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By R. W. Heckel, R. E. Trabocco

The recovery process in 400 Monel filings was followed, principally, by using the Warren-Averbach technique of X-ray peak profile analysis. The deformation fault probability, a, was 0.006 in samples of unannealed filings. a , the twin fault Probability , was approximately 0.002 in samples of unannealed filings. Both a and 0 were found to "anneal out" at 600°F. The effective particle size and mzs strain increased and decreased in the (111) direction, respectively, with increasing annealing temperature. The actual particle size was found to be almost equivalent to the effective particle size. Tile small values of deformation and twin fault probabilities accounted for the similarity in values of the effective and actual particle sizes. Stored strain energy and dislocation density calculations based on rms strain decreased with increasing annealing temperature. The dislocation density decreased from 10" per sq cm in the unannealed filings to 10' per sq cm in the partially re-crystallized filings. The square root of the dislocation density based on strain to that based on particle size indicated a random dislocation distribution in the unannealed filings. The dislocation arrangement changed to one with dislocations in cell walls with increasing annealing temperature. THE recovery processes which occur in metals are generally thought to be a redistribution and/or annihilation of defects.' Investigators' have shown that recovery processes can be characterized by X-ray line-broadening analyses. Michell and Haig4 measured the stored energy of nickel powder by calori-metry and found the value to be greater by a factor of 2.5 than that from X-ray data obtained by the Warren-Averbach technique.= Minor increases in particle size occurred up to 752°F (recovery), while above 752°F the particle size increased greatly due to recrystalliza-tion. X-ray microstrain values decreased between room temperature and 392"F, remained constant from 392" to 752"F, and decreased from 752°F to a negligible value at 1112°F. Faulkner developed an equation for calculating stored strain energy based on X-ray line-broadening data which gave a closer correlation of measured and calculated stored strain energy based on the data of Michell and Haig. The stored strain energy released during recovery is predominately dependent on the decrease in dislocation density which was p-enerated from cold work.7 Stored energy has been measured8 in alkali halides during recovery and recrystallization and 80 pct of the stored energy was found to be released during recovery. Dislocation distributions have been studiedg in a number of fcc metals by thin-film electron microscopy. Howie and Swann" found the stacking fault energy of copper and nickel to be 40 and 150 ergs per sq cm, respectively. ~rown" has pointed out that these stacking fault energy values should be corrected to 92 and 345 ergs per sq cm, respectively. The dislocation distribution of a metal is directly dependent on the stacking fault energy of the system. Metals of high stacking fault energy such as aluminum cross-slip readily and do not form planar arrays of dislocations. Metals of lower stacking fault energy such as stainless steels" do not cross-slip readily. Cold-worked nickel has been found to form a cellular dislocation structure after annealing.13 The relatively high stacking fault energy of nickel and copperlo to a lesser extent favor cellular structures of dislocations rather than planar arrays after deformation. The present study of recovery was carried out on a Ni-Cu alloy (Monel 400) to compare with prior studies for pure nickel and pure copper. X-ray line-broadening techniques were used to measure the effect of recovery temperature on rms strain and particle size and the results were compared with previous studies on copper'4-'7 and nickel., Calculations were also made on stacking fault probabilities, dislocation density, dislocation distribution, and stored strain energy as affected by temperature. EXPERIMENTAL PROCEDURE The nominal analysis of the Monel 400 used in this investigation was: 66.0 pct Ni, 31.5 pct Cu, 0.12 pct C, 0.90 pct Mn, 1.35 pct Fe, 0.005 pct S, 0.15 pct Si. The annealed material was cold-reduced in two batches, one 50 pct and the other 80 pct. It was originally planned to conduct line-broadening studies of these bulk samples; however, rolling textures that developed produced low-intensity peaks which were not suitable for line-broadening analysis. Filings were prepared at room temperature from both the 50 and 80 pct cold-reduced specimens, series A and series B, respectively, and were not screened prior to heat treatment or X-ray studies. Heating to the annealing temperature, 200" to 120O°F, was accomplished in a matter of minutes in a hydrogen atmosphere. Following heat treatment, some of the filings were mounted and polished for microhardness measurements with a Bergsman microhardness tester, using a 10-g load. A G.E. XRD-5 diffractometer using nickel-filtered Cum radiation was used to obtain all diffraction patterns. Only (111)- (222) line-broadenin data were used in the present study since the {400f peaks were too weak to use. The Fourier analysis of the (111) and (222) peak

Jan 1, 1969

By R. W. Diamond

Low-grade ores can be designated by two main classifications: (1) simple low-grade ores, and (2) complex low-grade ores. As a rule the first type has a relatively small metal content, although low- grade iron ores contain a rather high percentage of metal. As the simple type is the one that is ordinarily in mind when the term "low-grade ore" is used, the paper will be devoted mainly to ores in this general category. Cheap treatment is the prime requirement in utilizing low-grade ores of the simple type, although in some cases the value of nonmetallic by-products, such as limestone for fer- tilizer and silica for flux, allows a little more lati- tude than in the usual situation. When the costs are divided under the three headings-mining, milling, and smelting-it is apparent that the last group will not constitute an important factor as a rule because the high concentrating ratio makes the smelting cost per ton of ore fairly low.

Jan 1, 1949

By R. H. Ogburn

THE GROUND now being worked by the Fairbanks Exploration Co., near Fairbanks, Alaska, has been known to be gold bearing since 1901. In the early days it was worked by drift mining and other small-scale methods. In 1922, Hammond started prospecting the gold-bearing ground and obtaining options on the properties desired. Two years later the present Fairbanks Exploration Co. started taking up the options, and preparing to exploit the ground. For the prospect drilling Keystone drills were used, with holes at the points of equilateral triangles 600 ft. apart. Holes were also put down more closely spaced to determine the limits of dredging ground. In the first drilling casing was used to the bottom of the holes, but in later work the casing was put down only to the bottom of the thawed ground, and the rest of the hole put down without casing. The gold content was determined by panning, each 2 ft. of depth being determined separately. Where no casing was used the size of the hole was determined by using water to measure its volume. The greatest concentration of gold occurs at or near bedrock. All the gold-bearing streams head in one big dome. Gold, however, is not found clear to the head of the creeks, the pay being first found some distance downstream from the head.

Jan 1, 1933

By William F. Boericke

THERE was a time when the selection of fire brick was .left to the judgment of the head bricklayer of the plant, whose choice was not unaffected by a box of Christmas cigars from a friendly salesman. But the days are past when it was generally believed, with complacent philosophy, that bricks were bricks without much distinction, and should be bought on a price basis alone. Gone, too, is the belief that in certain types of industrial work the eventual failure of refractories was assured. Modern metallurgical practice, with its trend toward handling larger tonnages at higher temperatures, demands the use of refractories that cannot be supplied by random guess. The logical development is to inquire into the properties of the brick to be purchased, and this resolves itself into the use of specifications. In 1925, the General Refractories Co., with the active support and hearty cooperation of some of its larger customers, established a laboratory, at its Baltimore plant, for testing and research in refractories. This was the outgrowth of a growing appreciation of the value of research in the refractory field. Since then the work has become more involved' and the aims more ambitious, so that the present laboratory now employs a staff of 11 men working, under the direction of trained refractory technologists, on problems of research as well as the routine control of manufacture. It is believed s that `this type of laboratory is a comparative novelty among refractory manufacturing plants. It handles the testing and research work for all the 15 plants of the organization. Being at one of the works has the advantage of making it possible to carry on large scale plant tests on new products after the preliminary laboratory tests have been successfully completed.

Jan 1, 1929

By Charles E. Locke

DEPRESSION in all lines of the mineral industry except gold, which began in 1930 and continued, even worse, through 1931, had its effect on ore concentration. Construction was limited to the completion of plants already begun. Every possible economy was adopted. Changes and improvements involving expense were postponed. Research was largely abandoned. Operations became highly efficient and costs were cut down, although this did not necessarily mean a lower cost per ton because of the greatly reduced capacity at which mills were run. Lower metal prices caused the operators to seek the optimum ratio of concentration and grade of concentrates looking toward maximum economic recovery; that is, net profit. In the crushing field no marked changes occurred. The Symons cone crusher for intermediate work is in use almost everywhere. Its manufacturers claim that 900 machines have been installed in 21 countries, replacing two previous steps of crushing and yielding a product sufficiently fine to form a satisfactory feed for rod mills and ball mills. A new Telsmith crusher has appeared which has curved jaws something like the Symons cone and consequently the same advantage as the latter.

Jan 1, 1932

By Clyde E. Williams

MODERN steelmaking has gradually evolved from an inefficient small-scale operation, utilizing tiny units, to a highly efficient one utilizing large units almost completely mechanized. The leading position of the United States in the steel industry is due to the possession of easily assembled high-grade raw materials and large-scale highly developed plants. Modern integrated steel operation is largely one of material handling. Mining and transportation of iron ore, coal, and fluxes, coking the coal in by-product ovens, smelting the ore with coke and limestone in blast furnaces, converting the resulting pig iron into steel in the Bessemer, or in the open hearth when supplemented with scrap, and fabricating the resulting steel ingots in the shapes of commerce all are done on a huge scale, mostly by machinery, most of the labor being employed either in operating the machine or keeping it in repair. At the same time the quality and uniformity of the product have been greatly increased by the development of scientific knowledge and operating skills. Thus, the steel industry in this country is highly developed both mechanically and technically.

Jan 1, 1942

Prof. H. O. Hofman, Massachusetts Institute of Technology, Boston, Mass. (communication to the Secretary): When Mr. Stetefeldt quotes me as saying that " silver-assays are uniformly made by scorification," he has evidently not understood that I was referring solely to the practice of silver-lead smelting-works. Everybody knows that silver-mills do not employ the scorification-assay for regular work ; and it is equally certain that in very few, if any, silver-lead smelting-works will the crucible-assay be found in use for determining silver. The second part of the quotation, "as it is adapted to all kinds of ores and gives excellent results unless organic matter is present," although, of course, also intended in a restricted sense, might very well be extended to a general one. Mr. Furman, in his Manual of Practical Assaying,* says, on page 123: "We believe that the Colorado practice is preferable, as most ores will yield higher silver-results by scorification." The fact that the scorification-assay is the accepted one in Colorado is strong presumptive evidence for its accuracy, as exactness would nowhere else be more jealously demanded. Mr. Stetefeldt cites Albert Arents- as a supporter of his preference for the crucible-assay, although I had already done so in favor of scorification. Looking up again the reference, I find that I was justified in quoting him, as, while Mr. Arents advocates the crucibleassay for low-grade gold ores, not on account of the greater accuracy of its results, but because it is quicker and less expensive, he condemns it§ for the assay of silver-ores, and prefers the scorifier for rich goldores, and for coppery ores, and in general for ores containing both silver and gold. As I, like Mr. Stetefeldt, have kept no detailed

Jan 1, 1895

By T. P. Clendenin

THE northerly two thirds of Mexico falls into five main physiographic divisions, illustrated on the accompanying map. In form, these divisions are a series of strips, paralleling the northwest-southeast axis of the country.

Jan 10, 1951

By H. M. Manasevit, R. L. Nolder, L. A. Moudy

The observation that silicon-on-sapphire crystallo-graphic relationships exist which are unrelated to one another implies that there are regions of sapphire orientations containing these relationships which are separated by boundaries. The presence of these boundaries is demonstrated, initially on rounded cylindrical surfaces md more definitively on flat sapphire substrates with orientations along primary crystallograPhic zones. By means of reflection electron and X-ray diffraction techniques the crystallographic relationships have been studied. Two new relationships have been found, viz., (111) Si (1014) sapphire and (001)Si (1012) sapphire. Also found were multicrystalline relationships. The approximated boundaries between the crystallographic regions for each relationship are shown by means of a stereo-graphic projection. These studies also clarify discrepancies in the literature concerning the silicon-sapphire relationships on the (1120) sapphire substrate. SINCE the first report of the deposition of single-crystal silicon on sapphire in 1963' this epitaxial system has been the object of study by many semiconductor laboratories. In particular, there has been strong interest in the crystallographic relationships between the two materials. In 19652,3 we demonstrated that at least four distinct modes of orientation relationships can occur, namely, (100)Si (0112) sapphire, (111)Si 11 (1124) sapphire, (111)Si (1120) sapphire, and (111)Si (0001) sapphire. Each relationship could be obtained when the substrate plane was at the particular orientation indicated. Other workers as well as our laboratory concurred in general with the initial results. However, two discrepancies were observed. First it was observed by Joyce et a1.4 that on a (1120) substrate a (110) silicon deposit could be obtained. This was actually consistent with the (111)Si (1124) sapphire mode. Second, two other laboratories,5,6 as well as our own,7 have found a deposition on the basal plane which is different than our initial findings. Even though a (111)Si deposit was obtained, the crystallographic relationships were not identical to those previously found. Subsequent work in our laboratories has confirmed that the form found in these later investigations of the basal plane is by far the more predominant, and the original finding was an anomaly. The relationships which have been previously estab1.ished are summarized in Table I. It is seen that at present a rather small number of possible substrate orientations has been investigated. Therefore, it seemed appropriate that a systematic investigation of silicon epitaxy on various sapphire substrate orientations would be of value. It was expected that the answers to three questions could be obtained from such an investigation. These are as follows: 1) Since we know of at least four distinct modes of orientation relationships, over what range of substrate orientation do these modes occur and what is the form of the boundary expected between the different regions in which each mode occurs? 2) Are there other modes which occur on substrate orientations not previously investigated? 3) What is the explanation for the discrepancy between our laboratory's findings and those results reported by Joyce et al.4 concerning the relationships occurring on (1120) substrates? APPROACHES AND EXPERIMENTAL METHODS Two different approaches were used. Initially, depositions were carried out on rounded cylindrical surfaces which lay perpendicular to the (0112) plane.* By this means the presence of boundaries and their approximate positions could be determined. Finally and more definitively, depositions on flat sapphire substrates with a variety of orientations, mostly along primary crystallographic zones and about the (1120) plane, were studied by means of reflection electron diffraction and X-ray diffraction (using back-reflection Laue patterns and full circle goniometer techniques) in order to determine crystallographic relationships. The sapphire orientations investigated by these means

Jan 1, 1969

By R. J. Sherman, M. R. Achter

Creep rates have been measured for nickel at 1200°F in air and in vacuum, and related to the depth of surface cracks in the specimens tested in the two environments. The surface cracks were observed to grow faster in air than in vacuum in both short-time and long-time tests. Crack depths, however, could be correlated with creep rates only in the short-time tests. Although no cracks were observed in a relatively brittle Ni-Cr-A1 alloy creep tested at 1300°F, the appearance of alloy specimens fractured after interruption in creep indicated that there was a decrease of intergranular cohesion resulting from the diffusion of atmospheric gases into grain boundaries. PREVIOUS investigations1-3 have demonstrated that the effect of atmosphere on the high-temperature strength of nickel and nickel-base alloys may be reversed by changes in the stress or temperature of the test. At high stress and low temperature the creep-rupture life is longer in vacuum than in air, while at high temperature and low stress the relative strengths are reversed. A mechanism to explain this behavior was proposed based on two competing processes. Oxidation hardens and strengthens a metal, but adsorption of gas, by lowering surface energy, reduces the work required to propagate an intergranular crack. The controlling process is determined by temperature and stress. Basic to this mechanism is the concept that environment determines the ease of propagation of intergranular cracks and thus affects creep rate and rupture life. To explore the mechanism in greater detail, this investigation was undertaken to determine the effect of atmosphere on crack initiation and propagation rates in nickel1 and a relatively brittle Ni-Cr-A1 alloy.3 EXPERIMENTAL PROCEDURE The materials were the same as used previously. Nickel of 99.8 pct purity had the following impurity content: 0.02 pct Co, 0.03 pct Fe, 0.02 pct Mg, 0.03 pct Si, and 0.008 pct C. Rods were cold swaged from 1/2 in. to 3/8 in. in diam and machined into speci- mens with gage sections 1/4 in. in diam by 1-1/4 in. long. They were annealed in vacuum at 1600" F for 1 hr to achieve a grain size of 0.07 mm. The alloy was composed of 19.1 pct Cr, 3.6 pct Al, 1.7 pct Si, 0.57 pct Fe, 0.10 pct Mg, 0.027 pct C, 0.004 pct S, and the balance Ni. Sheet specimens of 0.500-in. width and 1.25-in. gage length were machined from 0.033-in.-thick strip and annealed in vacuum at 2000° F for 2 hr, resulting in a grain size of 0.036 mm. Large amounts of an intergranular phase were introduced as a result of the anneal. Creep tests on both materials, using equipment previously described by Shahinian; were conducted in air and in a vacuum of 1 x 10-5 mm Hg. They were continued to rupture and interrupted at various stages of the test. Although extensions were measured from dial gage readings of movement of the lever arm, it is considered that valid comparisons of creep rate may be made in this manner.l Two parameters were measured metallograph-ically* on longitudinal sections of nickel specimens interrupted during creep—the mean depth of surface cracks 2, and the density n as the number of cracks per unit length of surface. They were combined into one parameter by the relation p = n-d [1] As used here, p is equal to the total of crack depths per unit length of surface. RESULTS Nickel. It is well known that the incidence of intergranular cracking is increased with increasing rupture life. Indeed, it is evident in Tables I and I1

Jan 1, 1962

By R. C. Craze

During the past 20 years. research and development in the study of reservoir behavior have dealt principally with flow of oil through sandstones. Many reservoir studies of sand fields have proved valuable in promoting recovery efficiency. This paper discusses fundamental principles governing oil and gas production from sandstone and limestone alike and presents the results of investigations relating to the application of analytical techniques used for sandstone reservoir studies to the study of limestone reservoir performance. The characteristics of limestone porous systems, porosity-permeability relationships, distribution and occurrence of oil, and characteristics of flow through such systems are discussed. Recognition is made of the similarities or differences which these factors exhibit in limestone and sandstone systems. Comparisons between operating data for typical limestone and sand reservoirs are presented. It is indicated that the distribution and movement of fluids in and through porous limestones follow the same fundamental principles underlying such processes in sandstones. This fundamental similarity may readily be discernible in the performance of many limestone reservoirs. The volumetric balance and unsteady state radial flow equation, the fluid displacement equation, use of electrical analogue devices, and other analytical techniques to study the behavior of limestone fields appear fundamentally applicable, but do require thorough understanding of the properties of the formation, of the fluids, their behavior during flow, and adequate production operating data. Need for more complete coring and comprehensive examination of core properties is stressed. The results of "active oil" studies, and of flow and interference tests are presented. Well spacing, well completion, and efficient rates of production in limestone reservoirs are briefly discussed. INTRODUCTION Limestone and dolomite reservoirs constitute the largest source of supply of crude oil in the world. an estimated 60 per cent of present production coming from carbonate reservoirs. In many large geologic provinces such as Mexico. the Middle East, and more recently Canada, almost all the oil is found in this type of rock. In the United States, all of the major oil-producing areas except California and Pennsylvania contain oil-bearing carbonate formations. The discovery in recent years of large oil reserves in the Silurian, Devonian, and Ordo-vician formations in West Texas, in addition to the large reserves in the Permian, has accentuated the interest of operators, geologists, and engineers in limestone formations and in the many problems associated with understanding the performance of these reservoirs. The rapid increase in discovery of oil in limestone formations and the present-day position of prominence held by these fields in the production and reserve picture in all parts of the world emphasize the horizons opened to the reservoir technologist in the field of geological and production research. Pertinent to an interpretation of the behavior of limestone reservoirs are the methods of analysis which may be utilized and a possession of full knowledge of the many factors which influence the analytical procedures. During the past 20 years a well-developed science of reservoir engineering has been built upon the research of many workers who studied the fundamental nature of oil reservoirs, characteristics of the porous media, properties and behavior of the contained fluids, and the mechanics of flow. Application of these studies to production practice has resulted in greater recoveries and more efficient field operation. The major portion of this evolutionary process has been founded upon studies of sand fields. The applicability of these more thoroughly developed techniques for studying sand fields to the study of the behavior of limestone fields becomes a factor of technical and practical significance. In the light of the technological background available to the reservoir analyst, this paper discusses fundamental principles governing oil and gas production from sandstone and limestone alike and presents the results of investigations relating to the application of analytical techniques used for sandstone studies to the study of limestone reservoir performance. LIMESTONE RESERVOIR CHARACTERISTICS The characteristics of limestone and sandstone reservoirs are similar in many respects and they both may occur under similar structural conditions. Fundamentally, the distribution and movement of fluids in and through the porous limestone media follow the same basic principles which dictate such processes in sandstones. Herein lies a fundamental similarity, which may readily be discernible in the performance of many limestone reservoirs. In some limestone fields, as in many sand fields, widely varying formation properties and distribution may reveal themselves in deviations in the performance of the reservoir, in the behavior of wells, and in fluid flow through the rock, and make difficult the delineation of reservoir behavior. Only by reservoir studies, core analyses, and coordinated laboratory and field experimentation can the effects of the many influencing factors upon the nature of limestone production be determined. FORMATION CHARACTERISTICS The chief difference between limestone and sandstone, aside from their chemical compositions, is the difference in the geometry and origin of the porous systems in the two kinds of rock. In sandstone the porous system results entirely from the openings among individual sand grains which occur during deposition. The geometry of the openings between the sand

Jan 1, 1950

By John M. Tinsley, Calvin D. Saunders, H. K. van Poollen

In the past few years much con-sideration has been given to the evaluation of the effect of hydraulic fracturing on the productivity of wells. Generally, these studies included the evaluation of fracturing materials, fracture extension and formation damage due to the use of various fracturing fluids. Only little consideration has been given to the characteristics, and in particular the flow capacity, of the fracture itself and its effect on well productivity. This paper presents the results of laboratory investigations pointed toward fie evaluation of the efficiency of various fracrures with special emphasis on the flow capacity of these fractures. Data presented in this paper are the results of both an electrical model study and physical testing. Under consideration are (I) effect of overflush, (2) premature production of well after treatment, (3) "tailing-in" with coarse sand near the end of the treatment, (4) effect of propping agent size and concentration, (5) reduction in effective frac-ture permeability caused by formation caused by formation fines, silt and clays, and (6) effect of various fluids on formation strength and competency. The results of this investigation indicate that the flow capacity of a fracture is affected by any or all of the various parameters mentioned above. The authors believe that a better understanding arid utilization of these factors should result in more efficient formation fracturing. INTRODUCTION Hydraulic fracturing has become almost a standard practice of many companies for stimulating production from old and new wells. Although most companies utilize this service, techniques of application vary widely between companies and areas. Probably too often when a well in an area responds favorably to a particular technique all future wells in the same area are treated in a similar manner. Possibly a modification of the technique would result in a further production increase. Variables, of which many are extremely difficult to evaluate from field results, hamper the selection of procedure changes. Attempts are being made by a number of organizations to analyze statistically treating techniques from production data. This is a very worthy and necessary approach but very possibly laboratory investigations may aid in evaluating some of the variables which tend to affect the results of a fracturing treatment. Some of the factors cannot be studied from practical field experience and only laboratory tests can show the possibilities which might exist. One of the factors which appears to be of major concern today is the flow capacity of the created fracture and how it can be changed. Papers on this general subject have been primarily concerned with the size of propping agent and the extent of fracture. Papers have also been written on the possible permeability damage to formations by fracturing fluids. In addition, it might be possible that another type of flow restriction is prevalent. This would be a restriction of flow through a sand-packed frac- ture caused by foreign materials integrating within the propping agent. This paper presents preliminary data obtained in an attempt to evaluate the effect of some factors affecting flow through sand-packed fractures. No attempt is being made to offer a fracturing technique adaptable to all areas and conditions, but to furnish data tending to show the possible effects which might be caused by variations in procedures and materials. PROPPING AGENT PERMEABLLITIES A hydraulically induced fracture containing sand as a propping agent may theoretically be classified as a packed-sand system. The flow of fluids through such packed systems has been the subject of much research. Although there have been numerous methods proposed for the evaluation of such systems, most writers agree on the general properties affecting their flow capacity or permeability. These properties include porosity, particle size, sphericity and the roughness of the particle. In some methods of evaluation . the particle size and sphericity terms are combined to produce an equation which is a function of the surface area of the particles. In this study the permeability of various fracturing sands was both measured and calculated. The apparatus for the permeability measurements consisted of a 52-in. Lucite tube with a 2.5-in. ID. A screen and drain plug were fitted in the bottom of this tube to retain and hold the sand in place while allowing fluid flow. Two pressure taps consisting of thin, highly perforated

By Nicholas J. Grant, Yoichi Ishida, Arthur W. Mullendore

An inert particle -marker technique was developed to provide a direct measurement of grain boundary sliding during creep in tile interior of aluminum specimens. Groin boundary sliding in the interior as measured by this technique was found to be nearly the same or slightly lower than that measured on the surface. These data disagree with those obtained by the grain-counting technique developed by W. A. Rachinger. In tests where both techniques were used, the grain-counting technique gave large and variable values of grain boundary sliding. It is shown that the grain-counting technique gines erroneozcs results because of a preferred direction of grain growth during creep. A question which has long plagued those who study grain boundary creep is whether or not surface measurements yield a true representation of the deformation in the interior of a specimen. The first attempt to measure grain boundary sliding in the interior of a creep specimen was made by Rachinger.1 His technique is based on the measurement of average grain diameters, both parallel and perpendicular to the tension axis, followed by a calculation of the grain elongation from these measurements. The difference between total elongation, Et, and the calculated grain elongation, Eg, is considered to be the result of grain boundary sliding, Egb. Surprisingly large values of Egb/ Et (90 pct) came out of creep tests of pure aluminum at temperatures above 250°C (480°F), utilizing the Rachinger technique. This value is very much larger than the values of 8 to 15 pct measured by numerous investigators on the surface of a specimen. Values obtained on the surface by Rachinger, however, were consistent with those measured by the displacement of reference scratches. Chaudhuri and Grant2 repeated the Rachinger method for A1-10 pct Zn, and found the same large values of Egb/Et inside the specimen. However, from purely geometrical considerations, grain boundaries cannot slide without grain deformation; therefore, they questioned the validity of Rachinger's grain-counting method. Several authors2,3 have suggested that grain boundary migration during high-temperature deforma- tion may tend to restore the equiaxed grain shape in order to minimize interfacial energy. Rachinger4 tested this hypothesis and found that it did not hold. Grains elongated by rapid extension retained their elongated shape during a subsequent slow creep test. It appears that some other factor was responsible for the abnormally high values of .Egb/El. McLean and Gifkins5 made a survey of the effect of grain size on the ratio Egb/ Et, and proposed that the high values were the consequence of a small grain size. They failed to explain the low value of Egb/Et which Rachinger observed on the surface of the small grain size specimens, and suggested that the surface effect on the value of Egb/Et does not always occur. Many of the disagreements arising from Rachinger' s work stem from the fact that there was only one method of estimating grain boundary sliding in the interior of a specimen, and that method was of an indirect nature. If a marker line of some sort could be introduced inside of the specimen, one could make measurements just as clearly as on the surface. In the present investigation, the technique utilizes a layer of finely dispersed oxide particles inside the specimen introduced by hot press-bonding of two pieces of aluminum. Rachinger attempted a similar technique but with the oxide distribution he obtained there was so much interference with grain boundary motion that quantitative measurements were not attempted. MATERIALS AND EXPERIMENTAL PROCEDURE A) Materials Preparation. Two pure aluminum rods (impurity content in percent: Si, 0.002; Cu, 0.004; Fe, 0.002; Mg, 0.000: Zn, 0.000; V. 0.001) 1 in. diameter by 2 in. high were jacketed end to end in a 4-in.-diam cylinder of commercial-purity aluminum, 4 in, high, which had a l-in.-diam hole. The l-in.-diam mating surfaces of the two pure aluminum rods had been electropolished initially. This interface provided the oxide-film internal -marker plane after the hot press-bonding process, see Fig. 2. The composite was annealed for 1 hr at 900 F and hot upset more than 50 pct reduction in height in one step. The resulting slab was then rolled to 1/2 in. thickness; the pure aluminum test material was cut out and annealed at 900°F for 1 hr and cold cross-rolled to 1/8 in. thickness. The sheet was machined into specimens with a 1/8-in.-square cross section and a 1/2-in. gage length. The following heat treatment was given the specimens: Specimen 5A series: annealed at 1000°F for 5 min for grain-size control and then cooled to 700°F and held for 15 hr for stabilization.

Jan 1, 1965

By Elmer R. Kaiser

COMBUSTION of coal and transfer of heat from flames and gases to boiler surfaces continue to be of great interest to engineers here and abroad. Numerous investigations have been in progress to improve furnace and boiler performance and economy. The importance of better understanding of the processes and opportunities for improvement is apparent when it is remembered that heat from at least 500 million tons of coal a year the world over is being transferred to boiler water at efficiencies ranging mostly between 50 and 90 pct. Even slight gains in efficiency, economy, and labor saving become very significant when multiplied by the enormous quantity of fuel consumed. Also the competitive position of the large coal, oil, and gas industries in satisfying the fuel consumers is greatly affected by the achievements made through technical progress with each fuel. This paper is part of a continuing activity of Bituminous Coal Research, Inc., to extend the knowledge of coal utilization for steam generation and to seek promising directions for future research and development in cooperation with others. Particularly in the latter regard, numerous interviews were held during the last three years to seek the experience and advice of boiler and combustion-equipment manufacturers, electric-utility executives, and fuel engineers. A wealth of published information was also reviewed, which together with the interviews pointed to the advisability of further work on ash and sulphur control. For the present purpose a number of factors important to efficient heat liberation and recovery have been grouped as follows: 1—combustion, temperatures, and rates of heat liberation; 2—radiation, convection, and furnace and boiler configuration; 3—sponge ash, slag, and hard-bonded deposits; 4— low-temperature deposits and corrosion (cooling flue gas below dew point and air-pollution control); 5—the limitations of coal cleaning and boiler size and cost as related to fuel characteristics; 6—future possibilities and conclusions. The development of combustion apparatus for power boilers is progressing at a lively pace. There has been no letup in improvements in design of pulverized-coal-fired boilers, and there is a strong trend at present toward improving dry-bottom units. Spreader stokers with overfire jets and dust collectors as standard equipment are gaining favor. Less than 10 years in commercial use, cyclone burners are going into numerous installations here' and abroad.' Underfeed and traveling-grate stokers have long since been developed for heavy-duty operation, yet new developments in overfire jets and humidification of air blast have improved their performance. A water-cooled vibrating-grate stoker of German origin is being introduced into the United States and Canada." The primary objectives of an ideal coal combustion device are: capacity to burn the variety and sizes of coals likely to be economically available during the life of the unit; capacity to burn the coals automatically for a wide load range and rapid load fluctuations and to burn the coals completely to CO2, H2O, and SO2, which means without smoke and cinders, or carbon in the refuse; capacity to control and discharge all the ash in final granular form without ash adhesion to walls or tubes, and without flue dust; minimum furnace volume; minimum labor and maintenance; low initial and operating cost. Regardless of the method of burning, the gaseous products of coal combustion are N2, CO2, O2, H20, and SO?. By way of illustration, the coal analyses in Table I is assumed from an installation described by E. McCarthy.' When coal is burned with 20 pct excess air (theoretical air, 9.23 lb per lb of coal), the quantities of combustion gas shown in Table II are produced. In addition, the gases carry particles of fly ash, unconsumed cinders, soot particles, and small but significant amounts of vaporized oxides and sulphates of sodium, potassium, lithium, phosghorous, iron, and other metals. In recent years, germanium, one of the rare metals found in coal, has been shown to oxidize and vaporize at combustion temperatures and to be concentrated by reconden-sation at lower temperatures." Pulverized coal and cyclone flames" have peak temperatures of 3000' to 3500°F. Temperatures in fuel beds of large underfeed stokers reach maxima of 3000°F, sufficient to fuse almost any ash and to volatilize some of it. These peak temperatures are above the optimum necessary for rapid combustion, but they hasten heat transfer for ignition as well as boiler heat absorption. Furnace and gas temperatures increase with combustion air preheat. Low excess air has the same effect. Fine coal pulverization and highly turbulent combustion shorten the distance for fuel burnout, increase flame temperature, and speed up heat transfer. Rates of combustion of pulverized coal exceeding 200,000 Btu per cu ft per hr have been demonstrated in atmospheric gas-turbine combusters,

Jan 1, 1955

By Frank E. Woolley, John F. Elliott

Mathematical models of the transient thermal behavior of a high-temperature solution calorimeter1-3 have been developed. The thermal behavior of the calorimeter is appoxirrzated by linear lumped-parameter models, and hence is described by sets of linear ordinary differential equations with constant coefficients The response of the models to various inputs is shown to agree with the response of the real system. Application of the modeling to experimental design and analysis of data illustrates the usefulness of simple models of complex systems. The early eperiments1,2 with the high-temperature solution calorimeter indicated that the change in the temperature of the bath resulting from the addition of a solute sample to the bath involved not only the direct effect due to the solution process but also possibly a secondary effect arising from the change in coupling between the bath and the induction heating coil. Consequently, an extensive analysis of the calorimeter was carried out, and models of the transient thermal processes of the instrument were developed to aid in improving the design and interpreting the behavior of the system. This paper describes the dynamic modeling; the use of it in treating experimental results has been reported earlier.3 The high-temperature solution calorimeter was constructed to measure directly the partial molar heats of solution of solute elements in a variety of liquid metal solvents.1-3 The calorimeter consists of an induction-heated liquid metal bath into which small samples of a solute element can be dropped. The bath temperature is recorded continuously, and the change in the measured bath temperature with time, dTm = f(t), resulting from the solute addition are the raw data from which the enthalpy change caused by the addition is determined. To extract the rmodynamic results from the data, the temperature change must be compared with that resulting from calibration additions of known enthalpy change. Accordingly, it is necessary to understand the transient thermal processes arising as a result of the addition to the bath. Neither modeling nor experimentation alone could provide the required insight into the working of the calorimeter. The alternate use of both methods in conjunction greatly assisted the design of the equipment and experiments, and the interpretation of the data. THE PHYSICAL CHARACTER OF THE SYSTEM The essential parts of the calorimeter, Fig. 1, for model studies are the thermocouple, the liquid metal bath and the surrounding refractories. The system is the solvent metal bath and those refractories around it which undergo a temperature change as a result of an addition to the bath, and which determine the way the temperature of the bath responds to an input. The inputs are the combined transient thermal effects arising when an addition is made to the bath. They include the thermal effects of the addition itself and the results of changed coupling between the bath and the induction coil. The response is the variation in the measured bath temperature, dTm(t) = Tm(t) - Tm(O), from an initial steady state resulting from the inputs. It was assumed in this study that the physical properties of the various elements of the system are independent of the inputs and time, although these properties may vary as the result of changes in the composition and size of the bath during a series of additions. This separation of inputs and the system is equivalent to assuming that the system is linear, i.e., that its behavior can be described by linear differential equations with constant coefficients. Linear behavior can be expected whenever the departure of each portion of the system from its steady-state condition is small enough to cause negligible changes in the thermal properties of the materials and in the various heat-transfer coefficients. Radiative heat transfer is important in this system, so the assumption of linearity should be valid only for small temperature deviations. Several conclusions were drawn from operation of the calorimeter in earlier experimental studies: 1) Radiative heat transport from the top of the bath is a significant portion of the total heat lost from the bath. However, for small changes in the bath temperature the change in transport by this path could be assumed to be proportional to the change in the bath temperature. 2) A very small portion of the heat input is lost through the thermocouple to its water-cooled holder. The thermal resistance and thermal capacity of the thermocouple protection tube are small, so the temperature of the thermocouple should follow closely that of the bath. 3) The remainder of the total heat lost from the bath will pass by conduction through the crucible to, and through, the other refractories, eventually being absorbed by the water-cooled induction coil or by the water-cooled sides and bottom of the enclosure. 4) The thermal resistance between the bath and crucible is very small. Thus the thermal capacity of the crucible will affect the temperature of the bath very soon after an addition of heat to the bath. 5) The thermal resistance between the crucible and the silica sleeve is large, especially if a radiation shield is placed in the gap. The effect of the thermal capacity of the sleeve thus will be significant only at longer times. The thermal resistance through the packing below the crucible also is large, so the packing and the silica sleeve will have similar effects on the behavior of the system. 6) A large temperature drop exists across the gap containing the water-cooled induction coil. Thus for relatively small changes in the thermal input to the bath, the refractories beyond the sleeve

Jan 1, 1970

By Ernest L. Ohle

The newly opened Hayden Creek lead mine represents a variation from the usual Southeast Missouri type. Galena mineralization occurs in sandy dolomite cementing a conglomerate of granite boulders and in cracks in the boulders. The conglomerate occurs at the base of the Bonneterre formation on the slopes of two buried pre-Cambrian knobs. IN 1943 diamond drilling from the surface in an area 2 miles southwest of Leadwood, Mo., discovered a lead deposit of a markedly different character from the usual southeast Missouri type. Subsequent drilling of about 500 holes indicated several million tons of ore, and in 1950 a 701-ft vertical shaft was sunk into the orebody. This paper describes the geology of this interesting occurrence insofar as it is known from the drilling and the small underground exposure at the bottom of the shaft. Geology The location of the Southeast Missouri Lead Belt and of the Hayden Creek property are shown in Fig. 1. As shown here, there are two separate producing areas, one from which the larger tonnage has come, located near Bonne Terre, Flat River, Desloge, and Leadwood, and the other to the south around Fred-ericktown and including famous old Mine LaMotte. The best published description of Lead Belt geology is by Tarr.* In pre-Cambrian time in this area, an assemblage of granites and rhyolitic flow rocks was eroded to a mature topography. Sedimentation, beginning in the Upper Cambrian, filled in the valleys and gradually covered even the highest hills. The first formation deposited was the La-motte sandstone; it is successively overlain by the Bonneterre dolomite, the principal lead-prodbcing formation, then the Davis shale. the Derby-Doerun limestone, and a succession of Cambro-Ordovician cherty dolomites. Several of these formations may be found in direct contact with the pre-Cambrian as their deposition progressively overlapped the older rocks on the flanks of the igneous knobs and ridges. Immediately overlying the pre-Cambrian there is, not uncommonly, a thin basal conglomerate of granite or porphyry boulders, which is incorporated into the overlying sediments. Deposition of the lower part of the rock section was fairly continuous, and the Lamotte sometimes grades almost imperceptibly into the lower sandy Bonneterre. Since the sediments were deposited on an uneven floor, they tend to reflect the irregularities in that floor. Most of the steep dips found in the district, that is, dips in excess of 10°, are original dips and not caused by deformation. Such domelike structures in the sedimentary rocks around the igneous knobs have localized a considerable number of the orebodies in the district and particularly those in the Frederick-town area. Many of the larger orebodies, however, have no close relation to the pre-Cambrian topography. Most of the lead production has come from the lower 150 ft of the Bonneterre formation, where disseminated ore spreads laterally parallel to the bedding for great distances. Average stoping height is about 20 ft, but in a few places there are stopes over 175 ft high.

Jan 1, 1953

By L. Himmel, R. F. Mehl, C. E. Birchenall

The rates of self-diffusion of iron in artifically prepared wustites of various compositions have been determined using the decrease in surface activity technique. Similar measurements are reported for artificial magnetites of nearly stoichiometric composition and for natural hematite single crystals. These data, together with appropriate thermodynamic data derived from the present study or from the literature, are used to calculate the rates of oxidation of iron and its oxides, taking as a basis the theoretical rate equations developed by Wagner. The calculations are compared with experimental rate constant data for these same reactions and are shown to provide essential confirmation for the Wagner theory. For the most part, the results are also consistent with the previously proposed transport mechanisms in the oxides of iron. WHEN a metal is exposed to an oxidizing atmosphere at elevated temperatures, a superficial oxide layer is formed which then thickens according to some characteristic rate law. Provided that the oxide layer is dense and continuous and does not present any paths for gaseous diffusion, continued growth must inevitably involve the migration of the reactants—either the metal or oxygen or both—through the lattice of the solid oxide. This is true whether the reaction rate is controlled by the diffusion process itself or by a slow step in a reaction at one of the interfaces. If the overall rate is limited by diffusion, and if the concentrations or thermodynamic activities of the reactants at the boundaries of the oxide layer are independent of time, the familiar parabolic rate law is observed. Under these conditions, Wagner1 has shown that the rate constant may be expressed in terms of the mobilities of the reacting components and the appropriate concentration or activity gradients which are established across the growing oxide layer. In presenting the phenomenological basis for the theory, Wagner has emphasized the role played by lattice defects in diffusion processes in oxides. The essential validity of this theory has been confirmed by experiment for a number of simple systems including the growth of Cu2O on copper.'-' One of the objectives of the present study has been to extend the Wagner approach to the more complex process of the oxidation of iron and its oxides, and particularly to wustite, which is normally the major constituent of the oxide scales formed on iron at temperatures above approximately 570°C. For this purpose the rates of self-diffusion of iron in w?stite, magnetite, and hematite have been measured by tracer techniques and the necessary thermodynamic data have been obtained from equilibrium studies involving the oxides and their atmospheres. These data have subsequently been used to test the underlying assumptions of the Wagner theory as well as the detailed mechanism of the scaling of iron previously proposed by Davies, Simnad, and Birchenall.5 Lengthy treatments of diffusion and conduction phenomena in ionic crystals have been published." * The latest, by Jost,8 also summarizes much of the existing experimental data. In general, however, the oxides of iron have not been considered specifically and hence a brief review of the available

Jan 1, 1954

By H. F. Yancy

PooR results in coal washing and in ore concentration are sometimes attributed to the shape of the particles in the feed. It is well known that the shape of a particle influences its rate of fall in water. This is evidenced by the value of the constant C in the Rittinger equation for the velocity V of settling in water, V = C-D(d- z ), where C has the following values: 2.73 for roundish grains, 2.37 for long grains and 1.92 for flat grains. This report, which is based upon data obtained during the course of coal-washing investigations conducted by the U. S. Bureau of Mines in cooperation with the College of Mines of the University of Washington, gives the results of a method or procedure of screening in which the particles are separated into three shapes and shows the deportment of these shapes when coal is treated on a coal-washing table. The method consisted in first screening the coal with Tyler standard square-hole sieves, followed by screening tests of each of these products with screens of rectangular opening. For this purpose Tyler "Ton-Cap" screens were used; each square-hole product was subsequently sized with two Ton-Cap sieves so selected that their shortest dimensions were approximately 75 and 50 per cent., respectively, of the opening of the square-mesh sieves. For example: A product which is through 8 mesh (0.093 in.) and on 10 mesh (0.065 in.) is screened on slotted sieves which have openings 75 and 50 per cent. of the 0.065-in. opening in one direction and an opening of not less than 0.065 in. in the other direction. For convenience in discussion, the particles retained on the first slotted screen are termed "cubical"; those retained on the second slotted screen are termed "prismatic" and those passing the second screen are called "flat." (See Fig. 1.) The square-mesh screens separate particles according to two dimensions, length and breadth; the slotted screens divide them further according to the third dimension, or thickness. Prismatic particles have a mass of about two-thirds, and flat particles of about one-half, that of cubical particles of the same square-mesh size. The screen-

Jan 1, 1931

By R. H. Fillnow, D. J. Mac

IT has been demonstrated that alloys in systems structurally analogous to steel undergo reactions during heat treatment similar to those of steel, and yet very little work has been done on such systems, particularly from the standpoint of isothermal transformation. The literature shows that most of the isothermal work has been done on copper-alu-minum alloys.'-3 One paper has been reported on a eutectoid copper-silicon alloy,' and one on iron-nitrogen alloys.' There are no published reports of previous investigations on the isothermal transformation of a eutectoid beryllium bronze. At least two papers have been reported on isothermal age-hardening phenomena in beryllium-copper alloys of lower beryllium content.5,6 No information on eutectoid transformations in this alloy is given in Rimbach's book, "Beryllium." ' This paper reports the results of an investigation on the isothermal transformation characteristics of a eutectoid beryllium bronze. Materials Used and Procedure The eutectoid beryllium bronze used in this investigation was centrifugally cast at the Ampco Metal Co., Inc.. Milwaukee. Wis. A master beryl-lium-copier alloy, purchased from the Brush Beryllium Co., was used to make the beryllium addition to the copper. The alloy was melted under a protective carbon cover and Centrifugally cast into a graphite mold preheated to 920°F. Some trouble with segregation of beryllium in the melt was encountered but was eliminated by violent stirring during melting and pouring. Since very thin .specimens were used for the various heat treatments, only one casting of the four prepared was necessary for the complete isothermal study, thus eliminating any discrepancies caused by a change in composition. The analysis of this casting was 94.035 pct copper and 5.965 pct beryllium. A slight trace of iron was found. The castings were sawed into specimens approximately 3/32 in. in thickness. The specimens were first given an "austenitizing" heat treatment at 788°C, well within the single phase beta region, in a vertical tube furnace. The specimens were then quenched individually into an adjacent molten salt bath and held there for a definite time, after which they were quenched into water at room temperature. Temperature was held to ± 2°C in the salt bath. No homogenizing treatment was given the specimens other than the soak at 788°C. Despite the fact that this was a cast alloy, no evidence of segregation or coring was found in the microstructure of any specimen, either as cast or as heat-treated. Upon completion of the heat treatment, the speci-mens were subjected to metallographic examination

Jan 1, 1951

By Gaudin. A. M., S. C. Sun

THIS paper presents the results of a study of the relationship of the electrokinetic or zeta potential to flotation phenomena. The relationship is established on the experimental evidence that mineral behavior in flotation and in cataphoresis is generally governed by the chemical properties and amount of the reagents adsorbed at mineral surfaces. Cataphoresis1-5 or electrophoresis is the name given to the movement of a charged particle in a liquid medium under the influence of an applied electric field. Mineral behavior in cataphoresis, as indicated by the magnitude and sign of its ionic charge, can be represented by the term zeta potential. In this paper, the zeta potential represents the difference in potential between the immovable liquid layer attached to the surface of a solid particle and the movable liquid layer in the body of the liquid, and is the result of the tendency of ions on the surface of the particle and within the liquid boundary layer to establish a condition of equilibrium. A high positive zeta potential means that the mineral surface is dominated by cations, a high negative zeta potential indicates domination by anions, and a low zeta potential indicates that the surface is influenced almost equally by cations and anions. In terms of observed quantities the zeta potential is given by the relation [z = 47ruu(300)$ Kx] in which z is the zeta potential expressed in in volts, u the viscosity of the solution in poises, u the velocity of particles in centimeters per second, x the impressed potential gradient in volts per centimeter, and k the dielectric constant of the solution in c.g.s. units. A convenient source for the derivation of the equation is the book by Thomas,6 The term zeta coefficient is an expression coined to denote the difference between the magnitude of the zeta potential of a mineral suspended in solution A, and that of the same mineral suspended in solution B, which consists of solution A and an additional chemical agent, but is at the same pH. For example, the difference between the zeta potential of galena particles in distilled water and that in any chemical solution at the same pH is a zeta coefficient. Or, when the zeta potential of a mineral particle is measured first in distilled water, then in a mixture of water and copper sulphate, and finally in a mix-

Jan 1, 1946