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Page Laboratory Methods...........................127 Special Analytical Methods.......................127 Improvements in the Accuracy of the Vacuum-fusion Method for the Determination of Oxygen in Steel....................127 Quantitative Spectrochemical Analysis of Mixtures of Gases.......131 Oxygen Samples from Open-hearth Bath...............133 Rapid Analysis of Sample for Alumina.................139 Accurate Carbon Analyses in Low-carbon Steel.............139 Laboratory Technique for Study of Reactions Involving Liquid Metal. . . . 142 Rotating Liquid Crucibles......................143 Stationary Crucibles.........................145 Jones and Laughlin Experimental Furnace...............148 Vacuum Melting..........................149 Measurement of Temperature of Liquid Iron and Steel;..........149 Pouring and Teeming Temperatures..................149 Bath Temperatures.........................151 Plant Methods.............................154 Methods of Studying Slags.......................154 Sampling Slag in the Open Hearth..................155 Viscosity of Open-hearth Slags....................155 Petrographic Examination of Slag...................156 Statistical Methods Applied to Study and Control of Chemical Relations in Bath...............................166 Rapid Method of -Correlation Applicable to Study of Steelmaking Reactions............................166 INTRODUCTION On Thursday morning, Feb. 16, 1939, a round table discussion was held on the subject of Experimental Methods in the Study of Steelmaking. Dr. John Chipman, Professor of Metallurgy at the Massachusetts Institute of Technology, and chairman of the A.I.M.E. Committee on Physical Chemistry of Steelmaking, presided. In opening the meeting, the chairman said: "The purpose of this round table is to discuss methods of study by which more and better information on the fundamentals of steelmaking can be obtained. It was thought that a round table discussion rather than a symposium would furnish the best opportunity for those actually using various methods of study to get together and discuss their common problems. For this reason attention will be focused upon methods of study rather than upon their results. We want new and current and up-to-date discussion.

Jan 1, 1940

Page Laboratory Methods...........................127 Special Analytical Methods.......................127 Improvements in the Accuracy of the Vacuum-fusion Method for the Determination of Oxygen in Steel....................127 Quantitative Spectrochemical Analysis of Mixtures of Gases.......131 Oxygen Samples from Open-hearth Bath...............133 Rapid Analysis of Sample for Alumina.................139 Accurate Carbon Analyses in Low-carbon Steel.............139 Laboratory Technique for Study of Reactions Involving Liquid Metal. . . . 142 Rotating Liquid Crucibles......................143 Stationary Crucibles.........................145 Jones and Laughlin Experimental Furnace...............148 Vacuum Melting..........................149 Measurement of Temperature of Liquid Iron and Steel;..........149 Pouring and Teeming Temperatures..................149 Bath Temperatures.........................151 Plant Methods.............................154 Methods of Studying Slags.......................154 Sampling Slag in the Open Hearth..................155 Viscosity of Open-hearth Slags....................155 Petrographic Examination of Slag...................156 Statistical Methods Applied to Study and Control of Chemical Relations in Bath...............................166 Rapid Method of -Correlation Applicable to Study of Steelmaking Reactions............................166 INTRODUCTION On Thursday morning, Feb. 16, 1939, a round table discussion was held on the subject of Experimental Methods in the Study of Steelmaking. Dr. John Chipman, Professor of Metallurgy at the Massachusetts Institute of Technology, and chairman of the A.I.M.E. Committee on Physical Chemistry of Steelmaking, presided. In opening the meeting, the chairman said: "The purpose of this round table is to discuss methods of study by which more and better information on the fundamentals of steelmaking can be obtained. It was thought that a round table discussion rather than a symposium would furnish the best opportunity for those actually using various methods of study to get together and discuss their common problems. For this reason attention will be focused upon methods of study rather than upon their results. We want new and current and up-to-date discussion.

Jan 1, 1940

By R. W. Snyder, W. H. Guilinger, B. S. Gottfried

Two numerical methods are presented JOT solving the equations Jor one-dimensional, multiphase /low in porous media. The case oF variable physical properties is included in the Formulation, although gravity and capillarity are ignored. Both methods are analyzed mathematically, resulting in upper and lower bounds for the ratio of time step to mesh spacing. The methods are applied to two- and three-phase waterflooding problems in laboratory-size cores, and resulting saturation and pressure distributions and production histories are presented graphically. Results oJ the tuo-phase flow problem are in agreement with the predictions of the Buckley-Leuerett theory. Several three-phase flow problems are presented which consider variations in the water injection rate and changes in the initial oil-and ujater-saturation distributions. The results are different physically from the two- phase case; however, it is shown that the Buckley-Lez~erett theory can accurately predict fluid interlace velocities and displacing-fluid frontal snturations for three-phase flow, providing the correct assumptions are made. The above solutions are used as a basis JOT et~aluuting the numerical methods with respect to machine time requirements and allowable time step for a fixed mesh spacing. INTRODUCTION Considerable progress has been made in recent years in obtaining numerical solutions of the equations for two-phase flow in porous media. Douglas, Blair and Wagner2and McEwenll present different methods for solving the one-dimensional case for incompressible fluids with capillarity (the former using finite differences, the latter with an approach based upon characteristics). Fayers and Sheldon4 and Hovanesian and Fayers8 have extended these studies to include the effects of gravity. West, Garvin and Sheldon, l4 in a pioneer paper, treat linear and radial systems with both capillarity and gravity and they also include the effects of compressibility. Douglas, Peaceman and Rachford3 consider two-dimensional, two-phase, in compressible flow with gravity and capillarity and Blair and Peaceman1 have extended this method to allow for compressible fluids. No one, however, has examined the case of three-phase flow, even for the relatively simple case of one-dimensional flow of incompressible fluids in the absence of gravity and capillarity. In obtaining a numerical technique for simulating forward in situ combustion laboratory experiments, Gottfried5 has developed a method for solving the one-dimensional, compressible flow equations with any number of flowing phases. Gravity and capillarity are not included in the formulation. The method has been used successfully, however, for two- and three-phase problems in a variable-temperature field with sources and sinks. This paper examines the algorithm of Gottfried more critically. Two numerical methods are presented for solving the one-dimensional, multi-phase flow equations with variable physical properties. Both methods are analyzed mathematically, and are used to simulate two- and three-phase waterflooding problems. The numerical solutions are then taken as a basis for comparing the utility of the methods.

Jan 1, 1967

By John A. Wolfe

The brightest spot in the mineral economy of the Philippines is the rapid development of reserves and production of copper. If economic conditions remain favorable and the political climate is encouraging, production of this metal should increase at a rate of 25% per year for several years, long enough to rank this country as one of the major copper producers of the world. In 1965 the copper content of the Philippine concentrates was approximately 60,000 tons. It should total about 80,000 tons in 1966. A major part of the increase will come from the rich Lepanto mine located in Mountain Province, North Central Luzon. Daily production of ore increased from 1200 to 2000 tons at the end of 1965. The ore, consisting of enargite and luzonite, averages nearly 3% copper and 0.12 oz. of gold per ton. It is an under- ground operation with a cutoff grade of 2%. The ore is associated with extensive silicification under a volcanic cap rock. Further expansion to increase ore production to 2600 tpd is under way.

Jan 4, 1967

By N. Brown, R. Kossowsky

Plain carbon steels with 0.48 and 0.95 pct C were quenched and tempered at 705°C to produce carbide dispersions with spacings on the order of 1 p. The morphology of the structure consisted of a carbide-dislocation network. The strengthening due to the dispersion was found to vary linearly with M-½ where M is the mean free-ferrite path determined by the entire network. No preyield microstrain preceded the upper yield point. After prestraining, the lowest stress at which dislocation movement could be detected was 104 psi; this frictional stress was independent of the dispersion and prestrains up to 6.5 pct. The Cottrell-Petch equation for grain-size strengthening was used to discuss the dispersion strengthening in this investigation. The results support an impurity mechanism for the upper yield point rather than one based on the Johns ton- Gilman theory. IT was pointed out by Gensamerl that the mean free path in the matrix is the important variable which controls the degree of dispersion strengthening. Gensamer's data on steels showed a linear relationship between the yield point and the logarithm of the mean free-ferrite path. The first theory was by Orowan,2 who suggested the mechanism of dislocations bowing between particles, with the resulting relationship that where a is the yield point, P is the distance between particles, and G is the shear modulus. The Orowan equation applies to that range of dispersion where P is large compared to the particle size and the particles are not coherent, so that the matrix is essentially free of internal stresses. As was pointed out by Orowan, there are different degrees of dispersion which, in turn, will influence the strength-controlling mechanism. However, in this investigation, we wish to confine ourselves to the region of coarse dispersion, where the Orowan mechanism should, intuitively, be applicable. It was soon evident that the data, which existed at about the time that the Orowan theory was proposed, did not agree with the Orowan equation in that the actual strengthening was always greater than the theoretical predictions. Thus, Fisher, Hart, and pry3 modified the Orowan theory by suggesting that the Orowan process took place in the microstrain region preceding macroscopic yielding and the subsequent, rapid work hardening in the form of residual dislocation loops around the particles largely determined the observed macroscopic yield point. The F-H-P theory stated that the increment of strengthening due to the work-hardening mechanism was proportional to f3/2 where f is the volume fraction of the precipitate. F-H-P used data by Shaw, Shepard, Starr, and Dorn4 on A1 3-5 pct Cu to support their theory. Roberts, Carruthers, and Averbach5 were the first to make a microstrain study of dispersion strengthening, and they found that for steel the Gensamer relationship was obeyed. Hayman and Nutting6 suggested that in the case of tempered steel 1) the ferrite grain boundary was the primary obstacle and 2) the carbide particles simply formed part of the grain boundary obstacles. They found that the strength varied as G"" where G is the ferrite grain size. Turkalo and LOW' determined the structure of quenched and tempered plain carbon steel using a replica technique; they concluded that the carbide particles did not necessarily lie in the ferrite grain boundaries. When they defined the mean free-ferrite path as being determined by both particles and the ferrite path boundaries, their data obeyed the Gensamer relationship. Meiklejohn and skoda8 showed that the strengthening from iron particles in mercury was a function of the particle size and the distance between particles. Dew-Hughes9 explained the Meiklejohn and Skoda results by the following theory: 1) grown-in dislocations which surrounded the particles were produced by the thermal stresses during the time the material was cooled to the testing temperature, and 2) the observed strengthening was associated with the cutting of the grown-in dislocations by the glide dislocations. Ansell and Lenel10 proposed a theory in which the glide dislocations pile-up or surround the particle until the number of dislocations in the pile-up is sufficient to yield or fracture the particle. The resulting theory says that the yield point varies as p-1/2, where P is the distance between particles. The Ansell-Lenel theory is almost identical to the

Jan 1, 1965

[Contents AH-Metal Mining and Industrial Minerals Pipeline Transportation of Phosphate. (Paper by I. S. Tillotson, R. B. Burt, and J. A. Barr, Transactions AIME, 193, 273; Mining Engineering. March 1952. Discussion by Howard Howie.) 1066 B-Minerals Beneficiation The Effect of Zinc Deleading Operations on Lead-Zinc Selectivity at the Parral and Santa Barbara Mines. (Paper by C. L. Boeke an G. C. Gunther, Transactions AIME, 193, 495; Mining Engineering. May 1952. Discussion by I. M. Symonds, L. H. Lange, Norman Weiss, H. S. Wildman, C. F. Zeuch, E. H. Crabtree.) 1067 Jaw Crusher Capacities, Blake and Single-Toggle or Overhead Eccentric Types. (Paper by D. H. Gieskieng, Transactions AIME, 190, 971; Mining Engineering. November 1951. Author s supplement.) 1069 Screened Ore Use for Fine Grinding at Lake Shore Mines. (Paper by Bunting S. Crocker, Transactions AIME, 193, 499; Mining Engineering. May 1952. Discussion by Fred C. Bond, J. Myers, Norman Weiss, Harlowe Hardinge, Oscar Johnson, L. E. Djingheuzian.) 1069 The Third Theory of Comminution. (Paper by Fred C. Bond, Transactions AIME, 193, 484; Mining Engineering. May 1952. Discussion by Milton C. Shaw and Donald R. Walker; R. J. Russell.)1071 Flotation Rates and Flotation Efficiency.t (Paper by Nathaniel Arbiter, Transactions AIME, 190, 791; Mining Engineering. September 1951. Discussion by Gregoire Gutzeit and Porter Clements.) 1074]

Jan 1, 1952

By R. J. Wasilewski

Electrical resistivity variation with temperature was measured on a series of alloys containting up to 33 at. pct of oxygen over the range 77° to1500°K. The resistivity behavior is highly anomalous and itzconsistent with simple metallic conduction. Both composition and temperature-depended resistivity singularities were observed. A few experiments carried out on Ti-N and Zr-O alloys indicate the presence of similar anomalies. These observations, together with the published data on effects of substi-tutional alloying on the resistiuity of titanium, suggest that the anomalies are inhevent in the electron structure of this group oj metals. The existence of two-band conduction, and a significant shift of bands relative to each other with temperature and/or the electron concentration are suggested. CONSIDERABLE advances have been made in recent years in the alloy theory of simple metals. Very little, however, is known about the bonding in transition metals and their alloys.&apos; Titanium, with its relatively few electrons, may be expected to show simpler alloying behavior than the more complex transition elements. Its alloys with the interstitial elements appear particularly attractive in an investigation of bonding characteristics because of a) the simple nature of the solute elements, b) the remarkable similarity between the equiatomic structures Tic, TiN, and TiO, and c) the extensive solid solubility ranges of oxygen and nitrogen in a titanium reported.2,3 The Ti-O system was chosen for the most extensive investigation because of the relative ease of preparation of suitable specimens. Since the main object of the work was to obtain data on the bonding and its changes on alloying, electron-sensitive properties were primarily investigated. The present work describes the investigation on the electrical resistivity-temperature-oxygen content relationships. A few experiments were also carried out at selected compositions in the Ti-N and Zr-O systems. EXPERIMENTAL Materials and Method. Polycrystalline specimens were prepared in the form of hairpin strips some 50 by 5 by 0.15 to 0.50 mm by direct metal-gas reaction. This was carried out by controlled oxidation followed by a homogenizing anneal at a higher temperature. All the test specimens were fully homogenized as judged from the uniform microstructure and microhardness. To avoid preferred orientation, each strip specimen was annealed in the ß range prior to the oxidation, this procedure assuring random orientation in the strip;4 hence any texture resulting from the oxidation reaction itself affected all the specimens to a similar extent. Titanium used was of high purity (66 DPN, 10 Kg load; major impurities 0,-43G ppm, N,-70 ppm, C-25 ppm, Fe-14G ppm). The solute content of the alloys was determined by weighing, after the reaction with a known amount of oxygen. The specimens in which the discrepancy between the volumetric and gravimetric measurements exceeded 2 pct (or 0.2 mg for the low oxygen alloys) were rejected. The mean between the two measurements was then taken as the oxygen content of the alloy. Check analyses showed no measurable nitrogen contamination. All oxygen contents are given in atomic percent. Zr-O alloys were prepared in identical manner from hafnium-free crystal bar metal, cold-rolled to strip 0.25 mm thick. Ti-N alloys required very long reaction times at the maximum temperature available (1250°C). In order, therefore, to detect possible oxygen contamination, duplicate specimens were reacted in every experimental run, and one of these was analyzed both for oxygen (vacuum fusion) and for nitrogen (Kjeldahl). Only the specimens in which the check analysis showed < 1000 ppm O were then used for resistivity investigation. Since only relatively high nitrogen alloys (7.1 at. pct; i.e., 2 wt pct N,) were investigated, this oxygen contamination was considered permissible. Dc resistance was measured by the four-probe method as previously described.= The temperature was determined with a calibrated thermocouple placed in the center of the specimen hairpin. The errors in the specimen resistance values thus obtained were estimated at 1 pct due almost exclusively to the finite thickness of the potential wires and the consequent uncertainty as regards the true resistance length of the specimen. For the calculation of the specific resistance, however, no dimensional measurements could be carried out on most of the

Jan 1, 1962

By J. A. Faucher

The mining industry has undergone significant technological advances in metallurgical process methods in recent years. The 1000 tpd concentrator of St. Lawrence Colum-bium Metals Corp. portrays the continuing effort made by the industry to achieve economical concentration of new and difficult ores. During the active search for sources of uranium in the early fifties, radioactive minerals were found in the Oka district near Montreal. The compatatively small quantities of uranium which were found occurred in association with widespread columbium (niobium) mineralization which included perovskite, a calcium titanate containing roughly 40% Cb2O5; niocalite, a silicate containing some 20% Cb2O5; and pyrochlore, a calcium niobate containing 45 -70% Cb2O5 as well as fluorine and some water. An idealized formula for one type of pyrochlore is: A typical chemical analysis of pyrochlore is shown in Table I. An important feature of this analysis is the lack of tin, lead, sulphur and P2O5 which conforms with the requirements of most consumers. In general the cerium content varies with sodium content and any increase in Ta2O5 lowers the Cb2O5 content of the concentrate. However, Ta2O5 rarely exceeds 0.5%. The carbonatite host rock of the columbium mineralization has the average mineral composition shown in Table 11. In Table 11, the term "diopside" is used to cover all silicates except mica which is shown separately because of the problems involved with its separation during the concentration process. In some ore zones, small quantities of rare earth minerals, such as monazite are present.

Jan 1, 1964

By P. A. C. Wilson

Instantaneous outbursts of carbon dioxide in coal mines have occurred in Germany only in one part of the Waldenburg-Neurode mining district.&apos; This mining region comprises the northeastern fold of the "Innersudetian" coal basin. The basin (Fig. 1) is in the form of a geologic trough approximately 60 km. (37 miles) long and 30 to 35 km. (19 to 22 miles) broad and is enclosed on three sides by ancient truncated mountain ranges—the Riesengebirge, the Bober-Katzbachgebirge and the Eulenge-birge. Only the southeastern part of the trough is not enclosed by mountains of older rock formation. The floor of the basin before the building up of the coal measures was formed on the western, northwestern and northeastern borders by the material from Archean rocks (gneiss and mica schists); in the northern part over this was deposited the Silurian formation. The carboniferous period is represented both by the Lower ("kulm") and Upper Carboniferous, with an unconformity between the stages; that is, the kulm was tilted up and partly eroded before the Upper Carboniferous was deposited. The kulm is a salt-water formation (with marine fauna) but Upper Carboniferous rocks are nonsaline water deposits, with fresh-water flora only. The Lower Silesian coal measures were thus formed in a lime basin fed by the running water coming down from the mountains. As already indicated, the bottom series of the Upper Carboniferous formation, termed "Waldenburg strata" were laid down unconformably on the Lower Carboniferous. Over the Waldenburg strata there are the "Weisstein strata," an intermediate barren stage without coal beds, 400 to 500 m. (1300 to 1600 ft.) thick. Another unconformity followed, which is overlain by the &apos;(Saarbrucken" series, which contain the upper coal measures, and the (&apos;Ottweil" strata. In the last named, it is only on the southwestern fold that beds of coal are developed.

Jan 1, 1931

By J. B. Mackintosh

In a recent paper read before the Institute on this subject, Mr. G. C. Stone advances the theory that the precipitate obtained in Williams&apos;s volumetric process,* by treating the boiling nitric acid solution of a manganese salt with potassic chlorate., is not pure MnO2, but approximates more closely to the composition 10Mn02+Mn0. As the value of the process and the accuracy of our results mould depend on whether this was the fact or not, it has seemed to me, and to my associates, Messrs. Beebe and Colly, that it would be of importance to ascertain the composition of this precipitate, and to that end the following series of experiments has been undertaken. These experiments have all been based on the considerations: 1. That potassic permanganate has an oxidizing power equivalent to five atoms of oxygen for every two of manganese : K2Mn2O8 = K2O.2MnO.O5. 2. That the same amount of manganese in the state of binoxide has an oxidizing power equivalent to two atoms of oxygen : 2MnO2 = 2MnO.O2. If, then, we take a solution of permanganate of unknown strength, and reduce it to binoxide, the oxidizing power of the binoxide formed will be equal to that of two-fifths the quantity of the permanganate solution originally taken. While, if the precipitate obtained should not be binoxide, but an indefinite or definite mixture of bin- and mon- oxides, then, from its equivalent oxidizing power, we can calculate its composition. The analyses were conducted in the following manner. The amount of permanganate taken was decomposed with hydrochloric acid, and concentrated to expel the excess of water. Sufficient excess of nitric acid was now added, and the solution was boiled until all the hydrochloric acid was destroyed. The manganese was then precipitated by potassic chlorate; and, after standing some time to cool—a pre-

Jan 1, 1884

By H. M. Ziesemer

PRIOR to 1909 that mountain of porphyry, known as. Sacramento Hill, had remained hardly touched but had always aroused suspicions as to the presence of ore within.. During that year, exploratory work was started by underground methods; drifting and raising continued until 1913. It was proved that a mineralized zone existed, the limits of which had not been determined; so, because of the lower costs of exploratory work and the greater desirability of vertical sections, it was decided to prove the extent of the ore zone by churn drills. Drilling continued until the year 1917, when it seemed almost certain that the horizontal limits of the orebodies had been determined. Ore continued in depth in one direction beyond a point where it was economical to explore by churn drilling; this extension is still being developed by underground methods. The irregularities of the boundaries of the ore zones, together with the variable grades of ore encountered, made it necessary to drill on the corners of 100-ft. squares. Two ore zones were proved, known as the East and West Orebodies. The Sacramento Hill porphyry stock intruded into the Dividend fault. The fault ran roughly east and west with a dip to the south, having pre-Cambrian schists on the north against Paleozoic limestone on, the south. This intrusion was accompanied by a silica breccia on the south periphery, along the limestone contact side. The ore lay in the silica breccia and in the porphyry, some distance from the breccia. No ore was found in the heart of the porphyry mass on the north side, along the schist contact. The West Orebody is elliptic in shape, having a major axis of 1200 ft. (366 m.) and a minor axis of 800 ft. (244 m.); these diminish with depth until, at 300. ft., the axes are 500 ft. and 300 ft., respectively. The ore consists of chalcocite, some bornite, chalcopyrite, and considerable pyrite in a silicious gangue. About 30 per cent. of the copper is caused by

Jan 2, 1922

By R. A. Hadfield

It seems a specially fitting opportunity to present a paper on the alloys of iron and aluminum at the New York meeting of this Institute, owing to the fact that America has, more than any other country, originated and developed the manufacture of cheap aluminum. The Cowles, Castner, and Hall systems have all originated in the ever-busy brain of our cousin across the water. The problem of cheaply producing this valuable metal has been a difficult one, but to the writer it seems that the more arduous the task the greater the delight with which our American friend attempts to overcome the difficulties surrounding it, and the more vim he throws into the work. Another and equally striking proof of this is to be found in the recent appearance of the already wellknown remarkable work, The Mefallurgy of Steel, by Mr. H. M. Howe, of the Institute of Technology, Boston, Mass. It is to be hopel that this Institute will not be slow to recognize by some special mark its appreciation of this signally valuable and original work. The writer has been led to describe the following experiments, believing that so far no full and exact report has yet been presented to this Institute as to the effect of aluminum alloyed or combined with the metal iron. It has been a special object to make the material as far as possible a true alloy or combination of aluminum and iron, with as small quantities as possible of other disturbing ingredients, such as silicon, manganese, etc. In the material described in these experiments, the total amounts of other elements present (sulphur and phosphorus being disregarded as present in such small quantities) do not exceed about 0.5 per cent. Such material may therefore be probably taken as fairly illustrative of the effect of the metal aluminum upon iron. Since completing the experiments the writer

Jan 1, 1891

By D. J. Jr. McAdam

RESULTS of investigation of corrosion-fatigue of metals at the U. S. Naval Engineering Experiment Station have been presented by the author in four papers. 1,2,3,4 In those papers references were given to the work of Haigh in 1917.5 The investigation at Annapolis included a variety of ferrous and non-ferrous alloys. The experiments showed that even slight corrosion simultaneous with fatigue may cause failure at stresses far below the ordinary endurance limit. The experiments also showed that, for most metals, severe stressless corrosion prior to fatigue is much less damaging than even slight corrosion simultaneous with fatigue. The term "corrosion-fatigue" was restricted to mean the simultaneous action of corrosion and fatigue. The combined effect of corrosion followed by fatigue was called "prior-corrosion fatigue." A stress-cycle graph representing corrosion-fatigue is a curve approaching a horizontal asymptote, the ordinate of which may be called a "corrosion-fatigue limit." To avoid confusion in later discussion, the term "endurance limit" will be restricted to mean the fatigue limit obtained by tests in air with specimens as free as possible from stress concentration and from corrosion. The endurance limit as thus obtained presumably represents an inherent property of the metal.

Jan 1, 1929

By R. W. Gould, B. G. LeFevre, A. G. Guy

The resistivity anomaly known as the K state was studied in Ni-Mo alloys containing 10.5 and 14.0 at. pct Mo. Both these alloys exhibit a large K effect which depends on the mechanical and thermal treatment. On the basis of X-ray diffuse scattering studies which were correlated with resistivity measurements, it appears that the K state in dilute Ni-Mo alloys can be associated with changes in the degree of short-range order within the a phase. An interesting phenomenon that has received much attention in recent years is the K state. The K state is marked by anomalous changes in some of the physical properties of certain alloys without the occurrence of observable microscopic structural changes. One of the early pieces of work in this area was by Thomas&apos; who studied alloys of Ni-Cr, Ni-Cu, Ni-Cu-Zn, Fe-A1, Fe-Si, and Ni-A1. Upon annealing specimens which had been previously cold-worked or quenched from an elevated temperature he found an anomalous increase in resistivity over a certain temperature range. He also found that specimens which had been appropriately annealed to develop the K state showed a decrease in resistivity upon subsequent cold working. These effects are opposite to those found in normal alloys. Although the resistivity anomaly has been rather arbitrarily taken as the "definition" of the K state, there are several other interesting effects which accompany the resistivity increase. In Ni-Cr alloys,2, 3 for example, it was found that the hardness increases with increasing resistivity. It was also found that specimens which have been treated to develop the K state can be cold-worked for as much as an 80 pct reduction of area without an increase in the hardness. In Fe-A1 and Fe-Si alloys4 the K state is accompanied by an increase in flow stress and by a lattice contraction. In Ni-A1 alloys,5 specimens which have been treated to develop the K state also show an increase in elastic modulus. In Ag-Pd alloys6 the increased resistivity observed on annealing a cold-worked specimen is accompanied by an increase in the thermoelectric power and an increase in the Hall coefficient. The explanations of the K state phenomena are varied and depend upon the particular alloy in question. Several theories have been advanced to explain the increased conductivity with cold work on the basis of changes in the electronic configuration of the alloy as a result of local lattice distortions.7"9 Most investigators, however, believe that some type of local order in the solid solution, either short-range order (SRO) or clustering, is responsible for this effect. Theories concerning the relationship between ordering and the K state have for the most part been speculative, since there is little direct X-ray evidence that can be correlated with the above property changes. Much of the previous work on the K state was done in the Ni-Cr system where the small difference in the X-ray atomic scattering factors of the components nickel and chromium makes it very difficult to use X-ray diffuse-scattering measurements to determine the role of local order. In the Ni-A1 system, however, Starke et al.10 succeeded in detecting a connection between local order and the K state. It was found that a small but measurable K effect correlated with increasing SRO in the nickel-rich a phase. The manner in which local order might increase the resistivity of K state alloys is not completely clear. Since most of the known K state alloys contain at least one transition element, significance has frequently been attached to the presence of an unfilled d shell. It has been suggested that during the formation of the K state the number of conduction electrons decreases as a result of the transfer of s electrons to the d shell where they are more tightly bound.1&apos;11&apos;12 Koster and Rocholl13 have proposed that SRO can cause an increase in resistivity for alloy systems in which the number and mobility of charge carriers are reduced when the percent solute is increased. According to this hypothesis, the local environment of a given solvent atom changes in the same manner with increasing percent solute as it does with an increasing degree of SRO; hence the change in physical properties should tend in the same direction. In this hypothesis, SRO is considered only in a statistical sense, and the increased resistivity of the K state is attributed to a change in the mean distribution of electrons and holes in the s and d states as a result of SRO. From the work of Chen and Nicholson on Ag-Pd alloys,6 it appears that the K state can occur in systems for which the d shell is completely filled. These investigators explained the increased resistivity by picturing the SRO as small domains of some form of long-range order (LRO). According to ~ibson,&apos;~ the number of effective electrons can be reduced by the creation of a new Brillouin zone boundary near the Fermi surface of an alloy as a result of the changing crystallographic symmetry that accompanies the formation of a superlattice. This idea may be expressed in terms of the superzone concept.15 In the present work the role of local order in the formation of the K state in Ni-Mo alloys was investigated. The principal tools used in this study were X-ray diffuse scattering and electrical resistivity measurements; however, these data were supplemented by electron microscopic and field-ion microscopic data. The purpose of the work was to determine whether or not the K state in Ni-Mo alloys can indeed be attributed to the formation of SRO as has been proposed by previous investigators.

Jan 1, 1969

By M. B. Mirza, F. D. Wright

Models of photoelastic material were made to simulate a mine roof that had cracked over the edge of the pillars and at the center of the span. Models were restrained from moving laterally outward so they acted as flat arches. Uniform loading was approximated by loading the models along the bottom at eight points spaced equally along the span. It was found that for models with depth to span ratios of 1:3 to 1:6, the maximum stress at the top of the center crack could be calculated directly by the following formula: Elastic stresses in mine roofs composed of sedimentary beds are usually computed by assuming that the immediate roof bed acts as a fully restrained beam uniformly loaded by its own weight and by overlying strata. Very little work has been done to analyze stresses in roof beds or beams which contain vertical (normal to the span) or nearly vertical cracks. Yet every mining engineer has walked safely under roofs that show such cracks. As far back as 1933, Bucky&apos; made model studies of the effect of vertical cracks on the behavior of horizontal strata. He did not make any analysis of the stresses but did show that a cracked beam will stand safely under certain conditions, and also showed that a beam restrained at the ends can crack over the supports and in the middle without collapsing as long as the ends of the beam are not free to move laterally outward. The beam, or rather, part of the beam, acts like a flat arch and supports itself by pushing outward at its supports. In 1941 Evans2 treated analytically the problem of a beam cracked along so many planes perpendicular to the axis of the beam that no tensile stress can operate. He named this type of beam a "voussoir-beam" by analogy to the voussoir-arch. In 1962 ~a~cocks~ modified Evans&apos;s solution by including the effect of the shear stress component of the resultant force at the abutment. This paper gives the results of a photoelastic study of the stresses in a beam containing vertical cracks in the center of the span and over the supports. A

Jan 1, 1963

By John J. Gilman

F many years it has been suspected that a correlation existed between pits produced by etching and the density of dislocations in crystals. In 1953, the interest in this correlation was greatly stimulated when Vogel et al&apos; demonstrated a 1:l correlation between etch pits and dislocations in low angle grain boundaries of germanium. About two years ago, the author began attempts to produce etch pits at dislocation sites in zinc mono-crystals. These attempts met with success a year or so ago,&apos; and since that time a survey has been made of the etch pit patterns that are associated with various modes of deformation in zinc monocrystals. Unfortunately, the etching technique that will be described is too delicate for use as an accurate quantitative tool. Nevertheless, it has been of considerable assistance in clarifying the structure of plastically deformed crystals. Technique Many attempts were made to produce etch pits in high purity zinc crystals. It was found that several techniques would produce surface grooves at grain boundaries that had misorientation angles greater than about l°, but no technique was successful for boundaries with smaller angles. Among the things that were tried were: electrolytic CrO, (both etching and polishing concentrations), HNO, in various water and alcohol solutions, dilute HC1, many 0-0,-Na,SO, solutions, Cr0,-HC1 solutions, picral, electrolytic Na,S,O,, and electrolytic NaOH and KOH. A few attempts to use cathodic sputtering and thermal etching were also made.

Jan 1, 1957

By James D. McClung, H. J. Gluskoter, M. R. Geer

INTRODUCTION The purpose of coal preparation is to improve the quality of coal to make it suitable for a specific purpose by (1 ) cleaning to remove inorganic impurities; (2) sizing-crushing or screening, or both; or (3) special treatment, such as dedusting. The properties and quantities of impurities in coal are of major importance in the design and operation of steam generating equipment. Al- though boilers are often designed and equipped to use a wide range of coals, no boiler will perform equally well with all types of coals. All coals have certain properties that place limitations on their most advantageous use. These limitations are especially stringent for many of the older installations. Because of a general lowering of quality of raw coal in recent years, the need for coal cleaning has significantly increased. Among the factors contributing to the need for increased coal preparation are (1) increased demand for quality brought on by market and environmental requirements; (2) increased extraneous dilution caused by mine, health, and safety laws; and (3) depletion of the higher-quality coal seams.

Jan 1, 1979

By G. Howell Clevenger

FORMERLY great divergence of opinion existed in regard to the influence of copper in steel, as affecting its various physical properties. More recently the investigations of Stead,1 Breuil,2 Wigham,3 Burgess and Aston,4 Ball and Wingham,5 Miiller,6 Dillner,7 and others have shown fairly good agreement in the major points. Copper steel has been shown by these investigators to possess special properties which make it valuable for certain uses. The general range of composition of the useful alloys of copper and iron, and of copper, iron, and carbon, has been quite definitely established, for the former by Burgess and Aston,8 and for the latter by Breuil 9 and Stead.10 Stead 11 has removed one difficulty in reconciling certain of the earlier data by calling particular attention to the influence of carbon in copper steels. Another point which caused confusion in the earlier investigations, particularly in regard to " red-shortness," was the presence of sulphur. Failure to note the presence of sulphur often led to attributing " red-shortness " to the presence of small amounts of copper. Turner 12 has called attention to the fact that where copper exists in an iron ore it often occurs as the sulphide, so that the presence of copper in steel made from such ores might also, necessarily, mean the presence of sulphur. It is evident that the effect in this case might be quite different than where pure copper was added.

Jan 10, 1913

By A. W. Schlechten, R. F. Doelling

Parkes&apos; process crusts were vacuum distilled using a shortened Pidgeon retort. Zinc was effectively removed below 800°C and recovered as a zinc sheet easily stripped from the furnace liner. Lead dasdistillationazinc required about 950°C and the resulting lead condensate tillationtended to stick to the thin metal liner. Final purity of residue is limited only by nonvolatile metals such as copper. THE successful commercial application of vacuum distillation for the removal of zinc from lead, as described by W. T. Isbell,&apos; raises the question of whether or not a similar method can be used for other metal separations. Preliminary laboratory experiments on the vacuum distillation of Parkes&apos; crusts by one of the authors&apos; gave such encouraging results that it was decided to make a series of tests with large scale equipment to determine the results that might be expected in plant operation. The pilot-plant test results are reported in this paper. The great advantages of vacuum dezincing are its simplicity, the relatively low temperature of operation, and the fact that the zinc is recovered in the metallic state ready for use again in the desilveriza-tion of lead bullion. These same advantages and others would be realized from the vacuum distillation of the zinc-lead-silver crusts made in the Parkes&apos; process. Zinc readily will distill over at temperatures of 800" to 900 °C as contrasted with the 1200°C or more used in the Faber du Faur furnace. Furthermore, the recovery of zinc as metal is practically perfect since there is no loss by oxidation or fuming. If the vacuum distillation is continued and hastened by raising the temperature to around 1000°C, the lead will distill over at an appreciable rate and deposit in a warmer zone of the condenser. This lead will contain a small amount of silver, but it can be returned to the desilverizing kettles and there is not the chance of loss that there is in disposing of the rich litharge from cupelling. The lower temperatures required will mean a saving of fuel and less wear on the equipment. One further point is that the vacuum distillation could be run on a small scale practically continuously, so as to avoid the accumulation of large amounts of silver-rich material and the need of assembling a large crew for special cupellation runs. It should be pointed out here that the final purity of the silver residue will depend on the copper or iron content of the crusts, as these and other metals with low vapor pressure will not be eliminated. The idea of treating the silver-zinc-lead crusts from the desilverization of lead bullion by vacuum distillation is not a new one, but such experiments have not been reported, as far as can be determined. In 1912, T. Turner presented a paper3 before the Institute of Metals on the vacuum distillation of brass, and a member of the audience suggested that he try his method on Parkes&apos; crusts. In 1935, W. J. Kroll, noted for his discovery of debismuthiz-ing lead by calcium additions, published a paper&apos; on vacuum distillation of metals and pointed out possible applications in the lead industry. Principles of Separation The successful separation of two or more metals by distillation depends upon an appreciable difference in the effective vapor pressures of the metals in the alloy to be treated. The vapor pressures of the common metals have been determined with considerable accuracy; for example, at 800°C the vapor pressures of the individual metals which are of particular interest in this paper are about .as follows: Zn, 241 mm; Pb, 0.0553 mm; and Ag, 0.0000276 mm. Unfortunately,, data are not available on the activities of the components in the ternary system Zn-Pb-Ag, but it can be estimated that on the basis of the vapor pressures of the individual metals a good separation can be made by distillation. The preliminary laboratory tests previously mentioned&apos; supported this assumption. The pilot-plant size vacuum distilling furnace is shown in Fig. 1. It consisted of an abbreviated Pidgeon retort, 5 ft long with an ID of 8 in., heated by six silicon carbide elements placed symmetrically

Jan 1, 1952

By W. E. Ruder

IT has been pointed out by Stead 1 that grains of considerable coarseness may be developed in steels containing from 3 to 5 per cent. of silicon, and in a previous paper 2 the present author has shown that under the proper conditions of annealing single grains having an area of 50 sq. cm. may be obtained. It is the purpose of this paper to discuss in more detail the conditions, promoting the growth of these grains, in the hope that the experiments described may throw some additional light upon the general problem of grain growth in metals. These silicon steels lend themselves particularly well to such experiments because of the ease with which the change in structure may be followed and because of the fact that the effect of the carbon present is largely obliterated by the high percentage of silicon. This forms a solid solution with the iron, which acts very much like a pure metal. This alloy has been found to have but one critical point, viz., Are. This point, determined by Roberts-Austen for Hadfield&apos;s 4 per cent. Si alloy, was found to lie at 703° C. Vigouroux3, in working with pure Fe-Si alloys, finds this point to rise from 750° C. for 0.5 per cent. Si to 860° for 6 per cent alloy, with a flat region in the curve from 3 to 4 per cent. Si. No accurate determination of this point has been undertaken by the present author, but it has been roughly determined to lie between 730° and 750°.

Jan 12, 1913