Search Documents

By C. D. King

The key to maximum production of ingots for the war effort is maximum production of pig iron. For any given furnace and ore, the most important single influence on blast-furnace production is the quality of the furnace coke. It is generally recognized that undoubtedly deterioration of Pittsburgh coking coals will be accelerated by the depletion of some of the better grades of coal; the extension of mine mechanization, with attendant degradation of coal quality; and the opening of new coal fields, some of which are known to be fairly high in sulphur. All of these factors, contributing as they do to higher ash and sulphur, and not infrequently to inferior quality of coke, made it desirable that an extensive study be undertaken to determine the effect of washing some coals that closely approximate the average chemical composition of coking coals to be expected in the future, by the subsidiaries of the United States Steel Corporation in the Pittsburgh district. It was deemed advisable to study the improvement obtained by washing such coals and to determine the need for supplementing the existing coal washery at Clairton to assure continued maximum production of pig iron from presently available furnace stacks. The existence of the cog! washer at Clairton made ii possible to conduct tests on coals used in raw form and on similar coals after washing. This study covers an investigation of the quality of furnace coke as affected by washing coking coals, and is confined to the use of IOO per cent high-volatile Pittsburgh seam coals from Fayette and Greene Counties in the manufacture of furnace coke. It covers the improvement in chemical and physical properties as well as the degree of uniformity in coke obtained by washing these coals, and includes the effect on blast-furnace production and practice. The test period involved is four months; the plants, Clairton by-product coke plant, and the Carrie No. I and No. 2 blast furnaces at Rankin, Pa., Carnegie-Illinois Steel Corporation. Clairton By-product Coke Plant and Coai, Washer The Clairton by-product coke plant carbonizes 30,800 net tons of coal daily in 22 batteries containing 1482 ovens. Three oven sizes are used, commonly known as wide, medium, and narrow types, recognizing the difference in oven width. These ovens also differ in height and length. The present coal washer has a daily capacity of approximately 14,000 tons, leaving I6,800 tons to be carbonized in raw form. Washed coal is used on all the narrow ovens and on three of the six batteries with ovens of medium width, raw coals being used pn all the remaining ovens. The customary arrangement is 7

Jan 1, 1944

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By A. V. Deforest, C. W. Macgregor, A. R. Anderson

One of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing or the A.S.T.M., 1938. The work of Mann.' Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserves especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by P ALo plotting So = 1/A0 as a function of eo = ALr,o where A0 and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors.7'8 It was shown that the true physical behavior of the material in the tension test could best be represented P by plotting the average true stress, S = 2P as a function of 6 = q' = log —r = log ~9L where P, A, L, S, E, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximin load point to fracture. The construction of such curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain dificulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece diameters to fracture under impact conditions offers considerable experimental difficulty. In order to make it feasible to

Jan 1, 1942

By B. M. Larsen, T. E. Brower

Introduction and Summary By "thermochemical factors" we refer to those variables which affect the net heat which must be put into the bath in order to make a heat of steel from any given set of charge materials. This is admittedly only one phase of the production rate problem. The whole problem includes also consideration of rate of charging, flame radiation intensity, rate of optimum fuel input obtainable without undue damage to the furnace structure and any variations in conditions such as stirring, slag volume or viscosity which affect the rate at which heat can flow down and away from those exposed surfaces where the heat is first received from the flame. Because a given type of charge in a shop is often considered as being nearly constant in both physical and chemical characteristics from one heat to another, and because such a state of affairs may be thought of as resulting in a reasonably constant net heat requirement, this requirement is usually neglected as an invariable, inevitable matter, about which nothing can be done. With normally variable charge, and variable percentages of limestone and cold pig, however, the net heat requirement can be subject to very appreciable change; it may also be affected by such things as the currently popular procedure of blowing oxygen into the bath. To bring the general problem of production rate into better perspective, therefore, it seems worthwhile to try to evaluate the net bath heat requirement and the amount by which it may change through variation in different factors. Because our calculated values of net heat are admittedly uncertain, we have tried to check them in part by statistical data on actual production rates over rather large groups of commercial heats. The results of calculation of net heat requirements in a wide range of actual commercial practices may first be summarized briefly. We find a wide range between the extremes of different practices, as would be expected, with duplex practice (essentially blown metal plus hot metal) having essentially a zero net heat requirement, an all-cold charge practice somewhat over I million Btu per ton of steel and a high hot metal practice about 0.75 million Btu per ton. Over the commercial range of scrap plus hot metal practice, increasing the percentage of hot metal from 40 to 78 pct, with other factors nearly constant, decreased the net heat by only some 5-10 pct. The net heat is increased by about 1.2 pct for each I pct of the metallic charge present as cold pig. Calculated values of oxygen supplied by air varied from about 25 up to 60 lb per ton of steel, and in a 60 pct hot metal practice, an increase from 32 to 52 Ib oxygen from air decreased the calculated net heat from 0.88 to 0.74 million Btu per ton. Use of pure cold oxygen to substitute for about one half of the total charge ore (about 28 Ib oxygen replacing 145 Ib ore per ton of steel) decreased the

Jan 1, 1949

By G. A. Moore, D. W. Williams, C. E. Sims

During the past several years the steel casting industry has made studies of heavy castings in which the test bar has been taken from heavy sections rather than from attached or separately cast coupons. It has been noted that the ductility properties of these heavy sections are often lower than those normally expected. Such lowered ductility is usually accompanied by a spotty test bar fracture and the ductility values often can be greatly improved if a low-temperature aging treatment is given to the casting. A loss of ductility of this type is considered "abnormal," since it is not accompanied by an increase of tensile strength or hardness, and "temporary" when the ductility can be restored by aging, The cure of such an abnormal condition represents a real improvement in the quality of the steel. Some hundreds of previous investigations, largely qualitative in nature, have established beyond reasonable doubt that hydrogen is normally present in newly manufactured steel and that this gas, in small amounts, can cause a temporary ab- normal loss of ductility. The commonly observed association of high gas content and low ductility has given strong evidence for the presumption that hydrogen, possibly assisted by other gases, is the primary cause of the low ductility observed. Accordingly, the Steel Founders' Society of America has, since Nov. I, 1944, sponsored investigations at Battelle Memorial Institute whose primary objective is to obtain quantitative information on the relation of the amount of hydrogen and nitrogen in steel, together with associated methods of steelmaking and treatment, to low-ductility effects and porosity. In order that these investigations might proceed on a quantitative basis, hydrogen analyses of a precision considerably higher than any previously reported in the literature were necessary. 'The method chosen was selected entirely on the basis that it had the highest probability of freedom from uncontrollable errors and will be described in detail in another publication.' Briefly, the method used consisted of the hot extraction of solid pieces of steel weighing from 45 to 50 g in a highly evacuated quartz tube maintained at 1050°C (1925°F) for a period of approximately 40 hr. The greatest precautions were taken to eliminate blanks and insure a sound gas-collection system. vacuum and temperature conditions were maintained automatically. Mercury-filled risers were used for the introduction of samples in order that the System could be degassed thoroughly in

Jan 1, 1949

By T. R. Graham, R. G. Feustel, J. R. Long, R. S. Dean

The comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined. These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their- physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. Composition and Fabrication of Alloys The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys mill be referred to hereafter by their norninal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedurzs calculated to produce sheet $i6 in. thick, cold-reduced by 20, qo, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from 700' to r500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By D. R. Conlon, E. R. Brownscombe

Errors in measurement of reservoir pressure include: (I) gauge errors, and (a) interpretation errors. Gauge errors may be reduced by: (a) reading charts with a comparator microscope, (b) use of hard metal stylus points to give clear lines, (6) insuring temperature equilibrium, and (d) making multiple tests. Check calibrations are equally as important as check well tests. A statistical analysis of such check runs shows quantitatively the advantages of a standardized "zero pressure line'' and of the use of field calibrations made at bottom-hole temperature on the same chart run in the well. Interpretation errors include: (a) fluid heads, which should be corrected to the top of the perforations on the basis of well-fluid gravity and from the top of the perforation to the datum level on the basis of reservoir-fluid gravity, and (b) gradients around the well. Conventional shut-in periods may be entirely inadequate to overcome these, necessitating a reservoir study based on build-up curve data, reservoir history, core analysis and any other available information. Interest in engineering studies of the pressure changes in oil and gas reservoirs is increasing. This type of work yields important information and doubtless will be greatly extended in the future. One of the factors limiting the work, however, is the accuracy with which the reservoir pressures can be determined; for if the inaccuracies in the pressure measurements represent an appreciable percentage of the pressure changes, the engineer is seriously handicapped, and must delay the reservoir study until the reservoir pressure has changed a relatively large amount. This delay can greatly reduce the benefits of such studies, at least from the point of view of aiding the leasing, drilling and completion programs. Thus, from the point of view of reservoir analysis, it is frequently important to obtain the most accurate pressure data possible early in the history of any field—particularly for the gas-distillate fields now being developed. This paper deals with improvements in the measurement of bottom-hole pressures that permit pressures even as high as 4000 or 5000 lb. per sq. in. to be determined with gauge errors of only+ ±I to 2 lb. per sq. in. Since pressures out in the reservoir rather than in the bottom of the hole concern the reservoir analyst, differences between bottom-hole pressures and actual reservoir pressures are also considered. In general, errors in pressure measurement may be divided into: 1. Gauge errors: a. Errors due to inaccuracies in reading the pressure charts. b. Errors due to irreproducibility of the pressure element and recording system. c. Errors caused by failure to allow the gauge to reach temperature equilibrium. 2. Internretation errors: a. Errors caused by a fluid head between the gauge position in tubing and the pressure at the datum level in the reservoir. b. Pressure gradients in the reservoir.

Jan 1, 1946

By T. H. Dunn, P. L. Menaul

This paper discusses the results of an investigation made to develop a method of combatting corrosion of subsurface oil-well equipment caused by brines containing hydrogen sulphide. Carbon monoxide, aldehydes, and certain cyanide compounds were found by laboratory tests to effectively inhibit corrosion of steel by sulphide brines. Experiments were made for one year in eight wells in West Texas fields using formaldehyde as an inhibitor. It was found that the inhibitor treatment successfully prevented the severe corrosion previously experienced in these wells, and effected important net savings in operating costs. Introduction Corrosion of oil-field equipment has long been a problem in areas producing sour crudes. These areas include the major fields of Arkansas, Western Kansas, West Texas and New Mexico. Corrosion in these fields is caused primarily by the chemical action of hydrogen sulphide in the presence of water and by electric currents entering the wells through flow lines. Hydrogen sulphide is noncorrosive to iron or steel in the absence of water but under the usual conditions prevailing in oil wells where more or less water is present, hydrogen sulphide is very corrosive. This type of corrosion occurs over the pH range below 9, which includes all natural oil-field brines. If air is present in addition to hydrogen sulphide and water, corrosion proceeds at an extremely rapid rate. It was reported several years ago that a string of oil-well tubing was literally dissolved within 50 days where an air lift was used on a well producing considerable water and hydrogen sulphide. Air is generally absent in wells producing sour crude. After hydrogen sulphide corrosion starts, it proceeds with increasing severity and its correction becomes progressively more difficult. This characteristic of sulphide corrosion has been attributed to the formation of galvanic couples between the iron and steel equipment on one hand and the products of corrosion on the other.' Severe corrosion of subsurface oil-well equipment leads to a multitude of troubles. In addition to destruction of costly equipment, producing sands often are damaged by flooding with water leaking through corroded casing; bad mechanical conditions may develop in a well due to obstructions caused by corroded equipment lost in the hole, or partly collapsed casing; pumping operations are interfered with, and severe emulsification problems may result from the homogenizing action of corroded balls and seats.% A typical case of severe corrosion caused by hydrogen sulphide was reported in Howard County, Texas, where it was necessary to pull tubing once a week to repair leaks after the tubing had been in use for only one year. On one well in this area a string of tubing was pulled 11 times in 8 months; 11 joints of tubing being replaced because of leaks. In Ector

Jan 1, 1946

By T. W. Guy

IN approaching the problems of sampling coal, a brief statement of certain facts that are more or less taken for granted may be helpful: 1. The coal-mine operator needs reliable data as to the physical and chemical characteristics of his coal in order to plan and control intelligently its mining, preparation, and marketing. The consumer needs such data in order to select the equipment and the coal best suited to meet his requirements, to check the quality of fuel delivered, and the efficiency of its use. Various government control agencies require such data as a basis for classifications and establishment of limits, for use in carrying out the requirements of federal, state or municipal laws. 91. All such data must be obtained by analyses, measurements, or tests made on samples, which are taken to represent the coal tested. It is now becoming generally recognized that, in accordance with statistical laws, test results from samples are not expected to represent the exact qualities of the lot or lots from which they are taken, except within statistical, or "expected limits. Such limits are definitely specified by some present standards of the American Society for Testing Materials and the British Standards Institution. 3. Samples that give ash within satisfactory limits are usually assumed to be sufficiently accurate for other analyses, except under special condi¬tions such as meeting close specifications for coals showing wide variability in sulphur, fusibility of ash, or other quality. 4. In modern coal sampling the increment is recognized as the basis for taking samples. For a given accuracy the number and weight of increments specified are increased with: (a) the expected ash, and (b) the top size designation of the lot to be sampled. 5. It is extremely important that every sampler recognize that: the specified number and weight of increments are minimums, and that the precautions to be used in order to take them properly are also minimums; that in the reduction of the gross sample the sizes specified for the coal after each stage of the crushing are maximum; that the quantities specified to be taken after each crushing stage are minimum; that any short cuts or failures to meet the requirements specified will reduce the statistical accuracy of the results, although it is possible that one or two checks on a few results may seem to show otherwise.

Jan 1, 1943

By A. S. Appleton, M. B. Bever, G. E. Dieter

A gold-silver alloy was deformed by explosive loading at shock pressures up to 510 kbars. The stored energy and hardness increased over the whole range of pressures; the largest rates of increase were observed between 120 and 150 kbars. In this range, markings rkavacteristic of defornation twins first appeared; higher pressures produced markings in all grains. These effects are compared with those of conventional deformation processes and are discussed in relation to probable structural changes. In recent years, increasing efforts have been devoted to the investigation of the effects produced in metals by the passage of high-intensity shock waves of explosive origin. By properly utilizing the energy released by the detonation of a high explosive, it is possible to generate pressure pulses of the order of 500 kbars and higher. (One kbar equals l0 9 dynes per sq cm or approximately 1000 atm.) The passage of a shock wave through a metal occurs at pressures which are very much greater than the yield strength. As the shock front passes a point in the metal, the pressure rises almost instantaneously, and continues to act at the point for a few microseconds. Thus, metals subjected to explosive shock loading experience a nearly instantaneous increase in pressure, and a subsequent release of pressure, which is almost as rapid. Under these conditions mechanical twinning and shear transformations occur readily. smith1 has investigated the metallurgical changes in copper and iron resulting from exposure to explosive shock waves. He found an appreciable increase in hardness in both metals. In copper, a hardness greater than that resulting from 95 pct reduction in thickness by rolling was obtained, yet in the explosive deformation, the thickness of the specimen decreased only a few percent. After explosive loading, the micro-structure of copper showed markings characteristic of mechanical twins. The amount of stored energy resulting from explosive loading is of interest. Measurements of the stored energy of cold work as a function of strain, temperature, strain rate, and composition have been made with gold-silyer alloys deforyed by rolling, orthogonal cutting,3 drilling,4 filing, wire drawing, and torsion. The investigation reported here was also carried out with a gold-silver alloy and its results can be compared with those for the deformation of this alloy by more conventional methods. EXPERIMENTAL PROCEDURES An alloy containing 82.6 wt pct Au and 17.4 pct Ag was purchased in several batches from Handy and Harman Co., New York, as annealed rod 1/4 in. dim. The rod was cold-rolled to a sheet approximately

Jan 1, 1962

By Y. Nakada, B. Chalmers

The work-hardening behavior of surface layers of aluminum and gold single crystals was investigated by alternately deforming and then removing a thin surface layer by electropolishing or by etching. Aluminum crystals exhibited lower flow stresses after the surface removal; gold crystals did not. Abrasion of surface eliminated easy glide in both gold and aluminum crystals. By alternately deforming and removing the surface layer, it was shown that the abraded crystals work-harden preferentially under the abraded layer. It is suggested that this phenomenon is caused by the difficulty of propagating dislocations through the abraded layer. It has been demonstrated in numerous cases'-3 that the plastic behavior of metals in either single-crystal or polycrystal form is sensitive to the environment and to the condition of the surface; it has also been reported4-6 that single crystals of some metals, when deformed in tension, exhibit more work hardening near the surface than in the interior. A third type of effect that has been attributed to the special part played by the surface in plastic deformation is the influence of the dimensions of the specimen on the various parameters that define its plastic-deformation characteris- tics.?-'' Many of these experiments were made on aluminum, on which an oxide film is always present under available experimental conditions; many of the effects have been attributed to the oxide film, either in terms of its higher elastic moduli, which would cause local stress redistribution, or its higher strength, which would oppose the escape of dislocations at the surface of the metal. On the other hand, it has been suggested II,12 that the mere presence of a surface should be sufficient to produce the observed results. A rigorous examination of this question could, in principle, be carried out by comparing the behavior of aluminum with its oxide film with that of the same material without oxide. This experiment would present great difficulties. The most practical alternative is to compare aluminum with gold, which has no crystalline surface film at room temperature, and to study the effects of various surface treatments on gold. The experiments described in this paper fall into two groups, the objectives of which were to determine 1) whether single crystals of gold shared the property of aluminum that the removal of a surface layer after some plastic deformation reduced the flow stress for further deformation and, since the result of this was negative, 2) whether a surface treatment could be found that caused gold to behave in this way. I) EXPERIMENTS AND RESULTS All the tests described below were carried out on single crystals of about 6 by 6 mm cross section and of sufficient length to provide a gage length of about 10 cm.

Jan 1, 1964

By G. P. Gladis, R. H. Atkinson

PALLADIUM has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items-at least 100 times as rare as gold. Although both visual and spectrophotometric examination demonstrated that the color of palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400° to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu' of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith' deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-' make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.' It has received confirmation in the recent work of Dench and Kubaschewski,' and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968

By J. B. Reed, T. A. Read, H. Rosenthal

Although the season cracking of brass has been a subject of experimental investigation for more than thirty years, the mechanism that is responsible for this phenomenon is still obscure. While at- tempts to elucidate the stress-corrosion cracking of some alloys have been relatively successful, the principal accomplishments made in the studies of the season cracking of brass have consisted of improved techniques for the fabrication of articles of alpha brass, which reduce the danger of season-cracking failure in service. The primary purpose of the present paper is to collect the published experimental data which appear to be of importance to the development of an adequate theory of the mechanism of the season cracking of brass. Some of the possible mechanisms which have been proposed will also be discussed, together with some promising avenues of future attack on the problems. Several excellent survey papers on season cracking are available, including the recent ones by Croft and Sachs(1)2 and by Gibbs(2). The principal facts concerning season cracking, as presented in these papers, may be summarized as follows. The season cracking of alpha brass is a special type of stress-corrosion failure, which may occur in atmospheres containing ammonia, air, and water vapor. The stress causing failure may be either the

Jan 1, 1945

By Ralph A. Sherman, J. M. Pilcher

BY surface treatment of coal is meant the application of a material, either solid or liquid, to the surface of pieces of coal. The purposes of surface treatment are varied. They may be to identify or "trade- mark" the coal, to modify the burning characteristics, the coking tendencies, or the behavior of the ash, to prevent the freezing of wet coal, or to control the dust. The control of dust is the usual purpose of surface treatment. TRADE-MARKING COAL The application of color to the surface of coal for the purpose of identification and registration of the trade-mark has been practiced to some extent. In 1928, the Glen Alden Coal Co. began to color its coal and adopted the trade-mark, "Blue Coal." The Old Ben Coal Co. later followed a similar practice with "Green Coal." A commoner means of identification of coal has been the stenciling of designs or pasting labels on large lumps or in the distribution of small cardboard tags through the smaller sizes. The details of the method used to color coal have not been revealed. Usually all of the coal is not treated, because of the expense. Only enough pieces are colored to show clearly when distributed through the coal. The patent literature gives information on some of the methods proposed. Esselen and Weiss have patented the deposition of a coloring material in the valleys of the surface of the coal. Sperr covers the quenching of coke with water containing a pigment or dye that will deposit on the coke. He also suggests electroplating with copper or nickel. Glinsmann subjects the freshly fractured coal surface to the action of an alkali or alkali earth ferricyanide and a ferric salt. Barsky and Hanson specify a method for the application of the same chemicals covered by Glinsmann. COATINGS FOR IMPROVEMENT OF APPEARANCE As a purchaser often judges coal by its appearance, modification of the surface has been attempted from time to time, particularly of the surface of outcrop or stored coal, which has become covered with a brown film of iron oxides, but information is lacking as to the extent or success of the

Jan 1, 1950

By A. L. Ph. B. Holley

(Read at the Philadelphia Meeting, February, 1878.) THIS paper is an abstract and a discussion of results obtained by the United States Test Board in experiments upon 14 brands of wrought iron, most of which are well known and of high repute.* The iron was all intended for chain-cables; it was tested in the form of bars, usually of nine sizes, from 1 inch to 2 inches round, and also in the forms of single links and short chains. Not less-than 2000 tensile tests were made, each showing elastic limit, elongation, and reduction of area. This work was done with conspicuous intelligence and fidelity, at the Washington Navy Yard, by Commander L. A. Beardslee. Some important practical results and principles which he has developed, and others which he has confirmed, will be referred to. The chemical part of this work consists of 42 complete analyses (including slag), by Mr. Blair, chemist to the Board. EFFECTS OF COMPOSITION ON STRENGTH. Variations in the physical qualities of iron may he due to different composition, or to different treatment in manufacture, or to both these complex causes. In order to determine the specific causes of variation, one class of altering conditions should be made to vary largely, while the other classes should be kept uniform. Then another class should be varied, and so on, until the value of each is ascertained. As all the irons under consideration were intended to have that purity and refinement which was deemed indispensable in chain-cables, their chemical analyses are perhaps more important in proving that physical variations result chiefly from treatment, than in pointing out the specific effects of certain ingredients. While the subject of treatment-especially the increase of strength by greater reduction in rolling-may be the more important one, it can be best appreciated after we have familiarized ourselves with the gen¬eral chemical and physical characters of the irons. The typical facts are given in the following tables. * As the present object of the Board is not to compare the products of different makers, but to discover the physical effects of various composition and treatment, the irons are designated by letters rather than by their trade names.

Jan 1, 1878

The present paper records a chapter in the history of the development of an electrolytic manganese industry in the United States.l A relatively large pilot plant at Boulder City, Nev., for the production of electrolytic manganese was conceived as part of the national defense program to make this country independent of foreign importation of manganese ore. The first authorization, in November 1940, however, was for a plant of only several hundred pounds capacity. Improvements in process and subsequent additions to some sections authorized by subsequent appropriations have enabled the plant to produce as much as 2000 lb. of manganese a day for substantial periods of time. Since in pilot-plant operation frequent changes are made in the flowsheet, the electrolytic manganese plant was constructed so that equipment could be rearranged with a minimum of expense and time. Several different kinds of the various ¦ types of equipment were installed for many of the operations, so that the one most suitable for the process might be chosen. Pilot-plant operations were begun in November 1941 and have been continuous except for brief shutdowns for installation of new equipment. More than one-half million pounds of manganese have been produced. The improvements in process, selection of equipment, and operational procedure developed are recorded here. Development of the Process The work of early investigators on the electrolysis of manganese solutions has been reviewed by Shelton. Until the method of continuous production of manganese by electrolysis was perfected by SheltonZm4 and coworkers, no practical procedure had been devised. The method as originally developed by the Bureau of Mines will be described here only briefly. The manganese dioxide ore was reduced in a rotating kiln-type furnace at 650°C. in an atmosphere of "city" gas. The calcine was leached with spent electrolyte and enough sulphuric acid to produce a neutral leach solutioil containing 2 5 grams manganese per liter as manganese sulphate and zoo grams per liter of ammonium sulphate. Arsenic was removed from the solution by the addition of 0.0j gram iron per liter as ferrous sulphate followed by oxidation with manganese dioxide, and aeration, which precipitated the iron as ferric hydroxide. The solution, free from iron

Jan 1, 1944

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By R. I. Parsons, M. B. Standing, E. N. Lindblad

The recovery of the heavier components from a gas cap or retrograde pool is shown to be the greatest when the sand is cycled with a dry gas at a low pressure. This conclusion is in direct opposition to the belief that the most efficient production program is pressure maintenance and cycling at or near the dew point. The results are calculated from: (I) constant volume, variable composition pressure-volume-temperature tests on a mixture of trap gas and liquid from a producing well; (2) published equilibrium constant data and the measured composition of the dew-point material; and (3) the fact that in a sand section of homogeneous permeability, injected gas displaces reservoir gas nearly, quantitatively. The results are based on the simplifying assumption that variable permeability systems may be defined by the ratio of two statistical parameters, and that gas injected into an actual sand will behave as though the sand were composed of many layers, each of constant permeability. Introduction Pressure decline in gas-condensate type reservoirs is accompanied by the formation of a liquid phase throughout the reservoir. Over the past ten years the processing of the material from these types of reservoirs for the heavier hydrocarbon components and the return of the light fractions to the reservoir ("cycling") has become increasingly popular. It has often been stated that the purpose of such a program is to prevent the loss of the retrograde liquid phase formed in the reservoir. The purpose of this paper is to present the results of laboratory tests and computations concerned with several possible methods of producing a gas cap or condensate type of reservoir. The results show that the recovery of heavier hydrocarbons for this type of reservoir is not a maximum under conditions of cycling at or near the dew-point pressure. Instead, variations in permeability and the ability of the dry injected gas to revaporize condensate, point to cycling at a considerably reduced pressure as the optimum production-method. In addition the paper suggests a way of evaluating sands for their permeability variation. The calculations presented in the following sections of the paper are in terms of the production of the butanes and heavier fraction from the gas cap of a field which had an original pressure of approximately 3000 psi. Specifically, the calculations show: 1. To what extent the condensate formed in the reservoir after pressure decline can be recovered by the cycling of a dry absorber-plant gas through the sands. 2. Whether there would be greater recovery of hydrocarbons if cycling were instigated at the original reservoir pressure.

Jan 1, 1948

By Lester L. Hirst, Arno C. Fieldner, Henry H. Storch

EXPERIMENTAL work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogenation of bituminous coal and tar by the Bergius-.I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 lb. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydrogenation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. EQUIPMENT AND GENERAL PROCEDURE OF RESEARCH The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944