore is negligible and is assumed zero for purposes of calculating temperature change with time. These assumptions are believed to be reasonable because of the agreement achieved between calculated and measured borehole temperature in a well, to be discussed later. Further, the agreement at the wellbore indicates that temperatures in the formation were also approximately correct. since it is the formation temperatures that determine wellbore temperature after ceasing circulations SOLUTION OF THE DIFFERENTIAL EQUATION AND ITS APPLICATION The solution of Eq. 2 for the temperature behavior during and after a single period of mud circulation is

By John J. Egan, A. B. Kinzel, Walter Crafts

The demands of the petroleum and chemical industries for steels to be used in pressure vessels and similar structures at artificially low temperatures are continually increasing, and the writing of proper specifications with suitable tests becomes increasingly important. Likewise, the selection of suitable steels for such applications is of increasing concern to the metallurgist. It is generally recognized that highly alloyed steels of the austenitic stainless type retain their properties even at very low temperatures and represent the best technological solution of the low-temperature steel problem. However, in many instances less expensive carbon or low-alloy steels suitable for service within limited temperature ranges are available. The problem thus becomes one of defining the various factors involved in the production and fabrication of these less expensive steels and determining the temperature ranges in which their properties justify engineering application. Most of the applications involve welded structures, and the heat effect of welding as well as the nature of the weld metal are matters of prime concern. The first problem that the metallurgist faces is the determination of the type of test to be used as a criterion of the performance of the steel in low-temperature service. It has been generally recognized that the static properties of steel as determined in the ordinary tensile test undergo a gradual and relatively slight change as the temperature of test is lowered in the range of current interest; i.e., from room temperature to minus 120' C. It is further generally recognized that the behavior of steel under impact involving notch sensitivity is definitely affected at the lower temperatures. While the major subject of this paper is the effect of grain-refining deoxidizers, of low-alloy additions and of welding on the low-temperature notched-bar impact properties, an inquiry into the general behavior of steel under low-temperature impact testing is included. This is a pertinent portion of the investigation and the results thereof are

Jan 1, 1937

By D. S. Flett, A. W. Fletcher

Equilibrium studies on the extraction of nickel and cobalt with kerosine solutions of naphthenic acid have shown that an exchange extraction reaction occurs at pH 5.5. The nickel/cobalt separation factor is constant at 1.8 for constant total metal molarity and varying nickel/cobalt ratios. The separation factor decreases with increasing total metal molarity in the organic phase beyond 0.2 M and also decreases with increasing temperature. From the equilibrium data, it has been possible to derive a mathematical model for the separation of nickel from cobalt by exchange extraction in multistage systems. Experimental data from a continuously operated multistage mixer/settler apparatus has shown a reasonable correspondence with computer-calculated data. The effective separation of nickel and cobalt in sulfate solution remains a problem in hydrometallurgy and the hope that this would be solved by solvent extraction has not yet been fulfilled. With chloride solutions, advantage may be taken of the ability of cobalt to form anionic complexes with the chloride ion. It can then be readily separated from nickel, which does not form stable chloro complexes, by extraction with a suitable long chain amine. However, in hydro metallurgical operations, sulfate solutions are generally obtained in which no extractable anionic species are present. Thus, the possibility of using cationic extractants must be considered, and in this paper attention is directed to the use of carboxylic acids. The method of separation studied has been termed exchange extraction, which involves replacement of a metal in the organic phase with a more acidic metal in the aqueous phase. Thus, (BR2).+ (Az+)aqt=(AR,).+ (B2+)aq (I) where metal A is more acidic than metal B, R represents the acidic radical derived from the acid RH, and the subscripts e and aq refer to the organic and aqueous phases, respectively. Ashbrook and Ritcey' have used this method for the separation of cobalt from nickel using the sodium salt of di-2 ethyl hexyl phosphoric acid, which preferentially extracts cobalt. Some nickel is coextracted, and this is removed by exchange with cobalt ions in the feed solution by suitable countercurrent operation in a pulsed column. Much work has been carried out by a number of workers in Russia on the general use of exchange extraction for the separation of metal ions using car-boxylic acids. Gindin et aL a have demonstrated that this technique could be applied to the separation of nickel from cobalt using a C--C. carboxylic acid and have applied the technique to the production of high purity cobalt solutions for electrolysis. Further worka was concerned with the development of a process for the separation of nickel from cobalt in a pulsed column. This system permitted the separation of iron and copper from nickel and cobalt in one system. The procedure involved center feeding with acid backwashing at the top and alkali addition lower down the column. Thus the system operated under a pH gradient and the metals were distributed in the column in the order of their basicities. A similar application was studied by Gel'perin et al,4,5 for the removal of copper and iron impurities from a nickel anolyte by means of a C10-C,12 fatty acid fraction. Ginden et al,' and Fletcher and Wilson' have studied the effect of pH on the extraction of a number of metals with carboxylic acids. These studies showed that metals such as iron, copper, lead, zinc, nickel cobalt, and manganese are extracted at pH values close to the pH of hydroxide precipitation. Nickel is extracted at a slightly lower pH than cobalt and thus the nickel/cobalt separation factor has a value not much greater than 1. More basic work on complex identification has been reported by Fletcher and Flett: by Tanaka; and Jay-cock and Jones." These studies have suggested that at low loadings in the organic phase, the nickel and cobalt carboxylates appear to be dimeric and solvated by free carboxylic acid molecules. As the concentration of metal in the organic phase increases, the complex changes and larger polymeric species are formed. In order to permit assessment of the potential of carboxylic acids as extraction reagents for separation of

Jan 1, 1971

By David B. Reger

The value of carbon ratios in determining the boundaries of possible oil deposits appears to have passed the hypothetical stage. The theory that the ratio of fixed carbon in pure coals is an invariable index of incipient metamorphism in both surface and underground rocks and that it may be applied in defining the limits of petroleum, advanced by David White,' has been received with keen interest by many petroleum geologists. Detailed isocarb maps have been prepared of the Pennsylvanian area of North Texas and Eastern Oklahoma by M. L. Fuller.² A similar map of the coal-bearing area of West Virginia is given here. An isocarb3 is a line showing an equal fixed-carbon percentage, pure coal basis; the term has been proposed by David White to supersede a less expressive nomenclature. The term carbon ratio is applied to the pereentage of carbon in pure coal after water and ash have been eliminated. As a comparatively small number of analyses have been made on this basis, it is usually necessary to compute the ratio by dividing the fixed carbon of the proximate analysis by the sum of the fixed carbon and volatile matter of the same analysis. Many thousands of proximate analyses have been made by the West Virginia Geological Survey, covering nearly every county in which coal is found. Numerous others have been made by the U. S. Geological Survey and the U. S. Bureau of Mines, but as uniformity of results is best secured by adhering to one set of analyses, the tests of the West Virginia Survey have been cxclusively used.

Jan 1, 1921

By Mark D. Tabak

Measurments of the transient photoconductivity in fillns of amorphous selenium with blocking- contacts haue been used in studying the transport properties. The results shozu that the transport of free carviers cannot be explained in terms of a model using bulk trapping. Measurments of the photocurrent-applied field characteristic as a unction of sample thickness do not pvoduce the scaling lau,s approps-iate lo a range-limited model. THE investigation described here was undertaken to explore the mechanisms of transport in amorphous selenium films. These films are used in xerography, where a photoconductor is charged electrostatically and then exposed to light to form a latent image. The sensitivity that one can expect when operating in this mode is directly related to the transport properties of the photoconductor material. The study of photoconductivity at high fields in insulating materials is often complicated by contact effects. Injection from the contacts can easily mask the fundamental transport processes that are being studied. A technique is described in this paper that allows a study of photoconductivity and transport processes in amorphous selenium films without the complicating effects introduced by contacts. Accordingly, the samples are prepared using insulating films between the sample and the metal electrodes, where the electrodes are capacitively coupled to the surfaces of the sample under study. A transient measurement is performed with pulsed light, and the photocurrent measured near the beginning of the pulse before the field is distorted by polarization at the blocking elec- trodes. A similar method has been described by Manyl using pulsed electric fields in studying the high field transport in insulating cadmium sulfide. EXPERIMENTAL It is possible to eliminate undesirable contact effects and maintain uniform high fields across the sample by using blocking electrodes and measuring the current-field characteristic under transient conditions. The sample configuration is shown schematically in Fig. 1. Each of the gold electrodes is separated from the amorphous selenium film by a layer of insulating plastic (Formvar) approximately 2000~ thick. The electrode on the front surface is semi-transparent to allow illumination of the sample. The whole configuration is mounted on a KEL-F substrate, which is a transparent insulating plastic having a thermal expansion coefficient that allows low-temperature measurements without cracking the selenium film. Fig. 2 shows a block diagram of the measurement apparatus. Light was obtained from a 450-w Xenon arc lamp, the intensity of which was controlled by stainless-steel screen filters and monitored by a pho-tomultiplier which was calibrated periodically against a thermopile. A camera shutter operated at 1/200 sec provided the light pulse and a synchronized signal to the oscilloscope. The photocurrent transient is ob-served with a high-speed picoammeter (response time of 1 msec) the output of which is displayed on an oscilloscope. The applied voltage is constant throughout the transient measurement. The selenium films were prepared by evaporation of four 9's pure selenium shot supplied by Canadian Copper Refiners. Spectrographic analysis showed about 1 ppm of Te and Fe, 5 ppm of C1, and 0.05 ppm

Jan 1, 1968

By C. Scala, M. Gondouin

Published laboratory data have established that very significant streaming potentials can exist across mud cakes subjected to pressure differentials such as exist between a mud column and formation fluids. Since shale is similar in kind and in properties to a well-formed mud cake, it appeared possible that streaming potentials might also arise across shales. A practical consequence would be that the streaming potential contribution to the SP would be smaller than might otherwise be assumed since the SP is measured with respect to the "shale bare line". The resultant contribution would be the difference between the streaming potential across the shale and that across the mud cake. In order to investigate this possibility, a laboratory apparatus was devised for measuring streaming potentials under pressure conditions normally encountered in wells. Reported data on streaming potentids across mud cakes were verified. More important, appreciable streaming potentials were found across shale samples. As in the case of mud cakes, the shale potentials varied with the concentration and nature of the impregnating electrolyte. Dependence on pressure was In a different rela-tion than that for mud cakes, possibly because of the lower compressibility of shales. The differences in streaming potentials between the shales md mud cakes were generally small, although they might vary considerably in practice depending on the relative electro-kinetic properties of the particular shale-mud cuke combination. A "poorly eflective" shale with a "very eflec-tive mud cake" would produce the largest negative addition to the electrochemical component of the SP. Results of field experiments with pressurized wells were considered in the light of the laboratory results. INTRODUCTION Field experiments wherein the pressure of the mud column in a borehole was varied have often indicated the presence of a streaming potential, but its magnitude was not easily predictable and its sign sometimes changed from one formation to another in the same well.' In the interpretation of SP logs from standard surveys, nevertheless, the correct value of R,, is very frequently obtained, within the limits of field accuracy, using only the simple electrochemical expression of the SP provided that proper corrections are made for bed thickness, ion activity, etc.' Accordingly, it was apparent that the streaming potential component of the SP in a borehole was considerably more complex than commonly assumed and clarification was indeed necessary The close similarity in nature and constitution of a shale to a well-compacted mud cake suggested that a streaming potential might also exist across shales as pointed out by M. P. Tixier in 1953 and as recently emphasized by Wyllie." e practical consequence would be that the streaming potential across the mud cake would be canceled, at least in part, on electrical logs since the SP is recorded with respect to the shale potential as a base line. This appeared to be a plausible explanation for many of the effects observed but no supporting data were available. In 1955 preliminary experiments at low pressures were conducted in our laboratories which supported the hypothesis of the shale streaming potential and formed the basis for later studies at borehole pressures.* EARLY LOW PRESSURE EXPERIMENTS The early experiments were conducted primarily to determine the possibility of a streaming potential across shales. The shale used was a compact type designated as No. 7 from Reagan County, Tex. (Permian). Cut samples were saturated for over one month in .2 to 2.0-N NaCl solutions. In order to eliminate all electrode polarization effects, a dynamic method was used. A transient pressure of about 1 atm was applied across

By O. B. Bucklen, P. G. Meikle

INTRODUCTION The trend in the coal industry for many years has been to make every- thing "bigger and faster." This also held true for loading and storage facilities. Where once a million ton per year mine was rare, three to five million ton per year mines are not uncommon today in the bituminous industry. This greatly increased production, made possible through mechanization, required greatly improved loading facilities just to get the coal away from the mine. Also, there is a trend toward combining production from more than one mine and cleaning it in a single preparation plant. In addition to increased loading capacity, this frequently necessitates raw coal storage and blending facilities. The development of the unit train with its attendant economics, more than any other factor, has contributed to the widespread construction of storage and high-speed loading facilities. In the export market, the construction of ever larger coal colliers has contributed to a need for faster and larger loading facilities. In this climate of rapidly changing technology, any written account is faced with the possibility of obsolescence before its appearance. Thus, this chapter seeks to define the common and current practice in coal loading and storage facilities with the full knowledge that this practice is an ever-moving target. FUNDAMENTALS OF COAL STORAGE Storage of coal is becoming an increasingly important part of coal handling systems at mines, particularly since the advent of the unit train concept in transportation. In order to take advantage of reduced transportation rates on trainload shipments of coal offered by unit train movement, operators have found that storage is an economic necessity. In unit train practice large predetermined quantities must be loaded in relatively short periods of time as opposed to conventional practice where coal is loaded at a speed dependent on the production capacity of the mine and/or the cleaning capacity of the preparation plant. Two surveys of storage practices at mines reveal several objectives for storage.1, 2 Raw and/or clean coal storage is generally practiced in order to accomplish one, or a combination, of the following objectives: 1. To improve plant efficiency by distributing plant feed over the entire operating time, or to allow a preparation rate different from the production rate. 2. To limit interruptions of supply, ie, allow mine and plant to function independently with delays in one not affecting the operation of the other.

Jan 1, 1968

By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts'2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969