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By D. A. Augenstein, L. V. Amundson

Operators of coal preparation plants use equipment such as large-capacity dump trucks and bulldozers to haul, spread, and compact refuse material to conform to federal and state regulations governing the disposal of solid waste. For example, federal regulations require that refuse be spread and compacted in layers not more than 0.6 m (2 ft) thick. If the refuse layers or piles have poor load-bearing characteristics, movement of equipment over them becomes extremely difficult. The increasing cost and limited space for the construction of settling ponds extensively used for fine refuse disposal are leading to the growing practice of dewatering the fine refuse by means of vacuum disk filters and combining the resulting filter cake with coarse refuse for waste bank disposal. However, this filter cake usually contains more than 25% moisture. Therefore, when it is combined with coarse refuse, the moisture level of the total refuse may become high enough to impair the load-bearing strength of the refuse. Precisely this problem and the attendant difficulties of moving heavy equipment arose when vacuum disk filters were installed at a preparation plant in West Virginia. Combining the moist filter cake with the coarse refuse generally results in a 12% moisture level for the total refuse at this plant. At this moisture level, the refuse can still be handled with some dif¬ficulty by the equipment. However, the problem has frequently been compounded after rains. The experimental program described in this paper tested the following methods of improving the load-bearing properties of coal refuse: moisture reduction, addition of crushed coarse refuse, addition of fly ash, addition of lime, and addition of a mixture of lime and fly ash. In terms of a balance between economic and technical considerations, the most effective method was demonstrated by laboratory and plant tests to be a 2% to 5% addition of lime. Test Program During formulation of a test program aimed at improving coal refuse stability, a number of treatment techniques were selected for evaluation of their effect on refuse load-bearing characteristics. The reduction of refuse moisture was the first technique considered, since moisture content plays a key role in the bearing strength of a bulk solid. The reasoning was that a very small reduction in refuse moisture, provided it could be accomplished with minimal effort and cost, would be sufficient for eliminating refuse disposal problems most of the time. At the same time, it was recognized that periods of rainy weather would offset moisture-reduction measures. Other techniques selected for evaluation because of their potential for improving refuse-bearing strength at reasonable cost were: addition of crushed coarse refuse, the addition of fly ash, and the addition of lime. A simple one-dimensional laboratory compaction test was designed for evaluating the effect of each of these techniques on refuse-bearing strength. Those techniques that gave best results in the laboratory would then be tested in the preparation plant in West Virginia. Laboratory Tests The laboratory test for evaluating each of the techniques involved the application of weight to a load module placed on a refuse sample in a container. The distance the load module sank with an increasing amount of applied weight was measured, and the relationship between module displacement and loading was obtained. The refuse container was large enough to minimize the influence of wall effects, and to decrease the effect of the container bottom, a test was terminated when the load module sank to about three fourths the depth of the container. Initially, an attempt was made to conduct compaction experiments with samples of total plant refuse. However, the presence of + 0.13 m (+ 5 in.) material in the refuse interfered with the mechanics of the test, and the large amount of material required for a representative sample made testing extremely tedious and time-consuming. To avoid this problem and because it was believed that only the fine components of the refuse were the major cause of the stability problem, tests were conducted with 13 mm X 0 (1/2 in. X 0) material from the total plant refuse. The equipment consisted of a 0.46 m (18 in.) cubic container, a loading module with 62 cm2 loading area, weights totaling 450 kg, and a portable concrete mixer for combining water and additives with the refuse. Refuse samples of about 110 kg dry weight were used for each test. Experimental compaction test data were evaluated by plotting the linear displacement of the load module vs. loading. During compaction tests, the vertical displacement of the load module was measured at each loading value. The plot of

Jan 1, 1980

By E. I. Alessandrini, A. U. Seybolt

Selective oxidation (preferential oxidation of a single alloy component) can be an important oxidation mode in the case of alloys such as Si-Fe, Al-Fe, and so on, when heat-treating in atmospheres of low oxygen potential. It was the purpose of this work to identify the oxide films formed on iron containing 31/4 pct Si at low oxygen potentials, and to make some observations on the H2O/H2 ratios required to form them. EXPERIMENTAL METHOD HYDROGEN of varying water content offers a very convenient method of establishing a wide range of oxidizing power, or oxygen potential. The method chosen to provide a desired H2O/H2 ratio was to nearly saturate hydrogen at room temperature by bubbling the gas through water at room temperature, and then to wring out the excess water by passing the wet gas through a long glass spiral immersed in a refrigerated liquid at a desired dew point. After oxidation, the samples were examined by electron diffraction in order to identify any film which might be present. PREPARATION AND TREATMENT OF SAMPLES The samples were prepared from a Si-Fe alloy made in the laboratory using electrolytic iron and 96 pct ferro-silico11, vacuum-induction melted, hot-rolled then cold-rolled to 0.015-in. thickness. After the cold-rolling the samples were annealed at 1000°C. Transmission Laue X-ray patterns showed very little evidence of preferred orientation, but it is likely that a weak texture could have escaped notice. The chemical analysis was as follows: 3.34 Si, 0.01 Al, 0.001 0, 0.006 C, 0.002 N. Before each sample was oxidized, it was polished through 4/0 emery paper, cleaned and dried using benzene, carbon tetrachloride, acetone, absolute alcohol, and ether. The method of oxidizing the samples was as follows: Samples about 1/2 by 1 by 0.015 in. were held in the upper, cool part of a vertical vacuum furnace until the desired temperature was established in the furnace, Fig. 1. The sample was then lowered into the uniform hot zone where it was heated quickly to the desired temperature, and subjected to hydrogen of controlled moisture content (dew point) as mentioned previously. Temperatures from 400" to 1000°C were used, and dew points from room temperature to —78°C were explored. In general, the runs lasted about 6 hr, but a few runs were of different duration, as will be indicated later. After the predetermined period of time had elapsed, the specimens were withdrawn by the hollow stainless steel-quartz holder to a cool zone at the top of the furnace. EXPERIMENTAL RESULTS The results are summarized in Table I. Most of the electron-diffraction patterns were obtained by glancing-angle reflection, but in a few cases it was possible to strip the oxide films from the surface by a total immersion in a 3 pct bromine-methanol solution. Some of the thinner stripped films yielded quite satisfactory transmission patterns. However, both diffraction techniques yielded the same results; the patterns while most frequently showing a (low) tridymite, also showed a (low) cristobalite in some cases. A few patterns showed evidence of both phases. Because of the known nonequilibrium behavior of silica, it is not surprising that both forms of silica could coexist on one sample. It was noted that at fairly low dew points such as —40°C, there was a tendency for diffuse diffraction rings, suggesting a very small crystallite size. Also some subsequent experiments to be reported later show that thin silica films can be amorphous.

Jan 1, 1959

By H. O. McLeod, J. M. Campbell

This paper presents the results of the data obtained in the first stage of a long-range study at high pressures of the system, vapor-hydrate-water rich liquid-hydrocarbon rich liquid. The data presented are for the three-phase systems in which no hydrocarbon liquid exists. Tests were performed on 10 gases at pressures from 1,000 to 10,000 psia. One of these was substantially pure methane, and the remainder were binary mixtures of methane with ethane, propane, iso-butane and normal butane. Several conclusions may be drawn from the data. 1. Contrary to previous extrapolations, the hydrocarbon mixtures tested form straight lines in the range of 6,000 to 10,000 psia which are parallel to the curves for pure methane, when the log of pressure is plotted vs hydrate formation temperature. 2. The hydrate formation temperature may be predicted accurately at pressures from 6,000 to 10,000 psia by using a modified form of the Clapeyron equation. The total hydrate curve may be predicted by using the vapor-solid equilibrium constants of Carson and Katz' to 4,000 psia and joining the two segments with a smooth continuous curve between 4,000 and 6,000 psia. 3. The use of gas specific gravity as a parameter in hydrate correlations is unsatisfactory at elevated pressures. 4. The hydrate crystal lattice is pressure sensitive at elevated pressures. INTRODUCTION Prior to 1950 many studies had been made of the hydrate forming conditions for typical natural gases to pressures of 4,000 psia.""'"'"" Most of these attempted to correlate the log of system pressure vs hydrate formation temperature, with gas specific gravity as a parameter. One of the more promising correlations was made by Katz, et al, which utilized vapor-solid equilibrium constants. The only published data above 4,000 psia are those of Kobayashi and Katz7 for pure methane to a pressure of 11,240 psia. In the intervening years, most published charts for the high-pressure range have represented nothing more than extrapolations of the low-pressure data, with the methane line serving as a general guide. The reliability of these charts has become increasingly doubtful (and critical) in our present technology as we handle more high-pressure systems. The portion of our high-pressure hydrate research program reported here was designed to: (1) investigate the reliability of existing charts; (2) obtain actual data on gas mixtures to 10,000 psia; and (3.) develop a simple hydrate correlation that was more reliable than those which simply used specific gravity as a parameter. Binary mixtures of methane and ethane, propane normal butane, or iso-butane were injected into a high-pressure visual cell containing an excess of distilled water. Hydrates were formed and then melted to observe the decomposition temperature of the hydrates at pressures from 1,000 to 10,000 psia. EQUIPMENT The equipment consisted of a Jerguson 10,000-lb high-pressure visual cell, a 10,000-1b high-pressure blind cell and a Ruska 25,000-1b pressure mercury pump. The visual cell was placed in a constant-temperature water bath controlled by a refrigeration unit and an electric filament heater. A Beckman GC-2 gas chromatograph was used in analyzing the gas mixtures after each run was completed. EXPERIMENTAL PROCEDURE After evacuating the gas system, the heavier hydrocarbon was injected into the high-pressure mixing cell to that pressure necessary to give the desired composition. This cell then was pressured to 1,100 to 1,200 psia by methane from a high-pressure cylinder. The mixing cell holding the gas contained a steel flapper plate and was shaken intermittently over a period of 15 minutes. After mixing, the valve to the high-pressure visual cell containing excess distilled water was opened, and the gas mixture was allowed to flow into the cell. The temperature in the water bath was lowered 10" to 15'F below the estimated hydrate decomposition point. As a first check, the temperature was increased at a rate of 1°F every six minutes to find the approximate point of decomposition. It was again lowered 1.5° to 5°F to form hydrates. The temperature was raised to within l° of the estimated decomposition point and then increased 0.2F every 10 to 15 minutes until the hydrates decomposed. This procedure was repeated at various pressures to obtain 7 to 13 points for each mixture between 1,000 and 10,000 psia. After completion of the hydrate decomposition tests, the gas mixture composition was analyzed with a calibrated gas chromatograph. These gas analyses have an estimated error of ± .1 per cent.

By I. E. Puddington

The property of surface tension in liquids is said to have been known to Leonardo de Vinci in about 1500. Approximately'300 years later Thomas Young and others provided the ground rules relating surface tension to the wetting of solids and to the pressure drop across curved surfaces. In retrospect it seems remarkable that more than 100 additonal years were required for substantial technological use to be made of the-information. Thus super critical and freeze drying to avoid shrinkage of finely divided solids have only seen industrial use since the 1930's and doubtless additional possible applications will be equally slow in finding concurrence of conditions to make them attractive economically. The use of a second liquid phase that preferentially wets ,a suspended solid as a flocculant for that solid was pointed out in 1943 (1). Combining this phenomenon with mechanical energy to alter the morphology of the flocs or with surface chemistry to utilize it in the selective flocculation in mixed solids required more than an additional decade. A major stimulant in advancing surface energy based technology 'of suspensions was the report by D. I. Stock in 1952 (2) that mechanical agitation of a dry suspension of barium sulphate in benzene produced dense microspheres of the solid with highly desirable sedimentation characteristics. Investigation of this observation revealed that it resulted from small quantities of water in the system and mechanistically the phenomenon was identical with that reported in 1943.withthe addition of mechanical packing (3). Here then was a base from which to separate more efficiently suspended solids, to make small spheres from powders, to separate selected components from mixtures of finely divided solids or to break emulsions. Each of these possible branches of technology has been slow in developing on other than an experimental scale although considerable

Jan 1, 1979

By Morris Cohen, William P. Kimball

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expression for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: d= Zlxl(xl - P) + Zsxs(P - xs)/Zl(xl - P) + Zs(P - xs) [1] where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, Xl and 28 are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The 6 equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid- to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling, the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By William P. Kimball, Morris Cohen

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expression for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: d= Zlxl(xl - P) + Zsxs(P - xs)/Zl(xl - P) + Zs(P - xs) [1] where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, Xl and 28 are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The 6 equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid- to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling, the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By G. H. Cady, L. C. McCabe, D. R. Mitchell

While running certain float-and-sink tests, unit coal calorific values were determined for gravity fractions of a series of Illinois coals from several districts in the southern part of the state. When these values were plotted against specific gravity what appear to be characteristic curves of somewhat different shape were obtained for each district represented. This in itself seems noteworthy. The shape of the curves seems to indicate that the lightest fraction of the coal, which inspection shows to be largely vitrain, suffers the least deterioration in storage. It was also observed that on dilution curves established with dry ash and B.t.u. values the fractions of 1.35, 1.40 and 1.50 sp. gr., which constitute the greater weight per cent of a given coal sample, fall more frequently on a straight dilution line than do the lighter or heavier fractions of the same sample. In most instances there is a marked steepening between the 1.35 and the fraction of lighter gravity. In general the curve increases in steepness between the fractions of 1.50 and 1.70 specific gravity. The variations in the unit coal-specific gravity curves as well as those observed in dilution curves which appear to be pertinent to this problem are: (I) variation in coal substance with change in specific gravity, (2) variation in kind and quantity of mineral matter with the specific gravity of the fraction, (3) factors of analytical procedure which tend to introduce error in analysis, particularly in high-ash and high-sulfur fractions. DISCUSSION (A. C. Callen presiding) E. Stansfield, ? Edmonton, A1ta.-—The necessity of avoiding oxidation in grinding and in drying should be emphasized. My assumptions as to pure coal coincide with t,he author's but most of my curves are nearly straight lines. The low sulfur content

Jan 1, 1934

WHAT was certainly the greatest event of January, and perhaps it will prove to be the greatest of 1923, or even of the next decade, was the meeting of the premiers of the principal Euro-pean powers in Paris on Jan. 2, to consider what should be done with respect to German reparations. The French and British were unable to come to any agree-ment, and the conference broke up on Jan. 4. The French and British parted friends, but each with the determination henceforth to pursue its own economic and political way. This event was profound in its significance and perhaps will be calamitous) in its consequences. Following the disruption of the Conference at Paris, the French immediately began preparations to occupy the Ruhr district on the ground that Germany was in default on coal deliveries, without waiting. for Jan. 15, the next due date for reparation payment. This action by the French led to orders being issued by President Harding on Jan. 10 for the withdrawal of the remainder of the American troops on the Rhine. Thus ended the physical participation in. European affairs by the American army, whose vanguard landed in France in June, 1917. The French occupation of the Ruhr Valley, i.e., the great industrial region of western Westphalia, was made with a large military force. The Germans offered no physical resistance, and passed under French control with sullen resentment. The coal miners to a con-siderable extent refused to work and there was more or less disorganization of railway service. Before the end of the month the opinion was expressed that the French occupation was an economic failure and there were reports of French blast furnaces being blown out for lack of coke.

Jan 2, 1923

By L. L. Foley, C. V. Millikan

The discovery of Bromide production in the Fitts field, shallow production in Jackson County of Southwestern Oklahoma, abundant production in the Edmond field, and discovery of many small pools in all parts of the state, were the events that made petroleum history in Oklahoma in 1934. Wildcatting was much more active, as evidenced by a number of new discoveries. There was no important development in the older fields. The rapid decline of the potential of the Oklahoma City field was an important feature of the history of the year. The accompanying tabulation of oil fields (Table 1) is not complete. Many of the early records of operators and pipe line companies are lost and it will be impossible to work up complete statistics for a number of the older fields. The table includes most of the important fields of the state and includes fields of a number of different types. It is hoped that a great many additional fields may be worked up for next year's report. Fitts Pool.—The Fitts pool, in Pontotoc County, was discovered in 1933. Before the middle of 1934, the Pennsylvanian sands yielded -some oil at depths ranging from 1400 to 2800 ft. The Hunton series (Siluro-Devonian) produced most of the oil with considerable gas. In July, 1934, a well in sec. 25, T.2N., R.6E. was completed in the Bromide (Ordovician " Wilcox ") with an initial production of about 300 bbl. a day. Less than a month later a second Bromide sand well was completed in sec. 30, T.2N., R.7E., which made over 200 bbl. an hour. This started an active drilling campaign, which was accelerated when some of the major companies paid good prices for adjacent acreage. At the end of the year, 23 wells had been completed and the rate of development was increasing rapidly. It is a major oil field. The Fitts pool opened a new geological province for oil production. The structure is a faulted anticline in a graben. The producing formation (Bromide) and the Arbuckle lime below it crop out about 2 miles south of present production. The Hunton lime crops out about 2½ miles north. The field is in a sharply folded and faulted area on the northeast side of the Arbuckle uplift. Heretofore, it was generally considered not favorable for oil production, although some gas had been found in various places. The play has extended east into the McAlester coal basin, and southeast toward the

Jan 1, 1935

By B. T. Brady

Rock mechanics, like all engineering disciplines, must have a theoretical foundation. The subject of this chapter is the formulation of analytical methods that may aid in the rational design and determination of the stability of engineering structures in competent brittle rock materials. By an engineering structure in rock, we mean any (1) excavated sub- surface opening, (2) open surface structure, or (3) system of openings in rock that is virtually self-supporting-that is, not requiring artificial systems to carry structural stresses. One factor necessary for designing or evaluating a structure's stability is knowledge of the material's mechanical properties, such as stress-strain behavior and fracturing characteristics. The composition of most structural materials such as metals and concrete is uniform and reproducible to the degree that their mechanical properties in service are nearly the same as those measured in the laboratory. Consequently, a rational design can be made on the basis of published mechanical property values. The same equivalence does not exist for rock materials for two reasons: (1) the composition of even the most common rock types is highly variable, and (2) the problem of the size effect is present. Mechanical property tests not conducted at a scale that includes these effects in normal proportion will not be representive of the in-situ rock mass. Of course, the alternative is to perform the test in-situ. Comparatively few mechanical property tests have been performed in-situ because of the physical limitations of test equipment and the prohibitive cost. The current procedure is to design a structure based on small-scale laboratory measurements, with a safety factor usually determined by the experience of the design engineer. While this procedure is somewhat unsatisfactory, laboratory measurements can and do provide a useful basis for the initial design.

Jan 1, 1970

By George Rice

SOME form of longwall mining is generally used in Continental Europe; also in Great Britain where the coal is weak and friable, or the coal bed provides material for pack walls and filling, or where the bottom is soft and squeezes up easily, or the roof is pliable, or the bed is thin and brushing provides building material, or the thick multiple seams are mined in layers, such as the 24-ft. seam at Weymss, Scotland or the 10-yd. pitching bed near Coventry, England. Pillar methods have been retained in British fields where the coal beds are from 5 to 9 ft. (1.5 to 2.7 m.) thick, and free from thick partings or binders or without draw slate, which would provide waste rock for pack walls, or where the roof is hard and requires shooting to bring down and also the bottom or floor is comparatively hard. The room-and-pillar system, by which probably 95 per cent., of the coal of the United States is produced, is now found in only a few mines in Wales, where it is known as the pillar. and .(single) stall method. The American room-and-pillar system is not equivalent to the bord-and-pillar or stoop-and-room system. The essential difference between the bord-and-pillar and the average American room-and-pillar system is probably due to natural conditions. The majority of the coal mines in the United States have a depth of less than 700 ft. (213.m.). The bulk of the coal mined in Europe comes from a depth of more than 1200, ft., while the deepest mines in Great Britain, Belgium, and France reach 3500 to 4000 ft. In deep workings wide spans are impracticable, even with the use of abundant timber; accordingly, as the mines in the United States become deeper the rooms will become narrower and the pillars thicker, and the bulk of the coal will be extracted on the retreat. It is generally conceded, without reference to the cost of production, that the larger the pillars left on the first mining, the more thoroughly can the, coal be extracted. In Europe complete extraction is generally compelled either by the lessors or by the governments; whereas in this

Jan 2, 1921

By Philip W. Henry

There is a difference of opinion among engineers on the subject of depreciation in general, and still more on its application to any given case The committee which was appointed by the American Society of Civil Engineers to make a report on Valuation of Public Utilities, states "There is no subject connected with valuation about which there are more diverse views than those relating to depreciation;" and in the discussion which took place upon the presentation of the preliminary report of this committee in January, 1914, that part of the report dealing with depreciation called forth more discussion than any other. From this discussion it was evident that the word "depreciation" was not always used in the same sense, so it is quite important that some definition be adopted. As this paper relates to the proper method of treating depreciation by corporations or individuals operating oil properties, both of which must make a return of annual net income to the government in connection with the income tax, it will be in order to adopt the definition of the Internal Revenue Bureau. Under date of Mar. 29, 1910, the Commissioner of Internal Revenue of the Treasury Department stated "Deduction on account of depreciation of property must be based on lifetime of property, its cost, value and use." Again, on Form 1035, "Return of Annual Net Income" for miscellaneous corporations (Section 2, Act of Congress approved Oct. 3, 1913), a deduction from gross income is allowed for "Total amount of depreciation for the year." This item is defined more particularly as follows: "The amount claimed under Item No. 5 (b) for depreciation should be such an amount as measures the loss which the corporation actually sustains during the year in the value of buildings, machinery, and such other property as is subject to depreciation on account of wear and tear, exhaustion, or obsolescence. The amount taken credit for on this account in order to be allowable should be so entered on the books as to constitute a liability against the assets of the corporation. The amount claimed under this item should not cover losses in the value of stocks and bonds. Decrease in the book value of securities owned, so far as such decrease represents a decline in the actual value of such securities, should be deducted under item 5 (a) of the return. "Where depreciation of physical property is made good by renewals, replacements,

Jan 1, 1915

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of gas-solid reactions with special attention given to the hydrogen reduction oj dense spheres of hematite. This reduction process must pvoceed through a sequence of transport and chemical .reaction steps acting in series. Under typical experimental conditions, none oj the individual transport and reaction resistances may be neglected in the development of a physically significant model. A linear vate of thickening oj the product layer, usually taken as evidence of interface-controlled .reuction, may be observed even though transport resistances play a dominant role in the over-all kinetics. The temperature and pressure dependencies of all terms have been carefully evaluated in order to .make fill use oj arailable expe-inzental data in evaluation oj the model. FOR obvious technological reasons, the kinetics of reduction of iron oxides has become the subject of intensive experimental and theoretical investigation during recent years. Continuing efforts to construct mathematical models to describe the kinetics of reaction between a gas stream and a granular bed of solid particles have demonstrated the necessity of a thorough understanding of the reaction kinetics of a single particle within the system as a prerequisite to the construction of physically significant models of complex, reacting systems. This paper presents a critical examination of the transport and chemical-reaction processes involved in single-particle oxide reduction and develops the mathematical expressions necessary to evaluate their importance. Comparison of theoretical predictions with experimental results contributes important new understanding of the complex nature of this process. The reduction process has been studied under a wide range of experimental variables, and it is not surprising that apparent conflicts in observation and interpretation appear in the literature. The interested reader is referred to the reviews of Themelis and auvin"? and Manning and philbrook3 for a description of much of this work. The course of reaction commonly has been followed by measuring the oxygen weight loss from the particle as a function of time. A number of authors have suc- cessfully correlated their data in terms of a model which assumes that the reduction process is controlled by the rate of reaction at a single, sharply defined, advancing interface. According to this model, the interface will advance linearly with time. A mathematical model for gaseous reduction in a packed bed developed by the present authors in an earlier paper4 recognized that reduction must proceed through the series hematite (Fe203), magnetite (Fe30,), wiistite (Fe,O), and finally metallic iron. The reduction scheme permitted a stepwise topochemical reduction of the individual particles to metal or to the lowest oxide thermodynamically possible for the local gas composition in the bed. The limiting situations of theoretically dense and very porous oxide structures were considered. On the basis of available experimental evidence, the simplifying assumption was made in each case that all product layers would thicken linearly with time. A generalized single-particle model has now been developed to determine the significance of transport resistances in the product layers and in the gas film surrounding the particle. The analysis shows that the interplay of transport and chemical resistances is such that an apparently linearly advancing interface may be observed despite the fact that the reaction may be under significant transport control. Attention thus far has been focused on the development of a model for the topochemical behavior of dense spheres of hematite in atmospheres capable of reducing them completely to metal. The formation of successive product layers of iron, Fe,O, and Fe304 is assumed to follow the mechanism originally described by dstrijm.' All oxygen removal from the core occurs at the iron/Fe,O interface, intermediate oxide layers being propagated by sol id-state diffusion without change in the oxygen density of the core. Since fractional reduction is operationally defined in terms of oxygen weight loss, the kinetics of the over-all reduction of FeZ03 to iron is properly studied in terms of the gas-solid reaction occurring at the iron-wiistite interface. The fractional reduction of a partially reduced oxide sphere is given by: here refers to the radial position of the iron/Fe,O interface. This model is not universally applicable because, as explained in the earlier paper,4 a consideration of porous particles or of dense particles in atmospheres not capable of reducing wiistite must allow for the possibility of gaseous reduction at interfaces other than the one between iron and Fe,O. However, evidence that certain hematite specimens actually do follow the dense-pellet mechanism developed here is provided by the data of cewan' and of Bogdandy and

Jan 1, 1967

By Henry M. Howe

The transformation which steel undergoes in slow cooling, from the condition of austenite whelk above the transformation rage into that of pearlite plus either ferrite or cementite below that range, is subject to great lag. This transformation is essentially the pearlitizing of the austenite. Indeed the hardenillg of steel is due to this lag, which is made so great by extremely rapid cooling that a very large part of the transformation itself is restrained, so that the rapid cooling catches the metal in an only partly transformed state, that of martensite, and under favorable contditions even in an almost wholly untransformed state, as in the cases of Maurer's austenitic manganese steel. Hadfield's austemtic. manganese steel, 25 per cent. nickel steel, and other anstenitic alloy steels, arc austenitic even after slow cooling. It has long been known that this lag increases (1) with the rapidity of cooling, (2) with the presence of certain retarding elements, notably manganese and nickel, and (3) with the temperature from which cooling starts. The present inquiry touches the last of these influences, but incidentally it throws light on the first also. This influence of higher heating ill increasing lag manifests itself in different ways which, though they may at first seem unrelated, are in fact hut different aspects of one and the same thing. Thus, among heatings to different high temperatures, all of them above the transformation range: the higher the temperature to which the steel is heated (1) the lower is the temperature at which the transformation occurs in cooling slowly down, (2) the shorter is the time occupied in the actual cooling from above the transformation range to the room Temperature under given external conditions, Whether of slow or

Jan 1, 1914

By A. K. Sinha, K. M. Sinha

Several studies concluded by various agencies (Coal Outlook, 1982; Malhotra, 1977) indicate that both the national and international markets for utility coal, which have been growing in recent years due to the uncertainties in petroleum supplies, will continue to grow in the foreseeable future. The areas where the Gemand for utility coal is projected to increase sub- stantially lie close to the midwestern coal fields, in the southeastern US, and in western Europe. Illinois has all the elements necessary to become an important exporter of thermal coal (Library of Con- gress, 1981) provided the coal is desulfurized to meet the environmental restrictions. Because of its high energy content, Illinois Basin coal, if desulfurized, has great potential for competing in the utility markets both nationally and internationally. Sulfur in coal occurs in organic and inorganic forms. The inorganic sulfur in Illinois coal is almost exclusively pyrite. The pyrite can be liberated by grinding and removed from the coal by such techniques as froth flotation. The Illinois Basin coals reportedly contain (Gluskoter and Simon, 1968) an average of 3.57% sulfur. Out of this, 2.06% is pyritic, 0.08% is sulfate, and 1.46% is organic sulfur.

Jan 1, 1986

By L. R. Blair

Many hydrated silicates have been synthesized and sold for commercial use. However, this paper discusses only hydrated calcium silicates and, to a lesser extent, hydrated magnesium silicates. Synthetic calcium silicates were first formed by man when he found that mixtures of silica or silicates and lime in water set up to form cements. The material which was responsible for the cementing properties was calcium silicate hydrate, although this fact was not recognized until early in this century. In the early 19001s, synthetic calcium silicates, reinforced with fibers and formed simply by reacting calcium hydroxide and silica in water with fiber at atmospheric or under low pressure autoclave conditions, found increased use in thermal insulations and in building products. These insulations were found to have a low thermal conductivity and would withstand temperatures up to 650°C. This, combined with their very low densities (from 8 to 50 Ib per cu ft) and fairly high strength, also made them suitable for use as building products. Following the disastrous Morro Castle fire of the 1930Js, calcium silicate board products were used as partitioning material in all shipboard construction in the U.S. As autoclaving techniques were improved and developed, it was: learned that under hydrothermal conditions new and useful calcium silicates which could be used under more extreme temperatures (up to 980' C) could be prepared. These had high surface areas and other unique properties which suited them for use as fillers, pesticide carriers, low temperature insulating materials, and adsorbents for the removal of fatty acids from various solutions. Hydrated magnesium silicates have not been studied as extensively as the calcium compounds. Their first important use was in the filtration of dry cleaning solutions for the removal of fatty acids. With the introduction of detergents, it was found that these products lost their advantage because of their high affinity for the detergent chemicals. However, in recent years these chemicals are finding increasing use as decolorizing agents for fats and anti-caking agents for resins. Some materials with very high surface are finding new use as adsorbents. CALCIUM SILICATE HYDRATE COMPOUNDS AND THElR CONDITIONS OF FORMATION Within the past ten years much has been done in the field of calcium silicate hydrate chemistry. As a result of this work it has been found that at least 25 different forms of calcium silicate hydrate can either be formed synthetically or found as naturally occurring materials. The stability and composition relationships among these 25 compounds present a very complicated picture, and many of these very closely resemble other forms and are difficult to dis-

Jan 1, 1962

By W. L. Chu

It was observed that chromized coatings on low carbon steel could be embrittled by cooling slowly through the 475°C range. A higher chromium coating was more susceptible to embrittlement than a lower chromium coating. Coating structure and composition could be correlated with the chromizing process and prior carbon content of the steel. IT was recently observed that during the fabrication of rectangular tubings made with chromized thin gage 1010 steel, a high percentage of these parts were fractured readily in a brittle manner under the light impact-forming load employed. Ensuing investigation indicated the cause for such brittle failures to be the so-called 475°C embrittlement of the chromized coatings. The experimental work and results are briefly reported. Rectangular tube sections of normalized AISI C1010 steel, which had a cross-section of 0.5x1.5 in. and a wall thickness of 0.030 in., were chromized to yield coatings having several ranges of thickness, varying from 0.0005 to 0.002 in. Essentially, the chromizing process is similar to that described by Samuel and Lockington,' which consists of heating the parts in a sealed container at about 955°C for 4 hr in intimate contact with a chromizing mixture* samples in a hydraulic press, and the other employed a simple beam bending test of the flat sides of the tubing walls. Neither, however, was able to differentiate the relative brittleness of samples known to include both the brittle and tough types, since the impact-brittle samples were found to deform readily in a manner similar to the tough ones. Both the tough and brittle samples were studied by reflection microscopy. Observation showed that the microstructures of the steel cores were similar in content and distribution of inclusions as well as in the ferritic grain size. Results of Filar micrometer measurements showed that coating thicknesses+ of the brittle samples averaged 0.0007 in., whereas those of the tough samples averaged 0.0016 in. The micrographs of Fig. 2 illustrate the structural differences between coatings of both types of samples. By dissolving the steel cores in nitric acid, coatings of both the brittle and tough samples were isolated. Simple bending tests showed that coatings of the brittle samples cracked readily at about 90" bend, whereas those of the tough samples could be bent nearly 180° without cracking. The coatings as well as the steel cores were analyzed for carbon and

Jan 1, 1956

The Wheeler Condenser & Engineering Co., of Carteret, N. J., is now building a line of horizontal and vertical shaft centrifugal pumps for general services, as well as for condenser work.. This company has been building centrifugal pumps for over 20 years, most of them being used, however, in connection with condensers. The new line of pumps is suited for all services. A small motor-driven unit for tank or stand pipe operation is shown in Fig. 1. Referring to the sectional illustration (Fig. 2), it will be seen that this pump conforms to the most recent advances in centrifugal pump construction, having a two-part divided casing, with the suction and discharge nozzles in the lower half. The impeller is of the closed double-suction type, protected by labyrinth wearing rings. The shaft is protected from the water by bronze sleeves, which screw on to the shaft and extend clear through into the bearing bracket boxes. Bearings are of the ring-oiled type, and in the outboard bracket, is a ring-oiled thrust bearing, which is a refinement not usually found in double-suction

Jan 4, 1916

By M. A. Mayers, J. A. Thompson

In recent years, the problem of damage to coke-oven walls by expanding coal charges undergoing carbonization has engaged great attention on the part of research workers in this field, and has led to the development of many devices for estimating these pressures.l-14 Only in Russell's method" and in the Koppers ovens7 are conditions quite similar to those in commercial ovens. Tests even in these ovens are empirical because no information has been published to permit an evaluation of "scale effects." Owing to the relatively large wall area in these test ovens, the average wall pressure determined may be lower than that existing in localized areas. This factor may be compensated for in part by the testing of coal charged into the test oven at a bulk density that is as high as the highest that is believed to exist in commercial ovens. Both of these lacks might be filled by the development of an adequate gauge for the direct measurement of wall pressure exerted by the charge in commercial coke ovens in normal operation. Previous attempts to elaborate such instruments7,15 have resulted in units which, because they had to be water-cooled, probably produced changes in the conditions of carbonization, and which had to be removed from the oven before carbonization was complete, to avoid their destruction. Late in 1941 the Coal Research Laboratory undertook to develop such a gauge, in which gas pressure was balanced against the charge pressure and which thus would not require water cooling, on a suggestion made in 1937 by one of the present authors and William B. Warren, a former member of the Laboratory staff. The gauge heads themselves were to be simple and cheap enough so that they might be discarded after each run if seriously damaged. This would permit them to be left in place throughout the carbonizing period, when they could be pushed out with the coke. The basis of the design, of which the latest exemplification is shown in Fig. I, was that as the internal gas pressure within a flexible metal envelope was increased, the flexible wall would move away from a stop when the gas pressure just overbalanced the charge pressure. If the stop were an insulated electrical contact, the point of balance could be indicated by the breaking of an electric circuit. It was anticipated that, while the instrument must operate at high temperature, the presence of a strongly reducing atmosphere throughout the carbonizing period would so reduce the danger of scaling that mild steel could be used for the gauge. This expectation has been justified. Danger of attack on silica oven walls by the steel gauge body can be eliminated by cementing asbestos paper or an alundum or silica plate to the back of the gauge body. The gauge head itself has a relatively heavy mild-steel body, A, into which standard ¼-in. pipe B is screwed to conduct gas and electrical leads. The body is closed by a single bellows C, consisting of two annuli of 0.011-in. (o.a8-mm.) cold-rolled shim-steel spot-welded together at their outside edges. The lower one is

Jan 1, 1944

By J. A. Thompson, M. A. Mayers

In recent years, the problem of damage to coke-oven walls by expanding coal charges undergoing carbonization has engaged great attention on the part of research workers in this field, and has led to the development of many devices for estimating these pressures.l-14 Only in Russell's method" and in the Koppers ovens7 are conditions quite similar to those in commercial ovens. Tests even in these ovens are empirical because no information has been published to permit an evaluation of "scale effects." Owing to the relatively large wall area in these test ovens, the average wall pressure determined may be lower than that existing in localized areas. This factor may be compensated for in part by the testing of coal charged into the test oven at a bulk density that is as high as the highest that is believed to exist in commercial ovens. Both of these lacks might be filled by the development of an adequate gauge for the direct measurement of wall pressure exerted by the charge in commercial coke ovens in normal operation. Previous attempts to elaborate such instruments7,15 have resulted in units which, because they had to be water-cooled, probably produced changes in the conditions of carbonization, and which had to be removed from the oven before carbonization was complete, to avoid their destruction. Late in 1941 the Coal Research Laboratory undertook to develop such a gauge, in which gas pressure was balanced against the charge pressure and which thus would not require water cooling, on a suggestion made in 1937 by one of the present authors and William B. Warren, a former member of the Laboratory staff. The gauge heads themselves were to be simple and cheap enough so that they might be discarded after each run if seriously damaged. This would permit them to be left in place throughout the carbonizing period, when they could be pushed out with the coke. The basis of the design, of which the latest exemplification is shown in Fig. I, was that as the internal gas pressure within a flexible metal envelope was increased, the flexible wall would move away from a stop when the gas pressure just overbalanced the charge pressure. If the stop were an insulated electrical contact, the point of balance could be indicated by the breaking of an electric circuit. It was anticipated that, while the instrument must operate at high temperature, the presence of a strongly reducing atmosphere throughout the carbonizing period would so reduce the danger of scaling that mild steel could be used for the gauge. This expectation has been justified. Danger of attack on silica oven walls by the steel gauge body can be eliminated by cementing asbestos paper or an alundum or silica plate to the back of the gauge body. The gauge head itself has a relatively heavy mild-steel body, A, into which standard ¼-in. pipe B is screwed to conduct gas and electrical leads. The body is closed by a single bellows C, consisting of two annuli of 0.011-in. (o.a8-mm.) cold-rolled shim-steel spot-welded together at their outside edges. The lower one is

Jan 1, 1944