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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 R. C. Dalzell, A. E. Wells

In 1866, Thomas Graham1 called attention to the volume of gases, three times the volume of the sample, evolved from a meteoric iron heated in an evacuated porcelain tube. From that time to this the occurrence and significance of gases in metals have been the subject of investigation by many workers, among whom Sieverts,2 Iwasé3 and 0. W. Ellis4 stand preeminent. Sieverts and Iwasé concerned themselves with the solubility of a number of gases in metals in the liquid and solid states. They determined the absorption coefficients of these gases, and in all cases found a sharp change in solubility at the melting point of the metals. Ellis analyzed the gases evolved by solidifying copper and those occluded by the solidified metal. Lobley and Jepson5 endeavored to determine the effects of hydrogen, carbon monoxide and nitrogen on the porosity of copper that was allowed to solidify in the presence of each gas after 30 min. exposure to it in the

Jan 1, 1930

By T. S. Lundy, C. J. McHargue

HE diffusion rate of v48 in single crystals of bee vanadium has been determined at temperatures from 1002° to 1888°C. Standard techniques of lathe sectioning were used for specimens annealed above 1500°C while sectioning by grinding was used for specimens annealed at lower temperatures. As will be seen, the lower-temperature data is enhanced on an Arrhenius-type plot relative to values expected by extrapolation of the high-temperature data. Single crystals were obtained from Linde Co. In Table I the analysis supplied by the vendor is compared with an analysis at Oak Ridge National Laboratory of a sample after a diffusion anneal. The isotope v4' was prepared by the Isotopes Division of Oak Ridge National Laboratory. Proton bombardment of a titanium target in the 86-Inch ORNL Cyclotron was followed by a carrier-free chemical separation. Nineteen specimens, 1/2 in. diam and 3/8 in. long, were cut from the as-received vanadium single crystals. Each specimen was machined with the flat face perpendicular to the longitudinal axis. Specimens were polished through 1/0 emery paper and were etched with 25 pct HF-10 pct H2SO4-10 pct HNO3-55 pct H2O. The polishing and etching steps were repeated until a satisfactory surface finish was achieved. The isotope was electroplated onto the specimens from a neutral solution. Counting rates of the deposited layers were approximately 100 counts per sec. At temperatures above 1200°C specimens were annealed in a tantalum resistance furnace under an argon atmosphere. Temperatures were measured with a Pyro micro-optical pyrometer and a Pt-Pt 10 pct Rh thermocouple. At lower temperatures the specimens were sealed in evacuated quartz ampoules and annealed in Kanthal wire-wound horizontal tube furnaces. A severe reaction occurred at 1200°C between the quartz and the vanadium. This

Jan 1, 1965

By Gordon E. Agar

Several correlations have been proposed to relate energy consumption and size reduction in comminution, and although these are arrived at from different starting points, it is postulated that they are all statements of the same basic concept. To test this postulate, the dry ball mill grindability of langbeinite was determined, and the results were analyzed according to the various methods. An examination ' of the energy-particle size relationships proposed in the recent past revealed that they had much in common. In fact, the conclusion was tentatively drawn that these expressions were essentially the same, even though they were arrived at from quite different basic premises. The equations attributed to Charles2 and Holmes3 were shown to re- duce to the same single equation, W - A K-3, and the simulated continuous test used by Maxson et al.4 was shown to give the best experimental value of the required empirical parameter, ß. Furthermore, the size distribution parameter a in the Schuhmann equation, y - (x/K)2, was shown to be equal to ß in many cases. The kinetic approach used by Arbiter and Bhrany5 should give the same results as the Maxson test procedure; however, the batch operation used by Arbiter and Bhrany could not produce data that would be as precise as the simulated continuous technique. To test the validity of these conclusions, the simulated continuous method was used to obtain data on the dry grinding of langbeinite. The results are discussed in terms of the various equations and approaches. APPARATUS AND MATERIAL A ball mill with internal dimensions of 17.5 cm (6 7/8 in.) in length by 19.4 cm (7 5/8 in.) in diam was loaded to 50% of its volume with balls 3.2 cm in

Jan 1, 1969

A. M. CANDY,* Pittsburgh, Pa.-I think more stress should be laid upon the question of welding with the carbon electrode, which we ordinarily call graphite arc welding. Mr. Miller's photograph indicated that the original parent metal had been decarburized to a marked degree. It would be interesting to know the carbon content of the parent metal, and whether or not Mr. Miller has made any investigations to determine if the metal is always decarburized or whether in some instances we actually have carbon injected into the weld, which has been the understanding that has been quite prevalent. There were one or two other points that Mr. Miller brought out concerning which I desire to ask one or two questions: The illustrations that he presented were obtained with what, I suppose, would be termed a real low-carbon steel welding wire, which gives in the deposited metal grains that are more or less symmetrical, whereas the Roebling electrode, which is a mild steel of higher carbon content, apparently gives a columnar structure. I do not know which-of these I structures is more desirable, but assuming that the structure produced by the really low-carbon steel wire is the more desirable, would it not be true that the very low carbon content would, probably owing to high temperatures that prevail in the arc, result in a greater amount of oxidation and probably result in either carrying into the weld more oxide or producing more oxide on the surface as the operator progresses? The short arc is an advantage in all cases. Whether Mr. Miller's trouble is oxide or nitride, the short arc helps him out, because the closer the end of the electrode is to the work the less chance there is for either oxygen or nitrogen to get in. And whichever is the cause of the trouble, the short arc keeps it out by lessening the time in which the steel is molten and the amount of air that gets in. It also makes sure that the molten metal will not fall into the crater. Everything is in favor of the short arc.

Jan 4, 1919

By David L. Holt, Walter A. Backofen, Anwar-ul Karirn

ANNEALING the binary alloy, Mg-0.5 wt pct Zr in a hydrogen atmosphere results in extensive precipitation of zirconium hydride. The morphology of these precipitates has already been investigated.lm3 Squires, Weiner, and phillips4 found, following creep testing of the hydrided alloy at 450" and 500°C, that hydride denuded zones formed along grain boundaries that were aligned approximately normal to the tensile axis. Zone formation was attributed to diffusional creep by magnesium transport down the prevailing stress gradients.4'5 Recently, electron microprobe analysis by Karim, Holt, and Backofen6 showed the zones indeed to be zirconium-free and furthermore it was shown that in compression, zones formed along boundaries approximately parallel to the stress axis. Thus it was confirmed that the zones are formed by diffusional creep. Typical zone-formation is shown in Fig. 1. Karim, Holt, and Backofen also measured the con- tribution to the total strain, from diffusional flow, slip creep, and grain boundary shear: results showed that diffusional strain tends to saturate with increasing imposed strain, while grain boundary shear eventually becomes the dominant deformation mode. It was suggested in explanation that the precipitate-denuded zones are soft and easily sheared, such deformation contributing to the grain boundary shear measurement. A point to be emphasized is that the Mg-0.5 Zr alloy was not superplastic for the index of strain rate sensitivity of flow stress, m = a log log 6 was only 0.25. It was recognized that diffusional creep in a poly crystalline aggregate must be accompanied by boundary shearing.' The suggestion was that the non Newtonian-viscous character of diffusional creep in the Mg-0.5 wt pct Zr alloy is due to resistance to sliding of boundaries lying approximately parallel to the tensile axis.= The work described in the present note should be seen against the above background for it represents initial efforts to observe in a similar way diffusional creep in a superplastic alloy. Previous work with the ternary-alloy Mg-6 Zn-0.5 Zr, pellet extruded, showed it to be superplastic however it does not contain resolvable precipitates to act as internal markers for diffusional creep. Also the fine grain size of the alloy (0.5 p) made conventional metallography rather difficult. Solubility relationships in the Mg-Zn-Zr system are not well known, however making reasonable guesses about the probable phase diagram of the ternary, Mg-Zn-Zr, various heat treatments were attempted to produce hydride precipitation. Finally a 16-hr anneal at 495' in hydrogen was found to pro-

Jan 1, 1970

By W. S. Ayres

The construction of a new breaker at the Cranberry Colliery, Hazleton, Pa., was forced upon the operators, A. Pnrdee & Co., by a fire which destroyed the entire plant early in January, 1896. The loss included, in addition to the breaker, three boilerhouses and three engine-houses. The boilers were not injured, but the steam-pipes and connections were all broken and warped by the fire. The boilers were probably saved from injury by the presence of mind of the fireman., who started all his feed-pumps and filled the boilers with water. The hoisting-engines were more or less warped and cracked, but by patching and replacing the injured and broken parts, they were made to do satisfactory service in the new plant. It may be worthy of mention that the wrought-iron shaft of one of the hoisting-drums, 12 inches in diameter by 17 feet long, was so heated in the fire that the weight of the drum caused it

Jan 1, 1899

By H. E. Nold

THIS paper is an effort to explain in a simple manner the fundamental principles involved in examining a clay deposit for both quantity and quality and in operating a clay mine, either open-pit or underground, so that the best quality of finished material can be made from the raw material available. The writer is aware that what is recommended in this paper is everyday practice in many refractories plants and in some other heavy-clay products plants, but observations made while visiting practically every clay mine in Ohio have convinced him that the practices herein discussed are not as widely used as their importance warrants. It is true that the problem of mining for quality is more acute in refractories plants than in most heavy-clay products plants, yet some of the latter are finding it profitable to pay more than ordinary attention to the selection and blending of their raw materials. It is hoped that this short paper may prove helpful to some who are now finding it difficult to produce a uniform product of as high quality as their clay deposit seems to warrant. The coordination of the work of the clay mine or pit with the manufacturing plant, to the end that the best product possible be made from the raw material available, presupposes a rather intimate knowledge of the clay deposit. The knowledge must include not only information of the amount of clay-available but also rather detailed information about both vertical and horizontal variations in quality of the clay. This information should cover three things: quality, quantity, and location.

Jan 1, 1929

By M. N. Dunlap

Tries article summarizes the successful incorporation of a flash-flooding stream into the tailing-disposal system at the St. Joseph Lead Company's Federal Division mill, in St. Francois County, Missouri. The mill was built in 1906, by the Federal Lead Co., as its No. 3 mill for the concentration of southeastern Missouri lead ores, and damming Davis Creek was first considered in 1908. Plans were made also in 1925 and in 1937. Dam layouts varied from a reinforced concrete structure to a barrier built of tailings alone. All were abandoned because of liability that would be incurred by flashflood rupturing of an incompleted dam. By 1942 mill capacity had reached 12,000 tons daily and increasing tailing-disposal costs again focused attention on the Davis Creek basin. This time the problem of riskless dam building was solved. Moreover, most of the items that appeared in the answer were materials that normally required wasting and the major portion of labor involved performed functions that it would normally have done, without constructive benefit, elsewhere. The new layout also made possible advantageous changes in mill-water supply pumping; static head being reduced from 514 ft to 95 ft, friction head from 4900 ft to 2860 ft, and pumping can be done now at periods of low power demand. The following facts about the Davis Creek watershed explain the 36-year reluctance to reach these, and other, benefits. Size: 3600 acres. Outline: roughly pear-shaped, 2 1/2 by 3 miles at the largest dimensions. Topography: mostly hill land with steep valleys. Relief : 760 minimum to 1153 maximum. Maximum rainfall: 3.36 in. per hour. Permanent water: none natural. Now 2200 gpm discharged through 16-in. drill hole from mine pumps underground. Geology: the 17 acres near dam centerline is Bonne Terre dolomite covered with sand and gravel eroded from Pleistocene beds that cap some of the hills. The remainder of the pond basin is on Davis shale. Soil cover: mostly second-growth timber with some abandoned fields; all subject to careless burning, which reduces water-retaining ability. Flood history: flash-flooding that had taken at least one life. Downstream values: two railroad bridges before creek intersection with Flat River. Immediately below confluence, a highway bridge, a low-water crossing, a few business establishments and several blocks of residences. In July 1942 the following segments of an ingenious plan were put into operation. A ditch 270 ft long, 16 ft wide and 5 1/2 ft deep was excavated to bedrock in the gravelly soil along the proposed dam's centerline. This excavation, which exposed many gravel-filled channels, was run full of slimes drawn from a riser set in the top of an adjacent tailings-disposal

Jan 1, 1947

By K. E. Merklin, F. D. DeVaney

In the past most of the research in pelletizing has as its aim the production of a physically strong pellet. Now that this problem is solved, more attention is being paid to uniformity in grade and chemical composition. Consideration has been given in recent years to a study of additives which will make pellets partially or fully fluxed. Blast furnace tests show fluxed pellets to have advantages over both fluxed sinter and acid pellets. Lower slag volumes are used more frequently in the blast furnace and the uniformity of the charge, both physically and chemically, is becoming increasingly important. A considerable improvement can be secured by having all of the flux uniformly distributed through the pellets in a calcined state. A fluxed pellet, therefore, should be a superior product. The use of an ore burden that contains an appropriate quantity of fluxing materials is not new to the blast furnace industry. For years the Minette ores of France and Germany, the Clinton ores of the Birmingham, Ala., areas, as well as others, which are low in iron but contain calcium carbonate in sufficient quantities to give them self-fluxing properties, have proven economical. The adaption of the sintering process to the preparation of ore burdens provided a means for artifically associating the fluxstone with the iron ore prior to charging to the blast furnace. In 1944 Torpl discussed the effects of using lime in sinter made in Sweden on the sinter's metallurgical performance in a blast furnace. Hessle2 reported in 1945 on the advantages of using lime in sinter to increase the sintering plants' capacity and reduce fuel requirements. Robinson3 discussed the use of lime in Swedish sintering practice at the 1950 Blast Furnace, Coke Oven, and Raw Materials meeting. One of the suggested advantages was the combining of lime with silica to prevent the formation of a fayalite slag, which is difficult to reduce in the blast furnace. Nilson4 at the same meeting commented briefly on experimental work that had just started in the U. S. on the use of lime in sinter. The literature tends to indicate that most of this early work was directed towards improvement in sinter physical quality, and the fact that the feed to the blast furnace was partially fluxed was incidental. It was not long, however, before blast furnace advantages were being claimed. The matter was forcibly called to the attention of North American operators by reports of remarkable production records established by the Russians using fluxed sinter. The leading step was taken on this continent by the Steel Company of Canada in 1957; McMahon5 reported on the marked improvement in performance of an 18-ft blast furnace using fluxed sinter at its Hamilton works. Other North American operators quickly followed theStelco lead.

Jan 1, 1963

By E. E. Underwood, L. L. Marsh

Aluminum single crystals, alloyed with 0.042 atomic pet Cu and 0.11 and 1.1 atomic pct Mg, were subjected to constant stress creep tests, tensile tests, and hot hardness measurements within a temperature range of 300° to 866OK. Calculations based on Dorn's temperature-compensated time parameter, 6, gave a value of DH, = 27,000 cal per mol for the activation energy of early creep in aluminum single crystals. Correlations have been obtained for aluminum alloy single crystals with the parameter E for solid solution strengthening, as well as with the parameter F for solid solution hardening, by using a valence of three for aluminum. Limited measurements on tensile specimens show that the slip band density tends to decrease with increasing temperature and with decreasing solute concentration. INCREASING interest is being shown in the mechanisms of plastic deformation in single crystals during tensile and creep testing. The complexity of deformational processes in polycrystalline materials has led to a search for simpler experimental conditions. Numerous creep and tensile investigations have been conducted with pure, metallic single crystals. To a lesser degree, the effects of alloying elements on the tensile properties of single crystals have been determined. However: the literature dealing with the effects of alloying additions in single crystals under creep conditions is vanishingly small. This paper represents an attempt to narrow this gap in the knowledge of the subject. Previous investigations of creep behavior at the Battelle Memorial Institute1-1 have been of great value in the analysis of the present single crystal data. It is equally desirable, however, to ascertain the extent of correspondence between the behavior of single crystal and polycrystalline materials. For this purpose, correlations, similar to those developed for polycrystalline aluminum alloys by Dorn and co-workers, have been made with the single crystal data. The results from this study have tended to confirm and extend those correlations to the case of alloyed single crystals. Materials and Procedures Three dilute binary aluminum alloys were prepared for this investigation from 99.99 + wt pct Al, 99.8 wt pct Mg, and 99.92 wt pct (electrolytic) Cu. The nominal compositions of the alloys were 0.042 atomic pct Cu, and 0.11 and 1.1 atomic pet Mg. Precautions were taken to avoid contamination of the stock during melting and casting of the alloys. After a heat treatment of 8 hr at 925°F the alloys were extruded, then machined into) threaded tensile specimens with a 3 in. reduced section and a 0.505 in. diam. Spectrographic examination showed less than 47 ppm metallic impurities in each alloy. The single crystals were grown by the strain-anneal method, with a critical strain of about 11/4 pet giving the optimum results. In general, 3 in. crystals were obtained with the Al-Cu alloy, but smaller crystals in the magnesium alloys necessitated the use of 2 in. and 1 in. gage lengths with the low and high magnesium alloy specimens, respectively. After an electrolytic polish, the orientation of that portion of the specimen containing the largest single crystal was determined from Laue back-reflection photographs. Tensile tests were conducted at a constant load rate of about 2 lb per min. Creep runs were made in a constant temperature room, under constant stress at the higher creep temperatures, and constant load at the lower temperatures. The eloneation was measured to within ±5 microin. by a specially designed capacitance extensometer. The ex-tensometer arms were attached to the 3 in. specimens at the shoulders of the test piece or, where the crystals were smaller than 3 in., by knife-edge grips.

Jan 1, 1957

By D. Harker, M. J. Murphy

The mechanism by which age-hardening takes .place is still not completely understood. The principal theories range from the extreme of "precipitaiion-hardening" to that of "order-hardening," with many intermediate gradations. In the hope of obtaining new data on which to base a choice among the many theories, the authors have made electron micrographs of formvar replicas taken from metallic specimens at various stages of age-hardening. The results so obtained on an alloy of 2 per cent beryllium in copper and one of 20 per cent molybdenum in iron will be described in the following pages, as well as the technique used in preparing the replicas. Preparation of Formvae. Replicas of Metallic Specimens This section is concerned with the techniques that have roved successful in preparing formvar replicas for studying the microstructure of metals with the electron microscope. Because of its simplicity and accuracy, the formvar replica1 method developed in the General Electric Research Laboratory has been used exclusively, since it is much simpler than the silica replica method of Heidenreich and Peck2 and produces as good results. The formvar method to be described requires a technique acquired only by practice, and no foolproof set of rules can be given. it is a rapid method and a replica can be obtained in less than five minutes under favorable conditions. This does not mean that perfect replicas can be produced every five minutes, but rather that one can well afford to take several strippings* in order to produce a replica of high quality. The metallographic technique required for replica work—very fine polishing and etching with very dilute solutions—is described here. It can be said, in general, that almost any surface that has been carefully prepared for a photomicrograph at 1000 or more diameters can be used to obtain a replica for the electron microscope. Preparation of Metallographic Specimens The preparation of the metallographic specimens is somewhat more exacting than that usually given to samples to be used for inspection under the light microscope. After much experimentation, it was concluded that the best method consists in polishing the metal through to the coarse cloth, then etching and repolishing on final cloth until the layer of distorted metal is removed. After this procedure has been completed, a dilute etch—to approximately the depth necessary for a micrograph at 1000 diameters—usually produces a sur-

Jan 1, 1945

By B. D. Cullity

INTRODUCTION THIS investigation of bismuth-selenium alloys was made in an attempt to find a suitable material for use in thermoelectric generators. These devices are simply thermocouple circuits designed for the efficient production of electrical energy from thermal energy, which may in turn be derived directly from solar radiation or from the combustion of fuels. The requirements of a material for use in a thermoelectric generator are obviously quite different from those of a material used in a temperature-measuring thermocouple. Naturally, for power generating purposes, the thermoelectric power (voltage produced per degree difference in temperature between the junctions) must be as high as possible. Furthermore, in order to obtain reasonably high power outputs, the materials used in the generator must have an electrical conductivity which is as high as possible. Finally, in order to minimize heat lost by conduction to the cold junction, the thermal conductivity must be as low as possible. The relation between these several factors and the efficiency of conversion of thermal into electrical energy-the thermoelectric efficiency-has been discussed by Telkes1 in a recent review of the subject. She gives the thermoelectric efficiency as: [ ] For many materials, some of the desired properties (for example, high electrical and low thermal conductivity) are almost mutually exclusive; the problem thus becomes one of finding a material which has the optimum combination of properties. BISMUTH-SELENIUM ALLOYS Work on the equilibrium diagram of the bismuth-selenium alloys has been reviewed by Hanson,2 who gives the diagram reproduced in Fig I. There are two intermediate phases in this system, BiSe and Bi2Se3. The existence of an alpha and beta modification of BiSe has not been demonstrated satisfactorily and the writer found no evidence of it in the present work. BiSe and Bi2Se3 have, like bismuth, a rhombohedral crystal

Jan 1, 1948

By J. B. Morrow, D. H. Davis

THERE are two general approaches to the problem of increasing profits from an operation. One is to lower expense; the other is to raise income. Mechanical preparation of coal may be used for either purpose but a prudent consideration of many details must precede any decision lest the results be negative instead of positive. It is quite possible that any net gain will result from a combination of the two. Since mechanically prepared coal invariably is a better product qualitatively than a hand-picked coal from the same mine, it is a reasonable expectation that the customer will be willing to increase the producer's income by paying a higher price. Or there may be the possibility that a combination of mechanical mining plus mechanical cleaning will give a lower over-all production cost for the coal in the railroad car. More likely, there will be found a combination of these two factors. From the customer's point of view, the competitive delivered cost per B.t.u. considered in relation to such incidental factors as dust nuisance, handling properties, ash disposal, and ash fusibility determines what he will pay. In-a bulk tonnage such as coal, freight is a very considerable part of the delivered fuel cost, and obviously freight paid on incombustible ash has no economic attractions. INCENTIVE FOR CLEANING Coal is prepared in four major ways: l (1) by screening or sizing, (2) by mixing or blending, (3) by cleaning, including hand picking and mechanical cleaning, (4) by dustless treatment. By a combination of any or all of these methods, coal can be prepared to standard specifications. It is easily possible to have good cleaning and still get a poor final product because of faulty screening or mixing, while it is possible to produce a very acceptable product from mediocre cleaning if the coal is well screened and mixed.

Jan 1, 1950

Gach-Saran.—The most important development of 1937 has been the successful completion of initial exploratory wells in the Gach Saran (formerly known as Gach-i-Qaraghuli) field, about 125 miles southeast of Haft Kel. Two of these wells are rated at 33,000 bbl. per day at flowing pressures exceeding 800 lb. Drilling is proceeding with the object of delimiting the structure. Exploratory drilling is also being undertaken in several areas within the company's concession. In the producing fields the policy of controlled production has been maintained as in the past, and drilling has been limited to that required for maintenance of production and general control of the fields. Acid treatment to increase production when desired has continued to be successful in most cases. Table 1.—Crude Production in Iran Masjid-i-Sulaimana Haft Kel Total Year barrelsb Ton Barrelsb To Barrelab 1936 3,641,247 27,820,000 4,473,849 34,200,000 8,115,096 62,020,000 193P 4,375,112 33,110,000 5,693,849 43,480,000 10,068,961 76,590,000 * Net production; i.e., excluding surplus products re-injected to reservoir. 6 To nearest 10,000. " Correct to November, with an added estimated figure for December. Masjid-i-Su1aiman.—There have been no new developments in this field. The policy of returning, as and when necessary, surplus products to the reservoir has been maintained. Haft Ke1.—Drilling to explore deeper formations has been undertaken, but has not progressed far enough for conclusive results to be drawn. Gasoline retention in the crude by means of multistage pressure stabilization has been continued as in past years. Separation pressures are as follows: well-head separators, 500 lb.; central battery, 190, 85, 40, 20 and 10 lb. per sq. in., respectively. The stabilized crude is delivered to pipe line at atmospheric pressure, or ex the 10-lb. stage, in accordance with refinery requirements.

Jan 1, 1938

Discussion of the paper of G. Howell Clevenger and Bhupendranath Ray, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2437 to 2475. ALLERTON S. CUSHMAN,* Washington, D. C.:-I am very much interested in the subject matter of this paper. I have had occasion to speak to this question before. There has recently been so much written and said and claimed about the effect produced by the addition of small quantities of copper to steel that there is certainly an impression abroad that a new and wonderful cure-all has been discovered. Are we facing a method of alchemy by which, at the expenditure of very little trouble and only a few cents' worth of copper per ton, the well-known characteristics of steel with respect to some features are so marvelously changed as in effect to produce a new metal ? I am a great believer in the future of the iron and steel alloy field. I do not think that with all the advances we have made in metallurgy we have begun to scratch the possibilities of usefulness to mankind in the exploration of the alloy field, and I include in that alloy field even what might be designated as the dilute alloy field; that is to say, where a very small quantity of a metal alloyed with iron and steel confers upon it some new or extraordinary qualities. With respect to many of the physical characteristics of the copper-iron or copper-steel alloys I am not particularly competent to speak. With respect, however, to the investigation of corrosion problems and with respect to claims made with regard to resistance to corrosion, I am competent to speak insofar as I have specialized to some extent in that field and have given up a great deal of my time for a great many years to a study of it. Some years ago, being particularly interested in the study of corrosion problems, I received the very generous permission of a large manufacturing concern to use their large open-hearth furnaces any way I saw fit for exploring this particular field. There is not a metallurgist in this room who will not realize the generosity of a manufacturing company who would permit a man to pursue a theory and give him as his material to work with 60 tons of molten metal. At all events, I threw copper into the open-hearth furnace. I explored this alloy field, not in a ittle crucible in which I had to take out portions and have them

Jan 12, 1913

By P. Majani, F. P. Kokesh, M. Grosmangin

Determination of the quality of cementation of casing in oil wells in the past has involved inflow and circulation tests to insure that the producing zones were adequately sealed off from the adjacent zones. Existing logging methods, such as temperature and radioactivity surveys, may detect the presence of cement behind the casing. However, the qualities of the cement (i.e., its hardness and particularly its bond to the casing) are not indicated. The new logging method described in this paper operates on the principle that the attenuation of a sonic pulse transmitted by a casing is greatly increased when that casing is bonded to an outer annulus of hard material (such as set cement) which has an appreciably smaller sonic-wave velocity than that of the casing. The down-hole tool contains a source of recurrent sound pulses which are detected by a receiver spaced a few feet from the source The amplitude of the detected casing-borne pulse is measured, and the resulting signal is transmitted to the surface where it is recorded vs depth. Since amplitude is a function of attenuation, the log is readily interpreted. Laboratory studies have shown straightforward relationship between attenuation and such variables as source-detector spacing and per cent of circumference bonded. It is shown that cement not set or not bonded to the casing has compara- tively little attenuating effect. Field examples show not only the cement top, but also the variation in cementation quality below the top. Further, the increase of bonding with time and after squeeze cementation is depicted. The detection of poor cement jobs is confirmed by production tests and by formation-test results. It is anticipated that the method will have wide application in evaluating cementation quality prior to formation testing in completions and recompletions. The analysis it affords may aid in further improving cementation techniques. INTRODUCTION The main purpose of oilwell cementing is to isolate a production zone from other undesirable zones. To investigate whether this purpose has been accomplished, several logging methods have been used such as temperature logs, radioactive tracer logs, etc. While these logs all respond to the presence of cement behind the casing, they do not indicate the degree of bonding of the cement to the casing. Early in the application of sonic logging, it was noticed that considerable attenuation of sound signals takes place in cemented pipe and is often made evident on the standard Sonic log by cycle skipping.' The development of a circuit capable of continuously recording the amplitude of the casing-borne sound signal has made possible an extensive series of laboratory and field tests, which gave the following results. The amplitude of a sound signal after it has traveled in a firmly cemented pipe is only a small fraction of that recorded by the same device in free pipe. This provides a wide spectrum of energy levels; for given local conditions, empirical values of the amplitude can be correlated with the quality of cementation. Interpretations made in this manner generally have been confirmed by production tests, circulation tests and squeeze cementation. The purposes of this paper are to give a general description of the new logging method and to present some laboratory and field results. CYCLE SKIPPING Early attempts to study the quality of the cement behind the casing were performed with a standard Sonic log, which measures the transit time At, and were based on the well known phenomenon of cycle skipping.' Cycle skipping normally is interpreted as being a manifestation of weak signals at the receivers. The log of Fig. 1 was run with the recording instrumentation adjusted to enhance cycle skipping. A mirror-image presentation was used for better visual interpretation. The transit time of sound in steel is about 58 microseconds/ft (corresponding to a velocity of 17,000 ft/ sec), and the portions of the log where this value is recorded are interpreted as zones with no cement bond. Where cycle skipping produces a higher value of At, weak signals (or a high rate of attenuation) are indicated, and a good cement bond may be present. The occurrence of cycle skipping, however, depends too much on instrument adjustment to give a uni-

By G. E. Keller, G. D. Coe

Several methods have been devised for rapid determination of sulfur in coal using a high-temperature combustion furnace. The fundamental principles of the various methods are similar but the techniques vary widely. The method described herein is no different in principle from some of its predecessors but varies considerably in technique. Originally devised to overcome the low-accuracy criticism leveled against the others, the tube-furnace method has proved successful for limited applications. Work is being done to widen the applicability of the technique. Subsequent to the work of A. Vita1 in 1920, a number of investigators have published data dealing with the rapid determination of sulfur in coal using a high-temperature combustion furnace.2-5 These, together with several unpublished methods, involve wide differences in technique although they are all similar in principle. Investigation of typical details of procedure showed that poor precision or accuracy could be attributed to one or more of the following: 1) inadequate quantity of sample to be representative, 2) a delivery tube temperature too low to confine condensation to a washable area of the tube, 3) no provision for back washing the delivery tube, 4) incomplete absorption of the sulfur compounds due to inadequate bubbler, and 5) the false assumption that all of the sulfur is evolved as sulfur dixoide. The method herein discussed is no different in principle from some of its predecessors; the differences are in technique. Although the method is rapid—a determination can be completed in 5 min— accuracy has riot been sacrificed in order to achieve speed. MATERIALS AND EXPERIMENTAL WORK Fig. 1 shows the arrangement of the equipment. A metered volume of oxygen is passed through calcium chloride for removal of moisture, then through Ascarite for removal of carbon dioxide, and thence through a glass tee to the feed end of the combustion tube. Connected to the side arm of the glass tee is a rubber tube that is closed with a pinch clamp during combustion of a sample. The products of combustion are expelled through a Vycor bubbler, the end of which is submerged 3 cm below the surface of a 1 pct hydrogen peroxide solution contained in a 300 ml high-form beaker. At the completion of the 4-min combustion period the contents of the beaker are titrated to a yellow end point, using a methyl red indicator, with 0.05 N sodium hydroxide (or sodium tetraborate). The pinch clamp on the tube leading from the tee in the oxygen line is then opened and mouth suction applied to draw the hydrogen peroxide up into the bubbler past the ell, almost to the rubber tube connecting the bubbler to the combustion tube. This washing of the bubbler is repeated until no further acid reaction with the indicator is obtained. The hydrogen peroxide-sul-furic acid solution is then titrated to the final yellow end point. Test work conducted at the Robena Laboratory disclosed the following critical conditions that had important bearing on the precision of the method: Weight of Sample: Several series of tests wherein the sample weight ranged from 0.1 to 0.5 g of -60 mesh coal showed that the lowest variance (standard deviation squared) resulted from the use of 0.5-g samples; the variance was slightly greater when 0.3-g samples were used, and with less than a 0.3-g sample weight the variance increased rapidly with decrease in weight. Although the use of a 0.5-g sample invariably resulted in a very slight explosion as soon as the sample entered the hot zone of the combustion tube, this did not detract from the precision of the method. Temperatures: Mott and Wilkinson5 found that a combination of low temperature (1250°C) and low oxygen flow rate (less than 700 ml per min) tended to give high results due to formation of oxides of nitrogen. Although the method herein employs a much higher oxygen rate than 700 ml per min, as an additional precaution to assure accurate results, 1315°C (2400° F) is recommended as the most desirable furnace temperature. The temperature of the elbow of the bubbler should be at least 75°C to minimize condensation

Jan 1, 1961

By J. S. Orphanos

The requirements for controlling air and stream pollution are a most timely subject for concerned people. The coal industry has taken great measures to reduce pollution. With the use of more efficient scrubbing equipment on their thermal dryers, pollution has been considerably reduced. Furthermore, eliminating thermal drying completely by using centrifugal dryers (Bird screen bowls) to dewater fine coal products and meet consumer specification has completely eliminated air pollution. The coal industry is taking steps to eliminate stream pollution and the hazards created by tailings ponds. These plants are closing their water circuit by recovering all solids in solid-bowl centrifugal equipment. In doing this effectively and economically the water discharged into the streams does not contain any refuse solids. This provides a safe economical method.

Jan 1, 1976

By Harold Rose

THE peak of production from the Appalachian natural gas field was apparently reached about 10 years ago, and the annual production from Pennsylvania, West. Virginia and Ohio has now dropped to about two-thirds of the amounts obtained in 1916-and 1917. This falling off in production has occurred in spite of vigorous efforts and large expenditures by producing companies to maintain or increase their output. The greatly increased costs of development and handling are reflected in the present average value of natural gas at the point of consumption, which value in the three states referred to, has more than doubled in the past 10 years. While it is true that the natural gas production of the United States has increased during recent years, this increase has come from southwestern states, particularly from Oklahoma, California, Louisiana and Texas, which states are now leaders in the production of this valuable but fleeting resource. Pennsylvania, originally the leading state in natural gas production, occupies sixth place in the latest (1924) U. S. Bureau of Mines statistics. West Virginia, which held first place for 15 years, has dropped to third rank, and Ohio is the seventh state in the order of natural gas production. Domestic and industrial demands for gas are constantly increasing everywhere in the United States. These growing demands have accentuated the difficulties in the localities with depleted natural gas supplies, and serious shortages have already occurred during winter months in the Pittsburgh district. Some relief has been obtained by placing restrictions on the industrial use of natural gas, and by, increasing the price (which tends to reduce consumption). Yet these are but temporary expedients for checking gas consumption, which fail to solve the problem of adequate future supplies of gas.

Jan 10, 1926