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By I. R. Kramer

I. R. Kramer (Martin Co.)—In a recent paper Nakada and Chalmers24 reported some observations of effects of surface conditions on the stress-strain curves of aluminum and gold single crystals. It is of interest to compare these observations with the results published previously in this journal and to comment on their general conclusions. In brief, Nakada and Chalmers concluded that the removal of the surface layer of a prestrained specimen lowered the stress-strain curve for aluminum but not that for gold. Further, they concluded that the surface work hardening of aluminum is confined to a depth not more than l0-3 cm. In our results25 published previously, it was pointed out that when prestrained specimens of aluminum and gold were polished to reduce the thickness upon reloading the initial flow stress decreased markedly. Further if a sufficient amount of metal was removed, the yield point failed to appear. With continued application of the load the stress-strain curve became coincident with that of the virgin crystal. We have found this behavior in some 100 determinations to hold consistently for gold, aluminum, and copper in both single and poly-crystalline specimens. The amount of strain required before the curves coincided depends upon the amount of metal removed but it is usually less than 0.01. This type of behavior is the same as that reported for metarecovery by other investigators.29 For aluminum specimens which have been prestrained and then heated to temperatures above 50°C we have consistently found that the stress-strain curve was typical of the orthorecovery28 type. In this case the stress-strain curve always lies below that of the virgin specimen. With respect to Ref. 24 the curves for aluminum are always below that of the virgin curves, while those for gold become coincident. This observation indicates at least for aluminum that the specimens must have been heated to a temperature high enough to cause recovery by an alteration of the internal dislocations. In addition, a recovery would be expected because of the removal of the surface work-hardened layer. Nakada27 had reported that, with his particular apparatus in which a perchloric acid polishing solution was used, the temperature of the specimen increased 65°C. The curves presented in Ref. 24 for gold do not permit one to detect the initial flow stress upon reloading after the surface-removal treatment. In fact, contrary to the method used by Nakada and Chalmers, the change in the stress-strain curve produced by a surface-removal treatment cannot be described in terms of a decrease in stress at strains much higher than that at the initial flow stress because of the coincidence of the curves at the higher strain values. With regard to the depth of the work-hardened surface layer, our data show for aluminum single crystals (7.5 by 0.3 by 0.3 cm) that the initial flow stress remained constant after 12 x 10-3 cm had been removed from the thickness. This depth was independent of the prior strain. For gold crystals this depth is somewhere between 10 x 10-3 and 20 x 10-3 cm. Y. Nakada (author's reply)— Kramer states,28 "for aluminum specimens which have been prestrained and then heated to temperatures above 50°C, we have consistently found that the stress-strain curve was typical of the orthorecovery28 type. In this case the stress-strain curve always lies below that of the virgin specimen." However, Cherian et a1.26 discovered that aluminum polycrystals annealed at 32" and 100°C showed the metarecovery behavior. They showed that the orthorecovery behavior did not appear until the crystals were annealed at 150°C. Kramer suggests28 that the drop in the flow stress of aluminum crystals after the surface removal by electropolishing24 may be due to the recovery caused by the temperature rise which may occur during the electropolishing.27 However, as indirectly stated in Ref. 24, the current density used in these electro -polishing experiments was 0.15 amp per sq cm. According to ref. 27, this current density should cause a temperature rise of only 40°C. This may cause the metarecovery but not the orthorecovery. Furthermore, as stated explicitly in Ref. 24, the surface removal was accomplished by chemical etching as well as by electropolishing. The results were the same for both electropolishing and etching. During the etching, the specimen temperature did not rise above 35°C. Some aluminum crystals were placed in water at 35° C for 30 min. These crystals did not show the decrease in flow stress. Therefore, it is quite clear that the flow-stress drop after the surface removal is not caused by a high-temperature recovery. However, as Kramer points out,28 it is quite possible that the internal dislocation structure may have been altered because of the removal of the highly work-hardened surface layer. However, how much this rearrangement contributes toward the flow-stress decrease is not known at present.

Jan 1, 1965

By J Price, M. R. Geer, H. F. Yancey

COAL mine operators recognize coal as an abrasive material, because the wear of drilling, cutting, and conveying equipment is reflected as a cost item for replacement of parts. Similarly, industrial consumers of coal experience abrasive wear on all coal-handling equipment. Operators of pulverized fuel plants are doubtless most keenly aware of the abrasiveness of coal, because under the high contact pressures developed between coal and metal in pulverizers, abrasive wear is increased many fold. Moreover, experience in operating pulverized fuel plants has demonstrated that some coals are much more abrasive than others. Hardgrove' stated that maintenance costs entailed by the wear of grinding elements is often a more important variable than the cost of the power required to pulverize different coals. Craig2 also reports that one coal may cause pulverizer parts to wear several times faster than another. It is apparent, therefore, that those concerned with pulverizing coal could profitably employ a method for estimating the abrasiveness of different coals, just as they utilize standard tests for thermal value, grindability, and ash-fusion temperature to assist in selecting the most suitable and economical coal to use in a particular plant. The objective of this investigation was to develop a test procedure that would be suitable for general use in estimating the abrasiveness of coals. However, few, if any, of the standard tests now used for evaluating the properties of coal are the product of a single investigation or the result of a single investigator's efforts. Rather, in each case, a testing procedure was devised by one investigator, used by others on a wider variety of coals, and finally refined completely as the result of the joint efforts of a number of interested people. Thus, the test procedure for estimating abrasiveness developed in the course of this work may not be refined sufficiently in its present form for general use, but it may serve as the starting point from which an acceptable test procedure can be developed. The method has been used thus far on only about a dozen coals, and there has been no opportunity to attempt a correlation between experimental results and actual plant experience. Only wider use of the procedure by other investigators and correlation with plant experience can determine to what extent the method will have to be modified to render it suitable for general application. Test Method Although the literature contains no record of an attempt to devise a method for estimating the abrasiveness of coal that could be used industrially, several investigators have tested properties of coal that are closely related to its abrasiveness. The abrasiveness of a material generally is considered to be related to its hardness, and hardness tests for coal have been employed by Heywood,' O'Neill," and Mathes. Also, the resistance of coal to abrasion, a property that presumably is related to the abrasiveness of coal, was measured by Heywooda and by Simek, Pulkrabek, and Coufalik.2 11 these investigators tested only individual pieces of coal. Since coal is a heterogeneous material having components of varying properties, tests of this type can yield results having little more than academic interest. Only a test method that utilizes a representative sample of coal can give results that are useful industrially. The abrasion tests used for various other materials have been considered for adaptation to testing the abrasiveness of coal. The tests used for metals,7-9 paving and flooring,'" and rubber," cannot be used because coal is not sufficiently abrasive.~ The present experimental work was begun before World War II and was conducted by three research fellows"'" working under a joint agreement between the University of Washington and the Bureau of Mines. After a great deal of preliminary work with a variety of apparatus and materials, a test procedure was developed which consisted of rotating a test disk 2Yz in. diam in a steel mortar containing the coal sample. The shaft carrying the test disk at the lower end and a 100-lb load on the upper end was free to move vertically. The bed of coal in the mortar was kept fluid by low-pressure air admitted through a port near the bottom of the mortar. Measurable wear on an Armco iron disk could be obtained in this test procedure, but, despite extensive efforts to eliminate them, several major disadvantages remained in this test method. First, with most coals the amount of wear on the iron disk did not exceed a few milligrams. Second, a single type of disk was not applicable for all coals. A smooth iron disk gave satisfactory results with both bituminous and sub-bituminous coals, but hardly any wear with anthracite or coke. A disk having studs or projections gave more satisfactory abrasion losses with anthracite and coke and presented no operating difficulties with free-burning bituminous and sub-bituminous coals. It could not, however, be used with caking coals because these coals formed a

Jan 1, 1952

By G. Das, S. V. Radcliffe

The substructural features developed in tungsten as a function of annealing temperature (up to 2200°C) and type of material [undoped and doped powder metallurgy (PM) tungsten and electron beam melted tungsten] have been investigated by transmission electron microscopy. For doped PM tungsten wires, characteristic "par-ticulate" substructural features developed rapidly with increase in annealing temperature above 700°C. The features consisted of parallel rows of elongated or circular shapes (500 to 1000A diam) lying along the direction of the wire axis and were identified as internal voids by diffraction contrast experiments. In recrystallized doped PM rod, larger voids were observed and were identified by precision dark field analysis to be cubic in shape and bounded by (100) planes. In marked contrast with both the doped PM materials, recrystallized undoped PM rod exhibited only very occasional and randomly arranged voids. Furthermore, no voids were observed in either material after electron beam melting. The high concentration of voids in the doped PM materials is attributed primarily to vaporization of doping additions or their pvoducts situated at the original grain boundaries , whereas the few voids in undoped material are considered to be traces of microporosity which were not eliminated during sintering. A tentative mechanism is suggested for the dezlelopment of the voids in relation to the processing sequences (sintering and working) and to the subsequent annealing. In recent years, a characteristic substructural feature consisting of rows of small elongated or circular regions of light contrast lying along the direction of working has been seen in thin foil electron microscopy studies of annealed sheet, wire, and rod tungsten. These features were present in the published micrographs of sheet by Weissmann et al.1 and of wire by Meieran and Thomas2, although the authors did not draw attention to them. Wronski and Fourdeux3 observed similar features in sintered rod tungsten (it was not specified whether or not the material was doped*) and interpreted them on the basis of their ap- particles, based on extraction replica evidence from the fracture surface of the initial hot-rolled slab material from which the sheet was prepared. No diffraction contrast experiments on the features were reported in any of these studies. The present investigation was undertaken with the primary objectives of: a) identifying the nature of these substructural features in tungsten by electron diffraction contrast experiments, since the contrast for voids can be expected to differ from that for crystalline or glassy particles, and b) elucidating the origin of the features and their development. For the latter purpose, doped and undoped powder metallurgy tungsten was obtained as rod and wire to represent different stages of reduction during final processing. These materials were examined both in the as-processed condition and after annealing to successively higher temperatures. In addition, the same doped and undoped materials were examined after vacuum melting in rod form. I) MATERIALS AND PROCEDURE Doped powder metallurgy (PM) tungsten wire (commercial purity 99.9 pct W) was obtained in the as-drawn and surface ground condition (0.030 in. diam "ground seal rod"). Doped and undoped tungsten rod (0.075 in. diam) representing an earlier stage of final processing was obtained from the same commercial source (Refractory Metals Division, General Electric Co.). Lengths of both the doped and undoped rod materials were single-pass melted in an electron-beam zone refiner to examine the effect of vacuum melting on the substructure. Annealing was carried out in a tungsten crucible in a tantalum strip resistance furnace under a vacuum of l0-15 mm Hg. Longitudinal sections of the wire and rod materials were examined by light and electron microscopy. The preparation of thin foils suitable for electron transmission from 0.030 in. diam tungsten wire and the rod specimens was carried out by means of a high-precision microjet technique developed to provide lack of jet stability and precise control of the area thinned. The method is described in detail elsewhere.' The foils were examined in a JEM 6A electron microscope using a goniometer stage (±20 deg tilt, 360 deg rotation) and operated at 100 kV. To minimize contamination problems a 200 µ condenser aperture was used in conjunction with a useful beam current of 50 µA. II) RESULTS AND DISCUSSION A) Diffraction Contrast Analysis. In order to determine the optimum conditions for the development of the substructural feature, a series of isochronal 30 min annealing experiments were carried out on specimens of the doped PM tungsten wire. The transmission electron microscopy analysis showed that the as-drawn wire, Fig. 1(a), consists of 'fibers' whose long axis is closely parallel to the wire axis of (110). The fiber width averages some 0.5 µ. Dense disloca-

Jan 1, 1969

Jan 1, 1923

By John S. Brown

IN 1925 the writer undertook a detailed statistical study of all producing areas in the Joplin district as a basis for evaluating programs and measuring objectives. For this purpose, the published figures in the yearly volumes of Mineral Resources were used, supplemented for earlier years by publications of the Missouri Geological Survey and other local and less official sources. When all else failed, the available data were projected backward to hazard a reasonable guess as to the unrecorded early output of important areas. Fortunately, the proportion of such prehistory production is not a large factor in any of the totals. These results were used during the next few years to measure the relative importance of various producing areas and to predict the peak period of development of the all-important Picher field. For the purpose of this review, the charts have been completed to the end of 1950. During World War 11, the U. S. Bureau of Mines became interested in a similar study and issued comprehensive statistical tabulations of data up to 1945 ( Info. Circular 7383), which have been checked against the figures used herein. This tabulation, however, does not include all the earlier data used by the writer nor does it offer any estimates of the wholly unrecorded era in the beginnings of the earlier camps. The area covered in this study is shown in Fig. 1 on which are indicated the relative location and approximate outlines of the principal producing camps. This also shows the approximate yield to date of each major camp in terms of combined lead and zinc concentrates. The output of zinc concentrates is roughly seven times that of lead. Hence, the economy of the district has depended primarily on the price of zinc, with lead as an important byproduct. Over much of the productive period, lead concentrates averaged about twice the value of zinc concentrates per ton, and in certain mines or areas the proportion of lead to zinc was substantially above average. The Joplin district is largely flat prairie but is partly moderately dissected, partially wooded land with a relief generally less than 100 ft. The rocks are almost flat-lying, nearly parallel to the surface, and the chief ore formation is the Mississippian Boone limestone, including its cherty phases. This formation either outcrops in the producing areas or is covered by a thin veneer of Pennsylvanian shales. Virtually all the ore occurs within 400 ft of the surface, and a large part at less than 300 ft in depth. Most of the land was divided into small farms or town lots before mineral development; tracts seldom exceeded 160 acres, and averaged considerably less. Mineral rights followed the surface ownership, segregation was rare, and a system of leasing for mineral development became well established early in the region's history, many landowners deriving small to sizable fortunes from royalties. Because of the shal-lowness of the ore and other factors, prospecting and mining was cheaper than in almost any comparable mining district in the United States. This situation, coupled with the widely divided land ownership, offered a fertile field for promoters and speculators and led to the rise of many small mining concerns. Only in its later history, under stern economic compulsion, has control tended to centralize in a few companies. Under these conditions, any important new discovery or successful development had much the effect of a gold rush or an oil boom. Every property in the area was leased quickly, promptly drilled, and, if ore was found, it was soon on the market. Many companies and individuals participated, and the average producing lease-hold probably was about 40 acres in extent. Any important field thus was attacked by anywhere from 10 to 100 or more producers. Production zoomed, eventually steadied or wavered, and ultimately subsided, leaving a desolation of tailings mountains, cave-ins, empty housing, and wreckage. The object of this paper is to depict the pattern of this process, so far as metal production is concerned, and to note the way in which it reacted to economic and political pressures. Production Charts In Fig. 2 is charted the production record, in tons of lead and zinc concentrates combined, of eight of the principal camps, which together account for approximately 99 pct of the total district production, over the years from 1870 to 1950. This period covers all but the very minor beginning of mining history. Two important camps are divided by state lines; hence, it has been necessary to combine production records for the two portions, based on estimates that may be slightly in error. Certain camps are sub-dividable into important units for which separate figures are available in whole or in part and have been charted as fractions of the major unit. The corresponding price of zinc is shown above all the charts. Three camps, Aurora, Neck City, and Galena, show a remarkably symmetrical graphic pattern, which is interpreted as the norm. The curves rise steeply to a peak, level off for an irregular interval, and then drop sharply to zero on a slope corresponding roughly to that covered by the initial rise. The three portions of these charts seem appropriately characterized by the designations of youth, maturity, and decline. On the whole, with some irregularities, the production in each of the three periods seems to be almost equal. A fourth camp, Granby, fails to conform to the normal pattern. It exhibits a very long period of reasonably uniform, stabilized production corresponding to maturity, followed by a rather precipitate decline. Its youth is hidden in the era of prehistory. This habit of steady, long-continued production at an even keel is attributable to the fact that this camp, more than any other, was controlled largely by a single principal owner at any given period over most of its history and this permitted the imposition

Jan 1, 1952

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 James K. Gluck, William E. Galloway, Gary E. Smith, John P. Morton, Christopher D. Henry

INTRODUCTION Surface mining and in situ leaching of uranium have the potential to alter ground-water quality around mines and leach sites. Of particular concern is the fate of uranium and its associated trace elements: molybdenum, arsenic, and selenium. We wish to under- stand the natural processes that control trace element concentrations in ground water and how these processes will influence dispersion of the elements from a mineralized zone, both naturally and during and after mining or restoration. For example, it is commonly recognized that the trace elements are soluble in oxidizing ground water but are insoluble, and can be precipitated, in reducing ground water. Thus oxidizing, metal-bearing water leaving a deposit could re- enter reduced ground, causing the water to be re- reduced and the trace elements to be, reprecipitated. In a sense, this is recreating the original mineralization process. To accomplish the above goals, we have (1) examined the theoretical controls of concentrations based on the available geochemical and thermodynamic data, (2) determined the major ion composition and oxidation-reduction status of Oakville waters because of the influence of these factors on trace element solubility, and (3) determined trace element concentrations and distribution in Oakville ground water. The last approach is used to evaluate how well actual behavior follows predicted behavior. This report focuses on two elements, uranium and molybdenum, because they exemplify the results obtained. The report also is restricted to a regional study of Oakville ground water. Results of more de- tailed study in and around major uranium districts in the Oakville and much of the raw data that support the conclusions in this report are presented in Galloway, Henry and Smith (1980). This report is part of that larger study, which concerned the depositional systems, hydrology, and geochemistry of the Oakville. The U.S. Environmental Protection Agency funded the study, under grant numbers R-805357-01 and R-805357-02. Theoretical controls were determined by reviewing the available literature on aqueous chemistry and behavior of uranium and molybdenum. To aid in under- standing water chemistry, Oakville water analyses were run through a modified version of the computer model WATEQF (Plumer, Jones, and Truesdell, 1976). WATEQF calculates speciation of dissolved ions and determines saturation with respect to a variety of minerals. In the discussion below, ion activity products (IAP) are compared with the equilibrium constant (KT) for various reactions and mineral products. Values of log IAP/KT near zero indicate that the water is in equilibrium with a mineral. Values less than -1 indicate considerable undersaturation and values greater than +1 indicate oversaturation. Galloway, Henry, and Smith (1980) give a more complete discussion of the application of this approach to Oakville water chemistry. Eh-pH diagrams have been constructed or adapted from the literature to predict what form -- dissolved ion or stable mineral species -- uranium and molybdenum assume under various conditions. Construction of the diagrams has followed procedures described by Garrels and Christ (1965). This approach is particularly appropriate because the solubility of the elements is Eh-dependent, and Eh varies greatly within the Oakville aquifer. A number of assumptions or approximations are inherent in the use of Eh-pH diagrams and chemical models such as WATEQF and in the interpretation of water chemistry in general. Both Eh-pH diagrams and chemical modeling rely entirely upon available thermo- dynamic data, including free energies of formation and dissociation constants for various reactions. These values are known to varying degrees of accuracy. Most major ions and minerals are relatively well control- led; however, data for trace metals are much poorer. Thermodynamic data are not available for some minerals, and for other minerals, two or more divergent values exist. By necessity, we have relied on the judgment of others to evaluate thermodynamic data. Calculations by WATEQF and constructions of Eh-pH diagrams are based on an assumption of equi1ibrium. Equilibrium may not be comnon in low-temperature aqueous environments; at best, ground-water composi tion may be in a state of dynamic equilibrium, continuously changing due to changes in environmental conditions. Eh-pH diagrams show what phases are stable at equilibrium under given conditions; they do not prove that the phases actually exist. Many minerals persist or form metastably under conditions outside their equilibrium stability field. The kinetics of reactions, which cannot be evaluated here, are important in determining what phases occur. Kinetics may be less of a problem for ground water that travels and evolves slowly through a semihomogeneous matrix than for many other natural systems. Eh-pH diagrams show equilibrium fields only of phases included. They do not indicate anything about stability relative to phases not included in the diagram. WATEQF, obviously, cannot calculate the degree of saturation of a mineral not included in the program or for which the appropriate ions were not analyzed. Thus, a mineral that was not considered may be the most stable phase under a given set of conditions and may control the solubility of a trace element. Also, this study is limited exclusively to in- organic compounds. Organic material is known to be an

Jan 1, 1980

By Glenn C. Waterman

THE diamond drill is a very important tool in exploration and development testing and its use is increasing. In almost all cases results of diamond drilling are analyzed on the basis of grade and tons. A proper evaluation of core and sludge assays is important if drilling results are to be acceptable as a basis for geologic and engineering appraisal. The relatively wide variation in assay averages as calculated by various well-known combining methods indicates that the engineering choice of a method may affect the outcome of the drilling in terms of ore and waste. The problem of combining assay results from core and sludge samples has been discussed many times in conference and in the literature.'-' Most writers agree that the field of disagreement in methods is large and that the engineer on the job must consider features unique to his drilling, pick one of several combining methods, and depart from the rules when abnormal results come in. All the discussion to date can be summed up by the admission that as yet there is no fairly simple, generally acceptable combining method that is practicable over a wide range of drilling conditions, ground conditions, and ore occurrence. The combining problem is important in evaluating drilling results at Chuquicamata. Recently a reappraisal has been made of recovery variables and their effect on assays, with the result that a new combining method is offered which fits average drilling conditions and is mathematically reasonable. It is simple in application, fundamentally correct, and an improvement over most combining methods. At Chuquicamata diamond drillholes are used to outline the grade and position of blocks of normal and marginal grade oxide, mixed, and sulphide ore. Most holes penetrate all classes of material (and waste), and it is important for mining programs as well as ore reserves to know almost precisely the soluble and insoluble copper content of mineralized ground. At present three classes of ore are mined and treated differently. For an orderly sequence of mining operations which can provide regular daily tonnages of all three ore types and keep grade at certain levels with minimum variation, ore type and its grade must be predicted. Diamond drilling plus geologic mapping and bench sampling are tools for prediction. And drilling data are largely used to calculate grade of material more than a few meters away from bench faces. The orebody at Chuquicamata" is criss-crossed by millions of barren or mineralized weak to fairly strong slips and fault fissures. Mineralization is diverse and encompasses many quartz and oxide or sulphide-bearing copper veins, as well as seams and disseminated grains. Copper occurs in oxide or sulphide minerals or mixtures of these two mineral types. Rock conditions vary from intensely seri-citized (soft and porous) through clay-altered ground to almost fresh granodiorite. The result is an orebody which offers many obstacles to good and consistent core recovery in diamond drilling. Recovery varies considerably in the several alteration zones, the various types of oxide and sulphide ores, and the position and inclination of the drillhole within the complex fracture pattern. As core recovery drops sludge samples must be used with core samples to calculate grade. Many years of drilling at Chuquicamata indicate that in good grade oxide zones and in the sulphide areas core recovery is good and the ground uniformly mineralized. Moderate loss of core, therefore, does not markedly affect grade calculations based on core assays. An early core-sludge combining method used core assays at face value as indicating grade down to 50 pct core recovery, but below this recovery percentage sludge samples were used and weighted according to the standard Longyear chart. This method apparently did not introduce serious errors, but it abruptly used sludge assays with high weighting factors representing 100 pct return irrespective of actual percentage of sludge recovered. Recent drilling activities have been directed toward outlining the marginal ore areas. The non-uniform mineralization and generally poorer core recovery in such ground indicated that a more exact core-sludge combining method was required to equate wide differences between core and sludge assays and recovery. In fringe ore areas at Chuquicamata core recovery averages about 50 pct, from a minimum of 10 to 15 pct to a maximum of 100 pct. Sludge recovery is likewise variable and averages perhaps 80 pct even though holes are cemented as water return falls off. In a homogeneously mineralized area cut by many slips and faults, with hard and soft ribs, loss of core is loss of ground which has a grade similar to that of core recovered, and core assays approximate true grade. In this case sludge samples need not be used. However, it would be unusual to know beforehand that an area is uniformly mineralized, and in fact this condition is probably uncommon. Generally the distribution of valuable minerals in the ground does not exactly compare with their recoverability in core. Thus, in the usual case, loss of core decreases the

Jan 1, 1956

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

A perspective is presented of the steel plant sulphur distribution and elimination problem from coal to liquid steel ready for teeming, giving distributions of sulphur over a range of coke sulphur content, and some methods of sulphur control, in the blast furnace, external desulphuriza-tion between blast furnace and open hearth, distribution between fuel, slag, and metal, and methods and limitations of control of sulphur in the open hearth furnace. AS a part of the 1951 AIME symposium on sulphur in steelmaking, it was thought that a discussion of the distribution of sulphur throughout the whole series of operations, from coal and ore to finished steel ingots, might have some value in giving a perspective on the whole problem. The following discussion is an attempt to present such an overall picture. The order is that of the actual plant operations, beginning with a very brief consideration of the coking process. Sulphur in Coal and Coke Since by far the largest source of sulphur entering the steelmaking cycle is in the coal used to make coke for the blast furnace, it would seem reasonable to eliminate some of it, either from the coal, or the coke, or during the coking process. This has appeared impracticable up to the present, at least, for two main reasons: the low activity of the organic sulphur in either coal or coke, and because of price limitations involved in treating a low cost material such as coke. A variable portion, usually M or less, of the sulphur is present in coal in the form of pyrites or similar compounds, and a large part of this sulphur may be removed in the coal washery. Most of the sulphur, however, is normally present as "organic" sulphur, intimately associated with the coal structure. Its distribution prevents any separation by mechanical means. Its low activity makes improbable ' any rapid chemical removal, although hydrogen will remove sulphur from both coal and coke. Thus, prolonged recirculation of coke oven gas in the coking process would tend to leave a smaller percentage of the total sulphur in the coke residue. Table I shows a typical distribution of sulphur from coal into products in the coking process. As the sulphur in the coal increases, the sulphur in the coke tends to increase in about the same proportion. Sulphur in the Blast Furnace The best picture of the situation in the blast furnace is provided by a sulphur balance of raw materials entering, and of products leaving, the furnace. The difficulties in accurate weighing and sampling of the variable solid materials entering this process, and the number of hours required for the raw materials to descend through the furnace under variable operating conditions, make it difficult to obtain an accurate balance. However, balances made over periods of weeks or months tend to average out some of these uncertainties. Table I1 presents three typical sulphur balances similar to a number that the writers have calculated. In most of these the slag volume calculated from the sulphur balance is, in some instances more, and in other instances less, than the value corresponding to the best input and output balances of the other slag constituents (lime, silica, alumina, etc.). Probably the greatest source of error in these calculations is the sulphur content of the slag. Despite some possible inaccuracies the balances of Table II show rather definitely the following points: 1—That 87 to 95 pct of the total sulphur input is in the coke and 95 to 97 pct of the total sulphur output is in the slag. Also, that if any sulphur leaves the furnace with the gas it is relatively small, amounting to a possible 1 pct or less. 2—At the lower sulphur coke level of 0.86 pct the total amount of sulphur charged is 15 Ib of sulphur per ton iron increasing to 26 lb per ton at the higher sulphur, intimately associated with the coal struc-rare burdens containing sulphur-rich ores will the total sulphur burden fail to be nearly proportional to the content in the coke used. 3—The 7 to 9 pct of the total sulphur input from the limestone of furnaces B and C is due to the relatively high sulphur content of the stone, 0.226 and 0.265 pct, respectively. In the case of furnace A, the sulphur content of the limestone was only 0.06 pct which resulted in only 3 pct of the total sulphur input coming from this source. It is rather interesting to compare the sulphur balances of a typical ferromanganese furnace with

Jan 1, 1952

By J. A. Pusateri, M. A. Orehoski, N. R. Arant

Plant studies on commercial-size ingots and laboratory experiments with induction furnace heats have demonstrated that the major source of ingot cracks is associated with two conditions arising during top-pouring practice: 1—solidification during pouring, and 2—turbulence created by the impact of the stream. Methods of controlling the two factors were effective in eliminating or significantly reducing ingot cracks. BECAUSE the process of removing surface defects from hot-rolled product is so costly, the steel industry is striving constantly to develop methods of preventing, or at least decreasing, the occurrence of surface defects. Investigations have revealed steel-making and processing variables related to major surface defects, and controlling these variables has led to improvements in surface quality. However, the fundamental causes of major surface defects, such as ingot cracks, have not been determined; consequently such defects persist. At the Research and Development Laboratory of the United States Steel Corp. in Pittsburgh, a seam research program was initiated to determine the fundamental causes of certain major defects. As a part of the program, ingot cracks in killed, finegrained C1020 steel were selected for study. A cost survey indicated that, of the steels produced in sizable tonnages, carbon steels in the range of 0.18 to 0.23 pct C content require the most conditioning. Since this is particularly true of C1020, any im-provement of surface quality that might be effected from the study would be beneficial. Also, since the frequency of ingot cracks is exceedingly high for this grade, the steel would provide an excellent opportunity for a thorough study of the ingot-crack-ing problem. Why steels in this carbon range tend to exhibit more ingot cracks than do other steels was not considered in the investigation; the mechanism of ingot-crack formation was of paramount importance. Also, only the top-pouring practice was considered in the investigation, because this pouring procedure is used more extensively than others. In this study, ingot cracks are defined. as deep surface defects that sometimes are observed in an ingot prior to rolling but usually are observed during the initial stages of rolling on the primary mills. These defects may occur at any angle to the rolling direction but are most prominent in the transverse or nearly transverse direction. The appearance of ingot cracks on the rolled product varies with respect to their angle of formation and with the extent of rolling after their first occurrence. Ingot cracks are also termed "deep seams," "arrowheads," "irregular cracks," and "transverse cracks." Fig. 1 shows ingot cracks in a rolled bloom. This report summarizes: l—the exploratory investigation of commercial-size ingots; 2—the labor-atory investigations related to determining the source of ingot cracks and developing corrective methods; and 3—the plant evaluations of laboratory methods of decreasing ingot cracks. Exploration of lngot Cracks in Commercial Ingots Materials and Experimental Work: At the Du-quesne Works of the United States Steel Corp., five heats of killed, fine-grained C1020 steel were selected for the exploratory phase of the seam-research program. The heats were made by open-hearth practices that are considered most conducive to good surface quality. They were top-poured into 22x25 in. big-end-up hot-topped molds. One as-cast ingot and four other ingots rolled to the following cross-sectional sizes were set aside from each heat: 16x20 in.; 9 1/2x10 in.; 5x5 in.; and 2x2 in. The processing of the heats, from the time of charging in the open hearth furnaces to the end of the rolling operation on the primary mill, was observed carefully and recorded. The cast ingot and the four rolled ingots from each heat were examined for surface defects. The cast ingots were split longitudinally near the vertical center plane to expose the ingot structure beneath badly cracked regions. Also, a series of transverse sections was cut at about 1 in. intervals in a badly cracked area of one ingot. All sections were ground, polished, examined by sulphur printing and deep etching, and photographed. The rolled ingots

Jan 1, 1955

By R. G. Wayland

SINCE the installation at Kropfmuehl, Bavaria, of a modern flotation concentrator in 1938, the flake and fine graphite from the Passau area can now be delivered in about any normal specified carbon content of any size range up to a flake averaging about 0.7 mm. The graphite finds a wide German and export market for crucible manufacture, pencil leads, dry cells and other uses. A controversy over the origin of the graphite deposits is being resolved in favor of syngenesis rather than epigenesis. The syngenetic theory is newly supported by the yet unpublished work of Hartmann of the Bavarian Geological Survey. Development work and exploration for graphite in the area may be changed in direction as the syngenetic theory is accepted. Crystalline graphite is produced in the area east of Passau near the junction of Germany, Austria and Czechoslovakia, as shown in Fig. 1. This is the only graphite area of importance in Germany, and Gra-phitwerk Kropfmuehl AG is the only operating firm in the area. The plant and mine are located at Kropfmuehl near Hauzenberg, Kreis Wegscheid, about 10 miles east of Passau. A narrow gage railway from the mine connects with the German Railway at Schaibing Bahnhof. The Pfaffenreuth mines date from about 1730. Until the early 20th century mining operations were carried out in a haphazard fashion. During World War I graphite mining and milling was increased, since it had to cover almost all of the crucible needs of the Central Powers. Between the wars some 11 mines were operated by two large and several small companies, but under the Nazis these were consolidated by 1938 into the Kropfmuehl enterprise. Kropfmuehl built a modern flotation mill to treat its own ores and small amounts of custom ores and tailings from the area. Since Graphitwerk Kropfmuehl AG was an I.G. Farbenindustry subsidiary, it has been under Military Government Property Control and probably will be sold to private German capital. Geology The country rock of the graphite area is part of the "kristallines Grundgebirge," the series of old gneissic and schistose rocks that constitutes the bed rock of most of the Bohemian basin and rims the Sudeten-land. The gneissic rocks of the graphite area are considered to have been metamorphosed during the Carboniferous period. They are bordered on the north by granite stocks and penetrated by numerous smaller granite and pegmatitic intrusive rocks, as shown in Fig. 1. The gneiss is classed as a micaceous, coarse-grained cordierite gneiss by most investigators. It is much metamorphosed by the granite, particularly in the north near the larger granite bodies. Interbedded in the gneiss are the graphite seams and lenses, and also beds and lenses of crystalline limestone containing disseminated graphite in noncommercial quantities. The gneiss, together with the included graphite and limestone seams and lenses, is cut and displaced by a number of granite sills of medium to fine grain and by a large number of diorite lamprophyre dikes and a few syenite-pegmatite dikes. The lamprophyre dikes are of various mineral compositions and textures, but many are banded and richly impregnated with pyrite; while the syenite-pegmatite dikes are coarse-grained with good crystals of titanite, pyroxene, uralite and other green amphiboles. Most investigators and the miners speak only of diorite and granite dikes cutting the graphite seams. The diorite dikes are later than the granite and some of the faulting, as is evident from Figs. 1 and 2. Individual graphite seams and lenses may be mined for thicknesses of several feet up to several scores of feet, and for distances of several hundred feet. The aggregate thickness of a series of some 20 seams of graphite, limestone and interbedded gneiss at Kropfmuehl is stratigraphically about 450 ft. Laterally, the graphite in a seam may pinch out or grade into crystalline limestone. Graphite crystals also are found disseminated in the gneiss itself, although in unmineable concentrations. The faults that cut the graphite seams carry graphite for some feet or tens of feet away from the seams, apparently mechanically. Similarily, the graphite lenses themselves often contain mechanically introduced inclusions of wall rock, probably from flowage during folding. Graphite crystals make up 10 to 30 pct of the fresh, mineable graphite lenses at Kropfmuehl, averaging about 20 to 25 pct after hand-sorting by the miners. In weathered lenses, the graphite concentration is said to be as high as 50 pct. The associated primary and hydrothermal minerals are dom-inantly feldspar and calcite, plus quartz, pyrrhotite, pyrite, biotite and occasional garnet, hornblende, sphalerite and galena. Associated secondary minerals include kaolin, nontronite, mangano-oxide-silicates (mog), adularia and chlorite. The superimposed suite of siliceous cementation minerals present consist largely of opal, chloropal, chalcedony, jasper, and hyalite. The kaolin is of special interest since it too was mined as early as 1730 and was used in the well-known Nymphenburg porcelain from 1756 on. The kaolin is derived from the gneiss and the syenite pegmatites. The crystals of graphite vary in size within a given seam, but in seams more than a mile away from the granite on the north the average crystal-linity is less coarse, lowering the commercial value. The lenses in the Kropfmuehl-Pfaffenreuth area are the most developed, and are the only ones with deep workings now accessible. Other similar crystalline graphite lenses are known from older workings at Habersdorf, Oberoetzdorf, Ficht, Diendorf, and

Jan 1, 1952

By C. R. Watts

The feasibility of producing composites containing nickel or molybdenum fibers in a beryllium matrix was inrestigated. The composties studied were jabricaled by powder mallurgical techniques. The 1-mil-diarr nickel fibers reacled completely below 900°C, converling the fibers .from nickel to Ni5Be2,. As the /LO/-pressing temperalure as raised above 1110oC, tlie nickel diffused outward from the beryllide fibers. The solid solubility of nickel in beryllium was clboul 20 wt pet at the 1100°C pressing temperature a1 the zone-fiber interface. The 1.5-mil-diam molybdenum fibers slzolred no evidence of reaction and little evidence of diffitsion after pressing at 900°C. Between 1000° and 1050°C pressing conditions, the fibers began lo react , producing 1ayers of MoBe2 and MoBe12, respectively surrounding the molybdenurn core. The struture remained the same at 1100°C with no evidenre of solid solubility of the molybdenum in the berylium or vice versa. In recent years a considerable amount of attention has been devoted to the determination of methods for improving the mechanical properties of materials through the use of fiber or whisker reinforcement. Previous work with metal matrix composites indicates that the study of the chemical compatibility of the fiber and matrix is an area requiring greater understanding. The metal-metal or ceramic-metal interface is frequently subject to chemical reactions that may result in the formation of hard brittle intermetal-lic compounds and/or low melting point eutectic compositions. The reaction products may reduce both the low-temperature and elevated-temperature strength of the composite by weakening the fiber-matrix bond, producing premature failure at the interface. It is well-known that most metal-metal systems and many metal-ceramic systems of interest for structural composites are thermodynamically unstable,'-" particularly at elevated temperatures. If, however, the rate of reaction under the conditions of fabrication is sufficiently low. composites can be fabricated that can be used efficiently for indefinite periods at low temperatures and for short periods at elevated temperatures. This paper presents the results of a series of tests to determine the compatibility of nickel and molybdenum fibers with beryllium at various hot-pressing temperatures. Nickel was selected as a candidate fiber material primarily because the relatively ductile fibers might be useful as crack arresters in applications such as ballistic impact where crack growth can result in catastrophic failure. The high density and the reactivity of nickel were primary factors detracting from its selection as a possible reinforcement. Molybdenum with a modulus of elasticity of 52 Xlo6 psi is one of the few metallic materials having a modulus higher than beryllium (42 X lo6). Its high modulus, coupled with its refractory characteristics, made molybdenum an attractive candidate for a relatively stable fiber reinforcement for beryllium. Its density, being higher than that of nickel and over five times that of beryllium: detracted from its other characteristics. EXPERIMENTAL PROCEDURE The specimens were prepared from beryllium powder with a dispersed phase of fibers by powder metallurgical techniques. P-20 grade powder, Table I, from Berylco was used as the matrix material. Short lengths of 0.001-in.-nominal-diam nickel fibers supplied by the Sigmund Cohn Corp. and 0.0015-in.-nominal-diam molvbdenum fibers obtained from the General Electric Co. were used as the dispersed phase. The composite constituents were combined under an argon atmosphere by mechanically mixing the powders and fibers. The compositions used were nominally 1 vol pct fibers. After mixing. the composites were hot-pressed into a-in.-diam pellets under an argon atmosphere at 900°, 1000". 1050". and 1100°C at a pressure of 6000 psi with no hold time at these temperatures so that a comparison could be made between the resultant microstructure and hot-pressing temperature. The billet was heated at a rate on the order of 30°C per min to the desired temperature and then cooled at a somewhat slower rate. The microstructure obtained should be considered as characteristic of the integrated time-temperature history of the sample, as well as the maximum temperature attained. Upon removal from the hot-pressing dies. the specimens were cut. mounted. and polished by standard procedures. No etchant was used in specimen preparation. Photomicrographs, electron microprobe scans, and electron back-scatter pictures were made. X-ray dif-fractometer patterns were made of several of the specimens. but only the lines for beryllium could be resolved. Specimens for optical and electron microprobe examination were selected partially for the roundness of the cross section. A round cross section was taken to indicate that the body of the fiber was approximately normal to the surface and that therefore effects due to fiber material immediately below the surface could be neglected. RESULTS AND DISCUSSION The microprobe scans indicated that nickel reacted as low as 900°C, converting the entire fiber cross section to NisBe21. Fig. l(a). There was no evidence of further reaction from the optical or the back-scatter pictures, Figs. 2(n) and 3(a).

Jan 1, 1970

By Lawrence H. Van Vlack, Otta K. Riegger

Periclase-type oxides were examined microscopically after being exposed to siliceous liquids. The rate of grain growth was found to be inversely proportional to the grain diameter. Grain growth proceeds more rapidly at higher temperatures, but is retarded by increasing liquid contents. aMag-nesiowiistites with higher MgO contents grow less rapidly than those with higher FeO contents. The growth rate is reduced by the presence of a second solid phase. The silica-containing liquid penetrates as a film between the individual magnesiowus tite grains. This is independent of time, temperature, amount of liquid, or the MgO/ Fe0 ratio. When present, olivine and spinel-type phases can provide a solid-to-solid &apos;&apos;bridge" between magnesioustite grains. THIS paper presents the results of a study of the microstructures of periclase type oxides in the presence of a silicate liquid. The purpose was to learn more about the effect of service factors such as 1) time, 2) temperature, and 3) liquid content upon A) grain growth, and B) liquid location among the solid grains. This study was prompted by the fact that periclase refractories are known to have very little solid-to-solid contact when the phases which are present are limited to periclase and liquid. Such a micro-structure gains industrial significance because it permits fracture during service when stresses are applied at high temperatures. The details of ceramic microstructures have not received extensive attention. This is in contrast to the extensive attention given to a) the phase relationships pertaining to refractory compositions, and b) the details of the microstructures of comparable metallic materials. A brief review will be made of the pertinent phase relationships and microstructural considerations in general, as well as of refractory compositions. a) Phase Relationships. This investigation was limited to those compositions in which (Mg, Fe)O was the solid phase. MgO and FeO form a complete series of solid solutions. Pure MgO has the name of periclase. The related FeO structure is called wustite. Both have the NaC1-type structure: however, wustite possesses a cation deficiency so that the true composition is Fe<10 even in the presence of metallic iron. The phase relationships involving solid (Mg, Fe)O and a silicate liquid are shown in Fig. 1. In this case. the liquid is saturated with (Mg, Fe)o. There-fore its SiOz content is below that encountered in orthosilicate liquids. As a consequence the liquid phase specie:; are primarily the following ions: and 0-&apos; plus occasional Fe+ ions. Two features are of importance: a) the liquid contains relatively small species and b) the liquid contains large quantities of the same species as the solid. viz., Fig. 2 shows the system, FeO-SiOz, which will be used in some of the discussions that follow. This diagram is the right side, vertical section of Fig. 1. Here, as pre\iously, the composition at the FeO end of the diagram is nonstoichiometric, varying from Feo.950 when the liquid oxide is in contact with the solid iron, to about Fe 0, when the solid oxide is in equilibrium with an atmosphere of equal proportions of CO and C02 at the solidus temperature. The Fe/O ratio will be maintained in wustite in the presence of SiO,. However, the FeM/Fe++ ratio in the liquid will be lower because of the effect OIF the SiO, on the activity of the FeO. With the addition of MgO to wustite, the over-all composition (IvZg, Fe)@, has a value of x lying between 0.9 and 1.0 when the COz/CO ratio is 1.0&apos;. b) Microstructures. In general, published attention to refractory microstructures has been directed toward the phase analyses that accompany compositional variations. This is illustrated by Harvey6 in his work on silica brick and by wells7 in his work on periclase brick. In each case, a series of altered zones is encountered which provides a sequence of phase associations. If due consideration is given to reaction kinetics, such an examination reveals phases that are compatible with equilibrium studies. Admittedly, however, it is often necessary to determine more complicated polycomponent systems to account for all the phases present.8 Relatively little attention has been given to microstructural geometry in ceramic materials. Certainly less attention has been given to this aspect of ceramic microstructures than to the size, shape, and distribution of the constituent phases in metals. Burke has pointed out that the grain size of oxides follows the same growth rules as for metals, viz.,

Jan 1, 1962

Jan 1, 1924

By Harry K. Ihrig

The hot-working of iron and steel is an art dating back to antiquity, but until about 25 years ago, relatively few alloying elements were used, and these were present only in small percentages. With the exception of sulphur, the amounts of other elements in steels did not markedly affect their hot-workability. The references in the literature on the effect of other elements on the hot-workability of steel are usually reports of failure of these steels in forging or rolling.1-8 With the increased use of alloying elements, and their use in larger amounts, it was observed that many of the new steels were red short in certain critical ranges or at all hot-working temperatures. The stainless steels are particularly difficult to hot-work. The determining of the correct conditions for piercing, rolling and forging of these alloys by experimentation in the mill often results in large losses of these expensive metals. It also is found that the hot-workability limits of many types vary from heat to heat, and hence poor results are obtained on changing to a new heat after a previous one has rolled satisfactorily. To determine the effect on hot-workability of iron to which various elements have been added, it was necessary to devise a method that could be used on small quantities of metal. In such a method, the minimum number of variables should be present, and the procedure should be simple, quick and correlatable with large-scale hot-working operations. Sauveur,9 in the first Henry Marion Howe lecture in 1924, described the effect of carbon on the ductility of steels in torsion near their critical points. He found that carbon increases the plasticity of gamma iron. In the 1930 Campbell Memorial lecture,10 he gives the effect of carbon, chromium, and chromium and nickel on the ductility of steels under 2000°F. in torsion. Ellis11 has studied the malleability of steels at various elevated temperatures by means of a single-blow drop-hammer test. In this test the percentage decrease in height of standard cylinders is taken as a measure of their malleability. He has shown that in the low-alloy steels studied, carbon has a greater effect than nickel, chromium and vanadium. In 1938 the first tests were run on a new quantitative hot-workability test in the laboratories of the Globe Steel Tubes CO. Thum12 mentioned it in 1940. An illustration of the apparatus was published in January 1942.&apos;&apos; The effect of a few alloying elements on the hot-workability of metals was shown in a description of the test in 1944.14 Description of Test Method The method adopted after a trial of several others is a rapid twisting of bars to failure in a furnace. The standard-size bar was chosen as 9/16 in. It is prepared from larger pieces by forging and cold-

Jan 1, 1947

By C. S. Giggins, F. S. Pettit

The oxidation properties of Ni-Cr alloys with fine grains, coarse grains, and deformed surface layers have been studied at temperatures of 900" and 1100°C in 0.1 atm of oxygen. The oxidation rates of alloys containing between 10 and 30 wt pct Cr have been found to be dependent upon the grain size of the alloy. Finegrained alloys had smaller oxidation rates than coarsegvained alloys because of the selective oxidation of chromium at alloy grain boundaries. In this compositional range alloys with deformed surface layers behaved similar to fine-grained alloys due to recrys-tallization of the deformed surface layer. In the preceding paper1 it was found that during the oxidation of Ni-Cr alloys, the volume fraction of precipitated Cr2O3 could be greater at alloy grain boundaries than at other areas of the alloy surface. In the case of alloys with chromium concentrations equal to or greater than 30 pct,* the volume fraction of Cr2O3 *AIL compositions are given as weight percent unless specified otherwise. precipitated at grain boundaries and within grains on the alloy surface both exceeded the critical amount required for lateral growth of the Cr2O3 particles and the surfaces of these alloys were completely covered with a continuous, external layer of Cr203 during oxidation. However, in the case of alloys with chromium concentrations between approximately 5 to 30 pct, the volume fraction of precipitated Cr2O3 exceeded the critical value required for external scale formation only at grain boundaries.but not within the interior of the grains. Consequently, the surfaces of these alloys had external scales of Cr3O3 over the grain boundaries but internal Cr2O3 subscales with external scales of NiO away from the grain boundaries. Under these latter conditions, it was found that chromium could diffuse laterally in the alloy from those areas covered with an external layer of Cr2O3, i.e., grain boundaries, to areas where the Cr2O3 was present as a subscale. This diffusion of chromium resulted in an increase in the volume fraction of Cr2O3 precipitated in the sub-scale zone and continuous layers of Cr2O3 could be formed at the subscale front in these regions. For the alloys used in the previous studies,&apos; continuous layers of Cr2O3 were formed on Ni-20Cr alloys in the subscale regions after approximately 30 hr of oxidation at 900°C. For shorter periods of oxidation, the Cr2O3 layer was semicontinuous with the continuous portion at the subscale front emanating from points where the Cr2O3 had been formed as an external scale over alloy grain boundaries. Some lateral growth of a Cr2O3 layer in the subscale region was observed on Ni-15Cr and even Ni-10Cr alloys but this layer was never continuous after 30 hr of oxidation. These results indicate that the selective oxidation of chromium in Ni-Cr alloys with chromium contents between 5 to 30 pct may be dependent upon the grain size of the alloy. Fine-grained specimens in this compositional range should have a larger fraction of the surface covered with external Cr2O3 than coarsegrained specimens and the subscale areas required to be sealed via lateral diffusion of chromium should be smaller. It is therefore to be expected that a continuous layer of Cr2O3 can be formed on alloys in this compositional range after short periods of oxidation providing the alloy grain-size is sufficiently small. bo studieS2,3 have established that the oxidation behavior of alloys can be significantly influenced by pretreatments which produce mechanically deformed surfaces. It has been found that deformed surfaces usually promote the selective oxidation of elements in alloys and it is believed that these effects are due to rapid diffusion of elements in the deformed layer. In view of the previous results,&apos; which showed that alloy grain boundaries may play an important role in the selective oxidation of chromium in Ni-Cr alloys, deformed surfaces may promote the selective oxidation of elements in alloys as a result of the numerous grain boundaries formed on the alloy surfaces via recrys-tallization during heating to the oxidation temperature. The purpose of the present studies was to determine the effect of alloy grain size and surface deformation on the selective oxidation of chromium in Ni-Cr alloys at temperatures of 900" and 1100°C in 0.1 atm of oxygen. EXPERIMENTAL The average grain diameter of the alloys used in the previous studies1 was not less than 0.04 mm and alloys with compositions between 5 and 30 pct chromium had average grain diameters between 0.04 and 0.14 mm. Since the oxidation kinetics were already available for these relatively coarse-grained alloys, it was desirable to use these same alloys in the present studies. The surfaces of the alloys listed in Table I of the previous paper were deformed by using a Model F S.S. White Industrial Airbrasive Unit, which delivered a controlled mixture of 25 µ Al2O3 particles in a stream of dry air at high velocity against the surface of a specimen. The amount of surface deformation produced by this treatment was not determined but a re-crystallized layer about 15 µ thick was formed upon annealing deformed specimens. The grain size at the surface of the specimens was reduced to an average grain diameter of 0.01 mm by annealing the deformed specimens, i.e., grit-blasted,

Jan 1, 1970

By Harry K. Ihrig

The hot-working of iron and steel is an art dating back to antiquity, but until about 25 years ago, relatively few alloying elements were used, and these were present only in small percentages. With the exception of sulphur, the amounts of other elements in steels did not markedly affect their hot-workability. The references in the literature on the effect of other elements on the hot-workability of steel are usually reports of failure of these steels in forging or rolling.1-8 With the increased use of alloying elements, and their use in larger amounts, it was observed that many of the new steels were red short in certain critical ranges or at all hot-working temperatures. The stainless steels are particularly difficult to hot-work. The determining of the correct conditions for piercing, rolling and forging of these alloys by experimentation in the mill often results in large losses of these expensive metals. It also is found that the hot-workability limits of many types vary from heat to heat, and hence poor results are obtained on changing to a new heat after a previous one has rolled satisfactorily. To determine the effect on hot-workability of iron to which various elements have been added, it was necessary to devise a method that could be used on small quantities of metal. In such a method, the minimum number of variables should be present, and the procedure should be simple, quick and correlatable with large-scale hot-working operations. Sauveur,9 in the first Henry Marion Howe lecture in 1924, described the effect of carbon on the ductility of steels in torsion near their critical points. He found that carbon increases the plasticity of gamma iron. In the 1930 Campbell Memorial lecture,10 he gives the effect of carbon, chromium, and chromium and nickel on the ductility of steels under 2000°F. in torsion. Ellis11 has studied the malleability of steels at various elevated temperatures by means of a single-blow drop-hammer test. In this test the percentage decrease in height of standard cylinders is taken as a measure of their malleability. He has shown that in the low-alloy steels studied, carbon has a greater effect than nickel, chromium and vanadium. In 1938 the first tests were run on a new quantitative hot-workability test in the laboratories of the Globe Steel Tubes CO. Thum12 mentioned it in 1940. An illustration of the apparatus was published in January 1942.&apos;&apos; The effect of a few alloying elements on the hot-workability of metals was shown in a description of the test in 1944.14 Description of Test Method The method adopted after a trial of several others is a rapid twisting of bars to failure in a furnace. The standard-size bar was chosen as 9/16 in. It is prepared from larger pieces by forging and cold-

Jan 1, 1947

COAL is perennially -a subject of major interest at. Pittsburgh, but during the week of Nov. 19 to 24 it was especially to the fore because nearly two thousand persons gathered to take part in the second of the international conferences organized by President Baker of the Carnegie Institute. From the opening session on Monday morning when those attending were welcomed by President Baker and T. P. Gaylord, president of the Chamber of Commerce of Pittsburgh, until the party returned from the Clairton coke ovens on Saturday. afternoon, there was something going on all the time, and usually three sessions were in progress at once.

Jan 1, 1928

Jan 1, 1924

The United States has never been a large coal exporting nation, and normally such shipments, aside from those to Canada, have been relatively small. Since the first railroad was built across the Allegheny Mountains, the imports have been quite small also, although fairly large tonnages of Canadian coal have moved into the extreme northeastern and northwestern states at times. In Table 21 are shown all data available about these shipments from 1790 to 1939, inclusive.

Jan 1, 1942