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By Frank H. Reed, P. W. Henline, Harold W. Jackman

A SUMMARY of the consumption of coal in 1945 shows that the coke industry accounted for 17 pct of the total coal used. No substitute for coke and the blast furnace in the reduction of iron ore has gained sufficient prominence so far to be given serious consideration. However, while the same slot-type ovens are being built and used now as were in use a few years ago, the problem of obtaining suitable coking coals, both high- and low-volatile, has forced many operators to revamp coal-blending facilities. Until the beginning of World War II, high-temperature coke plants were able to secure the required high-volatile and low-volatile coals from two or three seams and from three or four mines. Thus, many of our coke oven plants were able to operate with storage bins for two coals only. The variance in raw materials was not great, and uniformity of blend was a relatively simple problem. Since the beginning of World War II, many and important changes have taken place. Demand for all coals increased greatly. Production, though kept as near maximum capacity as possible, could not meet the demands for coal generally, and particularly for the various kinds of coal which have proved to be satisfactory for specialized uses; coals were allocated as nearly as possible in the order of greatest need; storage piling was reduced to the minimum necessary to keep plants in operation; uniformity of quality could not be maintained, and with this last, uniformity of composition of blends for coking could not be maintained. Whereas before the war producers of metallurgical coke could fill their needs from three or four mines, by the end of the war it was not unusual to find shipments to a single coke oven plant coming from as many as 30 different mines, in a single month. Since many of the mines producing both high- and low-volatile coal for high-grade metallurgical coke are rapidly nearing depletion, the problem of seeking new sources and of blending a number of coals in each plant for the production of high-temperature coke is facing practically every producer in the United States at the present time, and is one which will probably continue for many years to come. Midwestern by-product coke ovens in the Chicago and St. Louis areas use annually from 12 to 15 million tons of bituminous coals which are transported 500 to 700 miles from the Appalachian coal fields of Pennsylvania, West Virginia, and eastern Kentucky. Approximately two-thirds of this coal is high-volatile bituminous. The critical transportation problem confronting the nation in 1943, and the growing scarcity of the best Appalachian coking coals, prompted the Illinois Geological Survey to propose a research program in which would be studied the coking properties of blends of low-sulphur, high-volatile Illinois coal with the high- and low-volatile coals from the eastern fields. Such blends containing Illinois coal, if substituted for the all-eastern blends normally coked,

Jan 1, 1948

By D. W. Lillie

It has been demonstrated that considerable bend ductility exists in bulk specimens of polycrystalline high-purity silicon. The possibility of hot-forming at 1200°C is suggested. EXCELLENT corrosion resistance in many media and low cross section for absorption of thermal neutrons (0.13 barn) would make silicon of interest to nuclear engineers were it not for extreme brittle-ness and the difficulty of fabrication by any reasonable means. The use of silicon for structural purposes also has been considered in view of its light weight and oxidation resistance. Johnson and Han-sen' have investigated the properties of silicon-base alloys and concluded that there was no way of making pure silicon or silicon-rich alloys ductile at room temperature. In view of reports of appreciable ductility in germanium single crystals above 550°C'." and some plastic deformation in single-crystal silicon above 900oC,' the present investigation was undertaken to define more precisely the limits of high-temperature ductility in pure silicon. After this investigation was begun torsion ductility in both germanium and silicon was reported by Greiner." Through the courtesy of F. H. Horn, a small bar of cast extra high-purity silicon was obtained and small bend specimens were made from it by careful machining and grinding. All of the reported tests results were obtained from samples from this bar (bar No. 1) and one other of similar source (bar No. 2). No complete analysis was obtained but, based on analysis of similar semi-conductor grade material, metallic impurities were under 0.01 pct total. Vacuum-fusion analysis for oxygen showed a value of 0.0018 2 0.0003 pct for the first bar tested and metallographic analysis showed no evidence of a second phase. Bend tests were carried out on an Instron tensile machine using a bend fixture with a 1 -in. span loaded at the center. Supporting and loading bars were 0.250 in. round and the load was applied by downward motion of the pulling crosshead of the machine. Specimen thickness and width were approximately 0.10 in. and % in. respectively. Loading rate was controlled by holding crosshead motion constant at 0.02 ipm. In some cases a smaller specimen was used on a 5/8-in. span with a 0.129-in.-diam loading bar. The entire bend fixture was surrounded by a hinged furnace and all heating was done in air atmosphere. Temperature measurement was made with thermocouples fastened directly to the bend fixture within less than 1 in. from the specimen. Autographic stress-strain curves were recorded during each test, and breaking load, total deflection, and plastic strain could be obtained from these curves. Stress was calculated from the beam formula S = 3PL/2bh2, where P is the load in pounds, L the span in inches, b the specimen width in inches, and h the specimen thickness in inches. This formula is strictly correct only in the elastic range but has been used to calculate a nominal stress for convenience in the plastic range. The stress given is the maximum stress in the specimen. Results The results of the complete series of tests are shown in Table I. The first group of tests (specimens Nos. 1-6) showed the beginning of plastic flow at a test temperature of 900°C, so two additional tests (Nos. 8 and 9) were made at 950°C on small-size specimens from bar No. 2. Specimen No. 8 was tested in the as-machined condition, and No. 9 was heat-treated in hydrogen at 1300°C for 2 hr, cooled to 1200°C and held 1 hr, cooled to 1000°C and held 1 hr, cooled to 900°C and held 1 hr, and finally cooled to a low temperature before removal from the hydrogen. It is apparent that the heat-treatment had a significant effect on yield strength and ductility. In addition, the magnitude of the yield point was conslderably reduced in the heat-treated specimen as is shown m Fig. 1 by tracings of the stress-strain curves. After obtaining a furnace capable of reaching higher temperatures specimens Nos. 10 to 13 were tested at 1100 and 1200°C. Strain rate was increased by up to a factor of 10 to see whether the ductility observed was excessively strain sensitive. Specimen NO. 10, strained at 0.02 ipm and 1100oC, was still bending at a deflection of 0.322 in. when the load rate was increased to 0.2 ipm, resulting in immediate

Jan 1, 1959

By H. Conrad, V. V. Damiano, G. J. London

The slip mode activated during the c axis compression of single crystals of commercial-purity ingot SR beryllium, high-purity (twelve-zone-pass) beryllium, and Be-4.4 wt pct Cu and Be-5.2 wt pct Ni alloys in the temperature range of 25° to 364°C was determined using two-surface slip trace analysis, slip-step height analysis, and electron transmission microscopy. All three techniques indicated the occurrence of copious pyramidal {1 122) (1123) slip in the alloys over the entire temperature range, the amount increasing with temperature. Pyramidal slip was also indicated in the high-purity beryllium by slip trace analysis and electron transmission microscopy, but the amount was somewhat less than in the alloys. For the commercial-purity ingot crystals, only a very small number of pyramidal slip lines were observed, and these were in the immediate vicinity of the fracture surface. No pyramidal dislocations could be detected by electron transmission microscopy in this material. Dislocatransmissiontions with Burgers vectors [0001] and +(ll20) were identified by electron transmission microscopy inthe (1122) slip bands, as well as those with the j (1123) vector. This was interpreted to indicate that the edge components of the 3(1123) vector dislocations activated during c axis compression dissociate upon unloading according to the reaction i (1123) — [0001] + 3(1120) THE microstrain c axis compression of single crystals of commercial-purity ingot SR beryllium (99.6 pct), high-purity twelve-zone-pass beryllium (99.98 pct), Be-5.24 pct Ni and Be-4.37 pct Cu alloys was described in a previous paper.1 This paper covers in detail the analysis of slip traces observed on two mutually perpendicular lateral surfaces of these specimens, and a detailed description of transmission electron microscopy studies performed on foils cut from the bulk crystals after they had been deformed to fracture in the c axis compression. Observation of slip traces on single surfaces of deformed single crystals are generally insufficient to positively identify slip or twinning modes. The use of two carefully cut and oriented perpendicular surfaces can greatly aid in the positive identification and index- ing of slip traces, although even this technique may be quite inadequate if more than one type of slip system operates and if an insufficient number of traces are observed on the surfaces. The problem is greatly simplified for symmetric cases like that for c axis compression of an hep crystal such as beryllium, in which the operating slip systems are all equally inclined to the direction of the applied stress, and each slip system of a given slip mode has an equal chance of operating. For such cases, the traces of any given slip mode observed on the surfaces cut parallel to the c axis are symmetrically tilted about the c axis. It is therefore possible to quickly determine whether one or more slip modes are operating. Confirmatory evidence in support of the observations made on the external surfaces can be obtained from foils cut from the deformed crystals and examined by transmission electron microscopy. This latter technique serves to identify not only the operating slip plane but also the Burgers vector of the dislocations which participate in the slip. For this purpose, a simplified technique based upon a double tetrahedron notation is used in the present paper. The planes and directions in the hep lattice are all designated by letters rather than indices and extinction conditions are easily determined if the Burgers vector lies in the plane contributing to the diffraction. RESULTS 1) Slip Trace Analysis. The standard (0001) stereo-graphic projection of beryllium is shown in Fig. 1. The two mutually perpendicular, lateral surfaces of the compression specimen are represented by the diametrical planes AA' and BB', also referred to as surface A and surface B. For the specific case represented (a Be-5.24 pct Ni specimen deformed by c axis compression at room temperature), the A surface is tilted 5 deg to the (10i0') plane and the B surface is tilted 5 deg to the (1120) plane. Two surface trace analyses may be facilitated by examining in turn the intersection of various great circle traces of specific pyramidal planes with two surfaces and comparing the angles made with the (0001) plane with those actually observed on the two surfaces. One then identifies the slip traces by trial and error on a best-fit basis. The (1122) type planes (it was found that slip occurred on these planes) are shown plotted on the stereographic projection in Fig. 1. One obtains directly the angles between the (0001) plane and the {1122) traces by measuring the angle from the periphery to the point of intersection along the lines

Jan 1, 1969

By John Wulff, Richard P. Seelig

THE importance of the pressing operation in the forming of articles by powder metallurgy depends to a great extent on the type of product to be made. While in some few cases the pressing is merely a means of compacting loose powder particles into a solid mass preliminary to a sintering treatment in most applications it constitutes a molding operation with the purpose of shaping the raw material in powder form into a certain predetermined, accurately defined part not altered in shape by sub- sequent sintering. In still other cases, no pressing at all but sintering in molds gives useful articles. A limited number of products are made by the simultaneous application of pressure and heat. The factors that control the product of the pressing operation are raw material, lubricant, type, size and shape of die and compact, magnitude and time of application of pressure, as well as temperature of pressing. All such factors need to be con- trolled; yet, depending on the function of the pressing operation, greater emphasis may be placed on processing factors other than the pressing operation. In any complete discussion of pressing, subsequent sintering cannot be disregarded. For the sake of brevity, the present paper has been limited to the mechanics of pressing and only occasionally refers to sintering. For the same reason, hot-pressing has been omitted as beyond the scope of this paper. In any survey of the literature on the pressing of metal powders, the 1938 paper of Balshin1 on the theory of the process of pressing deserves mention. The first attempts at an interpretation of pressing phenomena were made by Balshin1 and Rakovski.2 The experimental results of both are of great interest. Since the experimental results are not described, the work was repeated, using our own interpretation of the possible techniques, and is reported in the following pages. The basic theory of Balshin,1 based on a hydro- dynamic analogy, however, leads to but another way of plotting density and pres- sure against height of a pressed compact. Since it does not give any new insight into the phenomena, nor account for the influence of side-wall friction, a discussion of the theory has been omitted from this paper. DENSITY GRADIENTS IN COMPACTS The process of pressing metal powders in a die (disregarding for this consideration the powder filling and ejection operations) may be divided into three phases: (I) packing, (2) elastic and plastic deformation, (3) cold-working with or without fragmentation. It must be emphasized that these three steps do not follow each other in sequence; on the contrary, in practice

Jan 1, 1946

By Spencer R. Persik, Richard E. Munz

Measurements of many physical properties within an underground mine may be required as inputs to computer programs. These may be as simple as running/ not running signals from equipment, or they, may be representations of analog readings such as methane concentration. Similarly, outputs from computer pro- grams may control equipment located within the mine, as when air doors are opened or closed under computer control. This paper deals with the concept of electrical signal multiplexing and explains the role that multiplexing can play in comnunicating signals between the computer and locations within the mine. One multiplexer in particular, "DIRECTROL" (manufacturer by Cutler-Hamner Products), is examined in some detail, and its properties are discussed, including scan times, data security, recovery from cable failures, and recovery from power failures. Techniques of interfacing the multilexer to a computer are explained. Illustrations of the use of the multiplexer in mining applications are given.

Jan 1, 1983

By H. H. Hausner, O. V. Roman, F. V. Lenel, G. S. Ansell

The radial shrinkage during sintering of cylindrical compacts and loose aggregates of copper powder was measured. It was found to be nonuni-form from top to bottom of the samples and to depend upon the method of supporting them. The non-uniformity is due to the effect of gravity forces during sintering. Since gravity has an effect in sintering without externally applied stresses, no sharp dividing line can be drawn between conventional sintering and hot pressing. RECENT investigations of the sintering behavior of compacts1 and of loose powder aggregates2 have indicated that forces, other than those arising from surface tension effects, may play a role in shrinkage. In compacts it was shown that residual stresses from the pressing operation influence shrinkage behavior. In loose powder aggregates gravity forces due to the weight of the powder affect the ratio of shrinkage in the vertical and the horizontal direction. The main effort in the work reported here was to show that gravity plays a role also in the sintering of compacts. A few additional experiments were made confirming the effect of gravity in the sintering of loose powder aggregates. EXPERIMENTAL PROCEDURE Compacts and loose powder aggregates were prepared from irregularly shaped, electrolytic copper powder. Prior to use the powders were reduced 30 min at 400°C in dry hydrogen to remove surface oxides. Then the -325 mesh size fraction was separated from the -100 + 325 mesh fraction. The compacts were pressed at a pressure of 10,000 psi from 50 g of powder in a hardened steel die, 1 in. in diam. The height of the compacts was 0.725 i 0.005 in. An effort was made to get as uniform a green density distribution in the compacts as possible. The walls of the die were lubricated with a suspension of 3 pct of zinc stearate in acetone and the compacts were pressed using double action by first pressing the powder at 1200 psi with the die barrel supported, then removing the sup- ports and pressing to final pressure of 10,000 psi with the die barrel floating. The pressure was maintained for 10 sec. The compacts were sintered at a temperature of 925°C, generally for 1 hr. In order to maintain uniform temperature they were sintered in boats made from cylindrical copper blocks. The blocks were 2 in. in diam, either 2 or 2 1/2 in. long and, split to form the body of the boat and a lid. The body of the boat contained a cavity 1 3/8 in. wide, 1 in. deep and either 2 1/8 or 1 3/8 in. long. The longer cavity accomodated two samples, the shorter one only one sample. The uniformity of temperature distribution within the boats was checked with thermocouples welded to the top and bottom of the samples. The maximum variation between top and bottom temperatures was i 1/2°C. The actual sintering temperature was held constant within ±2°C. In order to determine the effect of gravity forces, i.e., the weight of the compacts, upon shrinkage, they were supported in the following ways during sintering: a) Full Bottom Support. The compacts rested either on a flat alundum disk or on alundum powders. b) Partial Bottom Support. The compacts rested on a graphite cylinder, 0.3 in. in diam which formed a projection on a larger graphite disk. It is difficult to balance the compact on the small projection. To avoid having the compact tip, a small hole was drilled through the compact and through the graphite disk and its projection. The graphite disk was then suspended from the lid of the boat by a thin iron wire which passed through the holes in the disk and the compact. c) Top Support, first type. A hole 3/32 in. in diam was drilled diametrically through the green compact 3/16 in. from the top of the compact. The compact was sintered suspended from an alundum rod (thermocouple protection sleeve) inserted into the hole. d) Top Support, second type. A hole was drilled axially through the center of the compact. The upper part of the hole from the top surface of the compact one fourth of the way down was 1/16 in. in diam; the lower part of the hole from the bottom surface three fourth of the way up was 3/32 in. in diam. The compact was suspended from the lid of the boat by an iron wire passing through the upper part of the hole and then tied into a knot. The loose powder aggregates were made by filling l in. deep, l in. diam cylindrical graphite molds with -325 mesh powder. To achieve uniform density in all the loose powder aggregates, the powders were settled in the molds by placing the

Jan 1, 1963

By E. Gilpin

Any estimate of the economic mineral value of an unvisited district is to the mining engineer largely a comparative one. If he knows that certain minerals characterize any given geological horizon he naturally draws upon his experience of the same ores as met by him cinder similar geological conditions. And if he has not had the personal experience, the investigation of the geology of a similar district as given in a trustworthy report enables him to lay a fair basis for conclusions. In a general way these conclusions are of value, and while they pronounce on the possible mineral fecundity of a given district, they

Jan 1, 1890

By John W. Cahn

IT is well established that the pearlite reaction is a nucleation and growth reaction, and that pearlite nucleates on grain boundaries or intersections of grain boundaries. It is also known that while the

Jan 1, 1958

By Henry Louis

Henry Louis, Newcastle-upon-Tyne, England (communication to the Secretary*).—In this paper Mr. Simons derives the various forms of revolving slime tables, of which the Harz and the Linkenbach tables are typical examples, from the old rectangular or box buddle. This I believe to be an error, at any rate if Mr. Simons attaches the same meaning as I do to the ((evolution" of a dressing appliance. By the '(evolution" of such an appliance I understand the progressive development and improvement of an appliance acting on a definite principle, such improvements having usually for their object the economy of labor in working the same, or the increase of its capacity; when an entirely new principle is introduced, I no longer look upon this as evolution from the old type, but as the origination of an independent type of appliance. The box buddle was no doubt the predecessor of the old Cornish round buddle, which was evolved from it with the object of saving the labor required to work the box buddle; both machines are horizontal-current separators, in which the separation of sands of different densities is effected by their differential rates of fall in a horizontal current of water of considerable depth. These appliances, though well suited to sands, are for obvious reasons not adapted to the treatment of slimes. The revolving tables of the Harz and similar types, on the other hand, act on the principle which I have called separation in thin films of water, and which Mr. Simons calls the film sizing principle, in which the resistance of the surface over which the pulp flows plays an essential part in determining the separation of the particles, and which is well suited to the treatment of slimes. Unlike the last principle, it will not work in deep bodies of water and cannot be used where considerable depth of material accumulates in the appliance, as in the box buddle and round buddle. As I have shown in my book, The Dressing of Minerals, p. 326, these revolving tables are a development of the appliance known variously as the flat buddle, flat table, or frame, the last name, which is the old Cornish one, being the one that I personally prefer. These primitive appliances, as well as the continuous-acting round tables described by Mr. Simons (his Figs. 10 et seq.) all work on the principle of separation in thin films, and are all adapted for the treatment of slimes; his buddles and round tables (Figs. 1 to 9) do not work upon this principle, and should therefore be sharply differentiated from the former. The evolution in each case of the continuous acting, more or less automatic, circular appliance from the primitive, intermittent, hand-worked, rectangular appliance has proceeded upon strictly parallel lines. The question of the evolution of the respective types involves a point of some importance as regards the principles of ore dressing.

Jan 1, 1915

AS you have seen, I have hitherto demonstrated to you the methods for bringing to their proper and pure bodies all metals of any kind of ore that you have found and mined. If these did not now serve human needs all these operations with so much expense and labor would have been profitless and in vain. Therefore I recognize that it is necessary in speaking to touch upon all their operations and to teach you to ma& use of the metals according to the works needed. There are, for instance, some metals that would serve poorly for certain works when reduced to their fineness and perfection. Also, many artificers, in order to avoid expense, are content with having a larger quantity of metals and do not care so much about their perfection. For this reason they willingly accept mixtures of one metal with another, for example, of silver or copper with gold, of copper with silver, and likewise of tin or lead with copper. Tin is accompanied by lead to avoid spoiling its nature completely. All this, however, is done with a definite proportion by weight and not by chance. These admixtures, as I have told you in another place, are called in gold, carats, and in silver, leghe. This, in fact, means nothing but the association of one metal with another, indeed, a soiling of their purity and fineness, to which they have been brought with so much hard effort and labor. But now leaving this discussion, I shall tell you in the present book as briefly as I can, in order, first of the alloying of gold with silver or copper, and then of that of silver with copper.

Jan 1, 1942

By R. W. Kraft

The normal Mg-Mg,Sn eutectic is a classic example of a Chinese script eutectic. When the alloy is unidirectionally solidified, a much simpler topo-logical arrangement of the phase particles can be produced although individual grains still usually consist of two or more interpenetrating lamellar systerns. Specimens from unidirectionally solidified ingots were analyzed metallographicall~ and crys-tallographically, and it was found that the interfaces between the lamellae had a common crystallograPhic character describable by: Lamellar interfaces II {220}Mg2Sn 1) {1011}Mg Arguments are presented to explain why this particular orientation relationship tends to occur and it is shown that this criterion can be nearly satisfied simultaneously on up to four different lamellar systerns between two interpenetrating single crystals. Finally, on the basis of this work ad other similar work which has previously been done on Al-CuAl2 eutectics, a general principle pertaining to low-energy interfaces between two crystalline Phases is proposed. WITHIN the past few years several investigators1-4 have demonstrated that the microstructures of many eutectic alloys can be significantly altered by uni- directional solidification. If appropriate control is exercised over the purity of the alloy, the growth rate, and the thermal gradient during unidirectional solidification, ingots can be made in which the phase particles are aligned predominantly parallel to one another throughout substantial portions of the ingot. The present author has also shown for at least one of the alloys that the parallel lamellae tend to assume a unique crystallographic relationship during

Jan 1, 1963

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By H. I. Aaronson, S. Toney

When the component grains of .ferritic hicrystals of an Fe-1.55 pct Si alloy are disoriented through an angle "6 " about a conzmon [ll0] axis, the tendency for preferential growth of austenite crystals along the grain boundary during transformation at elevated temperatures is small when 11 deg, but increases rapidly at larger angles. This type of orientation-dependence indicates that grain boundary diffdsion promotes preferential growth along large-angle boundaries. Morphological differences between austenite crystals formed at small-angle [1101 and [loo] boundaries suggest that precipitate morphology can be dependent on the dislocation structure of the boundary. ThE morphology of precipitate crystals nucleated at a grain boundary can be significantly affected by the structure of the boundary.' The limited amount of experimental evidence available in the literature indicates that the morphological effects of boundaries made up of arrays of dislocations, such as subbound-aries and small-angle grain boundaries, are different from those of boundaries having essentially disordered structures, i.e., large-angle grain boundaries. On the basis of indirect evidence, it has been concluded that large-angle grain boundaries give rise to the formation of grain boundary allotriomorphs (crystals which nucleate at grain boundaries, and grow preferentially and more or less smoothly along them)2 in the proeutectoid ferrite and the proeutec-toid cementite reactions in plain-carbon steels, and apparently also in many non-ferrous alloys.' At small-angle grain boundaries in a plain carbon steel, on the other hand, ferrite crystals were found to take the form of primary side plates. Similarly, Guinie, loys. Primary sideplates formed at a subboundary with a constant orientation tend to be parallel to only one, or occasionally two matrix habit planes, and a marked change in the orientation of the boundary is accompanied by a change in the habit plane. Previous studies on the morphological effects of grain boundary structure were performed on poly-crystalline aggregates. Information on the disorien-tation of the pairs of grains forming the boundaries at which the various morphologies appeared in these specimens was largely either qualitative or semi-quantitative. Precipitate morphologies accordingly could not be accurately and systematically correlated with grain boundary structure, and thus theories which have been proposed for the various morphological effects could not be satisfactorily tested. This investigation was undertaken in an attempt to remedy these deficiencies by studying the morphological effects of grain boundary structure with a method in which the boundaries are formed by matrix grains whose disorientations are known and controlled with reasonable accuracy. EXPERIMENTAL PROCEDURE The crystallographic requirements of this study were fulfilled by means of oriented bicrystals of silicon-iron. Disorientation of the component ferrite crystals was carried out about common, major crystallographic axes through angles ranging from 1/2 to 44 deg. The silicon content was low enough SO that the bicrystals could be partially transformed to austenite by heating to elevated temperatures. The silicon-iron used had the following initial composition: 1.55 pct Si, 0.04 pct C, 0.0031 pct N, 0.17 pct Mn, 0.020 pct S, and 0.002 pct P. The alloy was obtained in the form of 0.036-in. sheet. The procedures employed to prepare seed crystals in strips of this sheet, to reorient the seeds, and to grow them into bicrystals are essentially those described by Dunn and Nonken and aynes." The characteristics of the bicrystals are given in Table I. The "bicrystal type" indicates the crystallographic plane parallel to the broad faces of the strip in both grains and the crystallographic direction which was parallel to the long edges of the strip in both grains prior to disorientation. The angular disorientation of the grains, 8, which was performed about the direction normal to the plane of the broad faces of the strip, was measured between the [ 00l] directions. Orientation of the grain boundary, , was taken as the angle between the plane of the grain boundary and a plane containing the axis of disorienta-

Jan 1, 1962

By William H. Emmons

CONTENTS. [ ]

Jan 1, 1913

By A. M. Strauss

This contribution illustrates the application of the theory of period doubling to the description of the formation of microcracks in rocks. The fundamental mathematics is described and a method of prediction is proposed. The invariance (universal constants) of a generic microfracturing (damage) process is described. Finally, the method is presented as a deterministic method of predicting the failure of an engineering material while keeping track of the amount of damage that has occured at any point.

Jan 1, 1984

By Jerry L. Straalsund, D. Bruce Masson

A dew-point technique was used to determine the thermodynamic activity of zinc at 430°C in a series of e phase Ag-Zn alloys. The composition of the alloys ranged from 72 to 88 at. pct Zn. This range included the composition at which Massalski and King3 found a reversal in the composition variation of the crystallo-graphic c/a ratio, which they attributed to an overlap of the Fermi surface across the (002) faces of the Brillouin zone. The data is presented in a graph in which RT In yz,, where yz, is the activity coefficient of zinc, is shown as a function of atomic percent zinc. This curve has an unmistakable change in slope at the same composition that Massalski and King observed the beginning of the reversal in the c/a ratio. This change in slope of the thermodynamic data is also attributed to a Brillouin zone overlap. Equations are presented to demonstrate that the thermodynamic activity can be related to the density of states of the conduction electrons, and that the observed phenomena are consistent with this model. It is also demonstrated that the contribution of the density of states can be related to the excess stability, a phenomenological parameter recently shown by Darkeen" to be significant in the interpretation of thermodynamic data of metallic phases. The data seem to indicate that zone overlap has caused a spinodal point, and the resulting misci-bility gap, in the phase diagram. THE problem of developing an adequate thermodynamic model of solid solutions has proven to be difficult, and is still only partially solved. The main approach has been to develop a statistical model, such as that of an ideal solution, regular solution, and so forth, to which can be attached corrections for electronic, vibrational, magnetic, ordering, or other contributions. Such corrective terms are usually derived on an ad hoc basis, and it is difficult to predict in advance what their relative importance will be. This problem has been discussed in general terms by Oriani and Alcock,' who have reviewed several thermodynamic models and a few empirical correlations. The measurements described in the present paper were made to demonstrate in a special case the importance of one such corrective term, the contribu- tion of the energy of the conduction electrons of an alloy. It was our premise that the contribution of the energy of the conduction electrons to the thermodynamic activity of the alloy components could be detected; further, that such an effect would be observed at alloy compositions where other phenomena, also ascribed to the energy and density of states of the conduction electrons, are observed. The idea of the importance of the conduction electrons is hardly new. Hume-Rothery and his adherents have developed the well-known theory of alloy phases in which the sequence of phase fields in binary equilibrium diagrams, especially those involving the noble metals with the IIB, IIIB, and IVB subgroups, can be correlated by replacing the composition variable with the ratio of conduction electrons to atoms, e/a. Jones and others have developed a physical explanation for this correlation, in which they consider the solubility limits of phase fields to be restricted by an intersection between the Fermi surface and a Brillouin zone. The general features of the model are also quite well-known—presumably zone intersection causes the density of states to decrease at critical alloy compositions. The attendant increase in energy of conduction electrons in the original crystal structure allows an alternate structure to become more stable as the concentration of polyvalent solute is increased. In spite of the wide acceptance of these ideas on phase stability, there is only indirect* evidence, such as the variations in lattice parameter recorded extensively by Massalskizy3 and others, that Brillouin zone interactions occur. There are few experimental measurements, other than the correlations of the phase sequence, that substantiate the premise that the energy of conduction electrons affects the solubility limits of alloy phases. Much thermodynamic data of alloys has been found to be consistent with the theory; yet there is a lack of detailed data at compositions where zone intersection and overlap are thought to occur. One would expect that the energy of the conduction electrons would make a measurable contribution to the thermodynamic properties of alloys at compositions near zone intersection and overlap if the theory of Hume-Rothery and Jones is correct. This conclusion cannot be avoided, because the phase boundaries are determined by the requirement that the chemical potential of the components be equal in both phases at equilibrium. An electronic effect large enough to alter the stability of a phase should also affect the thermodynamic activity by a measurable amount.

Jan 1, 1969

By C. M. Young

THIS is an attempt to bring together some of the knowledge of the .coal-forming conditions obtaining during the Pennsylvanian period in the Western Interior Coal Province, to sketch briefly the present extent and character of the coals produced, and to show the beginning of cor-relation of beds over wide areas. Coals of later age than the Pennsyl-vanian are not included and, for reasons that will appear later, little attempt is made to cover the districts of eastern Oklahoma and western Arkansas, and northern Texas is omitted entirely. GEOLOGICAL CONDITIONS The conditions that made possible the formation of large coal beds in the United States were most favorable in the Pennsylvanian period, formerly known as the Upper Carboniferous. The geological conditions can be determined from the records, but not the reasons for them. Preceding the Pennsylvanian was the Mississippian, formerly known as the lower Carboniferous and still later as the sub-Carboniferous. Dur-ing this time, large bodies of limestone were deposited and at the close f the Mississippian they were warped upward and for along period were eroded. Then there began a period of subsidence, more or less inter-rupted at times, during which the Pennsylvanian strata were deposited (see table on page 2). " These consist of sandstones, limestones and shales, with occasional coal beds: At the beginning of the Pennsylvanian there was subsidence, which allowed the sea to extend over the eroded Mississippian surface to the north and east, extending over eastern and central Texas, a large part of Oklahoma, with a projection into Arkansas, over Kansas and part of Nebraska, all the northern and western part of Missouri, a large part of Iowa except a strip in the north, most of Illinois, practically all of Ken-tucky, northern Tennessee, most of Indiana, all of the eastern part of Ohio, practically all of West Virginia, western Maryland, the west end of Virginia, and a large part of Pennsylvania. The Ozarks were already

Jan 1, 1935

By S. E. Bretherton

MOST metallurgists appreciate the great need of a process for the extraction and recovery of valuable metals from complex ore, where the presence of one metal increases the cost of extracting the other metals to such an extent that not any of the metals can be extracted at a profit. We need only refer to some of the mines in Colorado, Utah, and New Mexico, where oxidation has taken place and the sulphur, zinc, copper, and some of the iron and other metals have been leached out, large bodies of oxidized ore remaining, rich in lead, silver, and sometimes gold. These metals have been concentrated by the removal of the other metals, leaving a very desirable ore for treatment in the blast-furnace for the production of lead bullion, and recovery of the silver and gold. If lead is not present, the gold and silver are usually recovered by some method of milling, or the ore is shipped to a smelter, where it is mixed with lead ore or copper-iron sulphide ore from some other mine. In these same mines, when developed to greater depth below the leached or oxidized zone, the ore is found to contain the original mixture of sulphur, zinc, copper, etc., added to, or I should say left with, the lead, silver, and gold values; but instead of adding to the value of the ore, the presence of these elements, especially zinc, makes the copper, silver, and gold of less value, and often worthless. Such was the experience of the oldest mines in Leadville, Colo., until methods of mechanical separation of the lead from the zinc were developed sufficiently to allow of some profit by the making of a concentrate rich in zinc to be shipped to the zinc smelter, and sometimes a lead concentrate which could be shipped to the lead smelter; but even in these cases the waste of the different metals is a very serious matter. In the very best concentrating plants some zinc will be left in the lead concentrate, to be lost and to give considerable trouble in the lead-smelting furnace. On the other hand, some of the lead, with a large percentage of the copper and silver, will follow the zinc into the zinc concentrate, to be, perhaps, recovered y smelting the cinder or clinker left in the re-

Jan 7, 1914

By Albert Sauveur

(Winces-Barre Meeting, June, 1911.) THE instrument about to be described meets so perfectly the special needs of the metal microscopist that there seems to be little doubt but its merits must be readily appreciated by those who have had any experience in the microscopical examination of metals. The Microscope-Stand.-The microscope-stand proper, Fig. 1, consists of a microscope-tube, provided with both coarse and fine adjustments of the best construction, and with a draw-tube, rigidly mounted on a bar supported at both ends on substantial and firm cast-iron legs. The height between the table and the under side of the supporting bar is 5 in. and the distance between the supporting legs 12 inches. This arrangement' affords free space below the objective for the examination of large specimens of metals, such as full rail-sections, without detracting in the least from the value of the instrument when applied to the examination of the usual small specimen, as explained later. Many metal microscopists frequently have to examine bulky specimens, and this is altogether impossible with the ordinary microscopes as well as with the special metallurgical microscopes which have been designed and described from time to time. Recourse must be had to all sorts of makeshifts for the proper support of large specimens, or, more often, the microscopist gives up the attempt altogether, or else resigns himself to the cutting of the bulky samples into small pieces to -be laboriously polished and separately examined. It is believed that an instrument permitting the examination of large as well as of small specimens with equal ease and accu-

Dec 1, 1911

By M. Shelef, A. W. Fletcher

The effect of alkali sulfates in promoting the sul-fation of nickel and copper in a bulk sulfide flota -tion concentrate by fluidized bed roasting has been studied in the laboratory, and it was shown that the various alkali sulfates promote sulfation to approximately the same extent. The sulfation of a mixture of synthetically prepared iron and nickel oxide and of nickel ferrite has also been studied. Nickel sulfation was promoted by high ratios of Fe:Ni and by the presence of sodium sulfate. THE work described in this paper was a continuation of earlier studies into the role of alkali sulfates in promoting the sulfation roasting of nickel sulfides1,2 in an endeavor to determine how the system was affected by the presence of compounds of iron and copper. The earlier work1 showed that, in the sulfation of NiO at 680°C, the reaction was limited by the formation of an impermeable film of nickel sulfate on the oxide surface. The relative effect of the various alkali sulfates in promoting nickel sulfation varied in the order: Li > Na >Cs > Rb > K A study of alkali sulfate/ nickel sulfate interactions at high temperatures showed that the promoting action was due to the fact that the nickel sulfate product layer sintered and agglomerated only when the more active additives were present. This resulted in the formation of discontinuities in the nickel sulfate layer so that diffusion of the sulfating gases to the NiO surface was no longer impeded and the reaction could proceed to completion. A similar explanation was used for the observation that sodium and lithium sulfates promote the oxidation of NiS to NiO at temperatures below 750°C since small amounts of nickel sulfate were formed during oxidation.2 It was of interest to study the effect of alkali sulfates on the sulfate roasting of a sulfide flotation concentrate which is typical of material treated commercially. In order to control temperature it is essential to roast sulfides in a fluidized bed and this technique was therefore used, although the batchwise operation of a small-scale laboratory reactor does not reproduce all conditions which prevail in full-scale continuous plant. The results obtained are therefore only comparative, and cannot be used for predicting the optimum conditions for metal extraction. The sulfation of synthetically prepared mixed oxides of nickel + copper and nickel + iron and of nickel ferrite was also studied to evaluate the relative effects of alkali sulfates with more complex systems. SULFATION ROASTING OF A SULFIDE FLOTATION CONCENTRATE The bulk sulfide flotation concentrate used in this work contained 7.92 pct Ni, 1.74 pct Cu, 35.66 pct Fe, and 31.28 pct S. The sulfide minerals present in order of abundance were pyrrhotite FeS, pyrite FeS2, pentlandite (FeNi)S, and chalcopyrite CuFeS2. Two samples described as coarse and fine were used. The coarse sample, which was a flotation concentrate (58 pct plus 300 mesh), was ground to 100 pct minus 350 mesh to produce the fine sample. Before roasting, the sample of sulfide concentrate was agglomerated by wetting witli a solution of the alkali sulfate (or water), thoroughly mixing, and drying at 110°C. This gave a cake which was gently crushed and screened, the -18 +100 mesh fraction being used for fluidized bed roasting. A similar-size fraction had been used by the authors in pilot plant work with a 4-in.-diam fluidized bed reactor.' In this work it was found that the molar ratio of additive to the total iron + nickel + copper content of the sulfide sample should be adjusted to a value of approximately 0.06, as this was the optimum amount necessary for nickel sulfation. Experimental. The fluidized bed reactor consisted of a quartz tube approximately 60 cm long and 30 mm in diameter resting in a vertical tube furnace. The sulfide bed (30 g) was supported on a bed of -4 +12 mesh quartz particles 3 cm high, which rested on a sintered quartz disc welded to the tube. The temperature of the furnace was controlled with a variable transformer to give a final bed temperature of 680°C. The bed was fluidized with air or mixtures of air + 10 pct v/v SO2, at a total apparent gas velocity of 60 to 65 cm per sec at 680°C. The SO2 was introduced into the fluidizing air stream only when the oxidation of the sulfides was completed. At the end of the roasting period the calcine was leached with boiling water and the

Jan 1, 1964