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By W. Mostowitsh

I. Introductory LEAD sulphate occurs as anglesite, and is formed in every roasting of lead sulphides or sulpho-salts containing lead. In smelting in the blast furnace an ore containing natural or artificial lead sulphate, a large part of the sulphur present goes to the formation of the intermediary product matte which requires further treatment for the recovery of the values it contains. It is therefore of importance to study the behavior of lead sulphate at elevated temperatures, both without and with reducing agents, especially as the information available gives data which are more or less conflicting. II. Decomposition of Lead Sulphate by Heat The dissociation of PbSO4 into PbO and S03 or S02 and 0 has been discussed by many metallurgists. The following data are considered to be representative. Doeltz and Graumann1 found that PbSO4 was not affected by heat at 800° C.; that dissociation began at 900° C., and was rapid at 1,000° when the salt lost in 1 ½ hr. 14.3 per cent. of its weight, the dry salt containing 26.43 per cent. SO3. Hofman and Wanjukow2 summarize their work upon the dissociation of metallic sulphates with the statement that the decomposition of PbSO4 begins at 195° C., but progresses very slowly, with the formation of the basic salt 6PbO.5S03 at 705°; that this salt undergoes a transformation at 847°, begins to be decomposed at 888°, to sinter at 896°, and to fuse at 910°; rapid dissociation begins at 952°, and is accompanied by volatilization of PbO; retardations at 958° and 962° indicate an acceleration of decomposition which, however, is not complete. Proske3 found that PbSO4 gave off at 900° C. in 30 min. only 0.63 per cent. of its SO3, and that the loss increased with

Jan 5, 1916

By Edward Keller

GOLD MOVEMENT ON SURFACE OF AURIFEROUS COPPER WHEN LATTER IS SUBJECTED TO OXIDATION SOME years ago the writer's attention was called to the fact that rolling-mill scales from auriferous copper do not have the gold content proportional to the gold contained in the copper from which they are derived. I So, later, he made a few simple experiments, which are described herewith. In: order to test the gold movement on the changing surface of a copper plate under the influence of oxidation, plates 6 in. by 8 in. by I in. (15.2 cm. by 20.3 cm. by 2.5 cm.) of converter copper, refined, of 99.29 per cent. purity, and leaded copper with a content of 95.65 per cent. copper, were obtained. Ten cuts were made through the thickness of the plates along the longitudinal center and the silver and gold content ascertained in each of the 10 samples in both plates, as shown in the accompanying illustration. The assay results, recorded in Tables 1 and 2, show that the gold distribution is relatively uniform in both plates, while silver has greater variations, especially in the leaded plate. The plates subjected to oxidation were placed in a red-hot muffle for about 2 hr., two small scorifiers being used as supports. Arranged alongside each other, they nearly filled the width of the muffle, and so were practically under equal conditions of heat and draft. The accurate observance of the time was not possible, however, because of other work, but the time of the exposure of each plate in a pair was identical. At the end of each period, each plate was plunged into water and completely freed of scale, which was carefully collected, dried, weighed, and analyzed. Samples of the plates had also been taken of the molten metal and duly analyzed. Table 3 contains the analytical data for the two plates and their several sheets, or layers, of oxide scales. These figures show that in the oxidations of the converter copper the silver is fairly uniform, while

Jan 1, 1919

Sec. 1. The membership of the Institute shall comprise six classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members. All shall be equally entitled to the privileges of membership, excepting that no member of any class whom residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the claw of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members.

Jan 1, 1934

By W. R. Hibbard

The term lineage was first introduced by Buergerl to denote dendritic branches, grown from a crystal nucleus during solidification from the liquid, with imper- fections in alignment of the order of 10 : to 10-4 cm. These imperfections are associated with distortions of the dendrites caused by the subsequent solidification of the inter-dendritic filling and are illustrated in Fig I. Buerger etched zinc single crystals made by the Bridgman3 method to develop this dendritic pattern and show lineage microscopically. Since maximum crystal growth in face-centered cubic metals occurs along the [IT] directions,2 lineage would appear in copper as small deviations of dendritic branches from these directions. Elam4 and others5"8 reported etching effects resulting from coring along the cube face traces of various copper alloy crystals. These traces were used by Samans8 to orient single crystals. Williamson9 noted a "lined structure (in alpha brass single crystals) consisting of an ordered arrangement of etch pits" which were probably traces of {IOO} planes but somewhat uncertain because they were never straight (that is, apparently lineage). Greningerl1 described the distortion and multiplicity of Laue spots in back reflection X ray photograms of copper single crystals showing lineage. The present investigation -includes metal-lographic, X ray, and property studies of lineage in large grain and single crystal specimens of copper. Preparation of Specimens specilnens 10 in. long 35 1/2 in. diam of oxygen-free copper (o.F.H.c.) (99.985 pet) were' melted vertically in graphite crucibles under an atmosphere of commercial nitrogen purified through a gas train including sulfuric acid, potassium chloride, magnesium chiorate, hot copper chips and phosphorus pentoxide. After a temperature of 1200°C had been maintained for 1/2 hr, the furnace was turned off and the specimens cooled at a rate of about 150°c an hour' This method of direct solidification was used by Greningerlo to produce single crystals with marked lineage and in this investigation produced a fair yield of single crystal specimens in

Jan 1, 1949

By W. R. Hibbard

The term lineage was first introduced by Buergerl to denote dendritic branches, grown from a crystal nucleus during solidification from the liquid, with imper- fections in alignment of the order of 10 : to 10-4 cm. These imperfections are associated with distortions of the dendrites caused by the subsequent solidification of the inter-dendritic filling and are illustrated in Fig I. Buerger etched zinc single crystals made by the Bridgman3 method to develop this dendritic pattern and show lineage microscopically. Since maximum crystal growth in face-centered cubic metals occurs along the [IT] directions,2 lineage would appear in copper as small deviations of dendritic branches from these directions. Elam4 and others5"8 reported etching effects resulting from coring along the cube face traces of various copper alloy crystals. These traces were used by Samans8 to orient single crystals. Williamson9 noted a "lined structure (in alpha brass single crystals) consisting of an ordered arrangement of etch pits" which were probably traces of {IOO} planes but somewhat uncertain because they were never straight (that is, apparently lineage). Greningerl1 described the distortion and multiplicity of Laue spots in back reflection X ray photograms of copper single crystals showing lineage. The present investigation -includes metal-lographic, X ray, and property studies of lineage in large grain and single crystal specimens of copper. Preparation of Specimens specilnens 10 in. long 35 1/2 in. diam of oxygen-free copper (o.F.H.c.) (99.985 pet) were' melted vertically in graphite crucibles under an atmosphere of commercial nitrogen purified through a gas train including sulfuric acid, potassium chloride, magnesium chiorate, hot copper chips and phosphorus pentoxide. After a temperature of 1200°C had been maintained for 1/2 hr, the furnace was turned off and the specimens cooled at a rate of about 150°c an hour' This method of direct solidification was used by Greningerlo to produce single crystals with marked lineage and in this investigation produced a fair yield of single crystal specimens in

Jan 1, 1949

By H. A. Wriedt

Zinc-vapor pressures in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C were measured by an isopiestic method. Thermody-na?nic properties of zinc in these solutions were derived directly and those of iron with a Gibbs-Duhem integration. Zirzc and iron exhibit large, positive, and moderately temperature-sensitive deviations from ideality. Excess enthalpies and Gibbs energies are positive in the ranges studied. It has been establzshed in relating published phase equilibria to the Gibbs energies of forming solid solutions that positive departures from ideality also exist in the fcc solutions. Tlze stability, as defined by Darken, of the bcc solutions is small but positive at 703.5"C. Its decrease with decreasing temperature indicates that a miscibility gap may exist in the stable or metastable bcc solutions at lower temperatures. The changes of thertnodynanlic properties relatable to changes in magnetic state are minor compared to other changes due to alloying. The accuracy with which the relation between lattice parameter and composition of the bcc solutions is known has been improved. Zinc increases the lattice parameter of a iron by O.ZOZA per unit atom action zinc to at least NZn = 0.25. TO our knowledge, only Ciganl has previously investigated thermodynamic properties of the bcc solutions of the Fe-Zn system. He measured zinc-vapor pressures in the temperature range from about 320" to 360°C by an effusion technique. We have measured the vapor pressures of zinc in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C by an isopiestic technique. This investigation and the pursuant thermodynamic computations are part of a program for studying several properties of these solid solutions. In the appendix we report a remeasurement of the relation at room temperature between the lattice parameter and zinc content. Related work not reported herein embraces measuring the diffusivity2 of zinc in ferrite at 700" to 900°C and the Curie point temperature3 as functions of composition. EXPERIMENTAL METHOD AND APPARATUS Purified iron at a series of constant temperatures was saturated with zinc at a series of constant zinc-vapor pressures, the range of conditions being so limited that the equilibrated solid solutions were ferri-tic. The equilibration was conducted in long capsules, Fig. 1, that had been evacuated, gettered with titanium, and sealed. The purified iron, part of a vacuum-melted ingot of electrolytic-iron stock (Glidden Co. 1044-grade), had the impurity contents listed in Table I. It was used in the form of millings about 0.001 in. thick. A zinc of 99.999 pct purity (United Mineral and Chemical Corp.) and later one of 99.9999 pct purity (Cominco Products, Inc.) were used, with no observed difference in results. Sufficient zinc was placed in the capsule (separate from the iron and kept at a different temperature) to supply the vapor phase and the iron alloy, while leaving a pool of pure liquid zinc throughout the run. The imposed temperature of the residual zinc pool fixed the vapor pressure of zinc throughout the capsule; condensation was avoided at other locations by making this the lowest temperature in the capsule. Two common complications of nonisothermal systems were, we believe, effectively absent from ours: first, molecular species other than monatomic have no appreciable concentration in zinc vapor at 700" to 900~~: second, the development of zinc-pressure differentials in the capsules was suppressed by use of relatively large-diameter tubing and the absence of diluents in the zinc vapor other than desorbed impurities. The specimens and zinc pool were located at two isothermal zones (each ranging within 1°C over several inches) of a wire-wound, 37-in.-long vertical-tube furnace. The required temperature distribution was achieved by external adjustment of the currents in three electrically isolated windings. The temperatures of the isothermal zones were controlled independently by ther-

Jan 1, 1968

By M. I. Sherman, J. D. H. Strickland

PRELIMINARY experiments in these laboratories showed that whereas pyrite1 produced only sul-fate the action of aqueous chlorine solutions on most other sulfide ores resulted in the formation of a mixture of sulfate and elemental sulfur, the production of the latter being favored by a very dilute solution of oxidant. The reactions taking place were obviously complex and only a detailed kinetic study could be expected to clarify the position and enable a prediction to be made of conditions leading to the rapid formation of metal salt and the economically desirable elemental form of sulfur. Galena was chosen for the first investigation as it is of widespread occurrence and is representative of a simple cubic lattice sulfide containing the monosulfide unit, S2-. Experimental Procedure The apparatus and general technique used in this work have already been described.' Analyses for chlorine and sulfate were carried out by the same methods as those used for pyrite. The lead in 1 ml aliquots of solution was determined polarographi-cally, after destroying chlorine with hydrazine hy-drochloride and making solutions 0.5 molar with hydrochloric acid. A large sample of Kansas galena, assaying at better than 98 pet PbS, was crushed and wet sieved to give fractions of —10 + 14, —20 + 28, —28 + 35, and —48 + 65 Tyler screen. The particles were almost perfect cubes and the apparent surface Per gram was calculated assuming each particle a cube Of side equal to the mean mesh opening. A volume shape factor, calculated as for pyrite, was exactly unity. The main apparatus was unsuitable for direct visual examination of the ore particles during the reaction. For this purpose a small cell from a Spekker Absorptiometer optical flats 1 cm apart) was l by a greased microscope slide after filling with oxidant solution. One or two ore particles were placed in the cell and the solution was stirred by a glass covered speck of iron wire activated by an external rotating magnet. The surface of an ore particle was examined under a binocular microscope at between 10 and 40 magnifications. Results Experiments were made under a wide variety of conditions, the form of presentation of the data being illustrated by Fig. 1, where the concentrations of chlorine, sulfate, and sulfur are plotted against time. The fictitious concentration of solid sulfur is used for convenience and is the molarity of sulfur which would be recorded if the elementary sulfur formed during the reaction were dissolved in the liquid iii the reaction vessel. As some lead sulfate is occluded with the sulfur on the ore particles the amounts of sulfur and sulfate formed during a reaction cannot be calculated

Jan 1, 1958

By G. R. Love, C. C. Koch

The changes in superconducting properties with aging time have been studied ,for the pecipitation reaction in a Tc-30 at. pct V alloy. Superconducting critical temperature, upper critical field, and relative critical current density were determined by ac susceptibility techniques. Aging produces changes in critical temperature of both matrix and precipitate which can be rationalized by compositional effects. maximum flux pinning (critical current density) occurs at a time during aging when subgrain boundaries are completely decorated with precipitates and the subgrain centers remain precipitate -free. The particular effectiveness as barriers to flux motion of planar defects which enclose regions of low deject density is discussed. THE precipitation of a second phase can dramatically modify the superconducting properties of type I1 super-conductors. According to Livingston and Schadler1 one might expect changes in the primary, secondary, and tertiary superconducting properties of the material. Changes in matrix chemistry caused by precipitation can alter the fundamental superconducting parameters; critical temperature, Tc, and thermody-namic critical field, Hc. The concimitant changes in electron mean free path (reflected in normal state resistivity) can affect the critical fields Hc 1, IIc2, Hc3. Finally, the presence of precipitate particles may hinder the motion of flux lines and may considerably improve the current-carrying capacity in high-field superconductors. The influence of precipitation on superconducting properties has been studied in a number of systems.2 Magnetization measurements have been used to study the influence of precipitates on flux pinning in lead-base alloys by Livingston3 and Evetts et al4 In these alloys precipitates induced magnetic hysteresis and flux trapping. The amount of hysteresis increased with the volume fraction of precipitate and decreased with coarsening of the precipitate. Jn an Al-Zn alloy5 and an A1-Ag alloy6 the initial precipitate size was presumably smaller than a coherence length and coarsening increased magnetic hysteresis5 and critical current density.6 The influence of precipitation on superconducting properties has also been studied in several of the commercially interesting Ti-Nb7-10 and zr-Nb11 alloys. The maximum in critical current density for these alloys was confined to a narrow range of either isothermal aging time" or isochronal aging temperature7 during the precipitation reaction. Thus, experimental evidence and theoretical considerations suggest there is an optimum precipitate size, spacing, and density, and a critical composition with respect to the matrix for flux pinning. What these "optimum" values might be and the relative importance of each is still not clear, although a few generalizations can be made. It is generally accepted1' that particle sizes smaller than the coherence length or larger than the inter-flux line spacing are poor pinning centers. In high Hc2 materials, precipitate sizes for maximum values of critical current density lie in the range of 50 to 2000Å,9,7 and there are indications that increasing dissimilarity between precipitate and matrix produces increasing pinning force.13 Because of several interesting features of the aging reaction in a Tc-30 pct V alloy, we have chosen to study the influence of precipitation on the superconducting properties of this alloy. The physical metallurgy14 and a survey of the superconducting properties" of the Tc-V alloy system have been reported. The Tc-V phase diagram is presented in Fig. 1. At 1500°C the Tc-30 pct V alloy is in the single phase 6 field. Samples quenched from the 6-phase field have a CsCl structure X-ray diffraction pattern at room temperature and it has been proposed that the 6 structure is closely related to the bcc lattice.14 When held isothermally below the eutectoid temperature, 115O°C, the 6 phase decomposes into the CsCl and hcp phases.

Jan 1, 1970

By R. A. Davidson, L. Silverman

RESIDENTS of many urban centers are becoming increasingly aware of the obscuring effect of fume and smoke discharge from power, metallurgical, chemical, and other industries; and they, as well as the legislatures of these affected cities, are agitating for cleaner air. Management's most pressing problem is to find an economical way to reduce process effluents in response to the growing pressure from population and legislative demands. The removal must be done, if possible, without handicap to the current operation, since the costs of relocating are often excessive or prohibitive. In fume recovery or disposal, an important item to consider is whether or not the material being discharged has any value. If it has commercial value, the cost of its recovery may offset or aid amortization. For this reason, in making a study of the specific problem in hand, a major factor was the nature of the material emanating from the stack: in particular, its particle size, size range, and its chemical and physical composition, as well as its potential value and utility when recovered (in either a wet or dry state). Should the product have no commercial value, it must be disposed of at minimum cost in a way to prevent recontamination. Initial studies were therefore made to determine stack concentrations and volumes of material evolved from the operations. The next phase of the study concerned the physical and chemical nature of the collected fume. The third portion of this paper describes the wet and dry collector studies undertaken to recover the fume. Cleaning Requirements for Ferroalloy Furnace Operation The basic need for any effluent collection equipment is the highest possible efficiency and the lowest tolerable resistance when the power consumption involved is considered. Since the electric furnace effluent is largely composed of fume of small size (less than 0.5u), it has high light obscuring properties, and even low concentrations will cause some loss of visibility and be evident to nearby residents. The permissible limit for fly ash emission in many cities is based on a weight value (viz, approximately 0.4 grains per cu ft), but the smoke density values are dependent upon a shade of color. In the case of the Los Angeles County code, emission is restricted to pounds per pound of material processed per hour basis (but not exceeding 40 lb per hr for any one given plant operation). If an average particle size of the fume from ferro-silicon alloy electric furnaces is assumed to be 0.4u (as shown later, this is the approximate mean size) and an average loading of 1 grain per cu ft (stp), each cubic foot of stack gas will contain approximately 75x10 10 particles (based on assumed, and confirmed, spherical shape and a standard deviation of unity). When it is realized that the air in metropolitan areas, which are also general industrial areas, contains approximately 5x108 particles, the tremendous light scattering effect of this concentration becomes apparent. Consequently, nearly 100 pct collection would be necessary to equal the average concentration. Fortunately, however, discharge from a high point above ground (50 to 100 ft) will result in at least a thousandfold dilution, or the stack concentration reaching the ground in the foregoing case might result in a ground concentration of ' particles. If the concentration at the source could be reduced by a factor of 100 (99 pct efficiency of collection), then a concentration of 75x10" particles would be diluted to 7.5x10' which would be very satisfactory. An efficiency of 90 pct (factor of 10 decontamination) at the source would result in a discharge of 75x109 articles which upon dilution yields 75x10 which is still 15 times the general air value. Another approach to this consideration is to use the value of concentration of 0.005 grains per cu ft for the value of a visible effluent as cited by Kayse.1 To attain this value with an average loading of 1 grain per cu ft would require an efficiency of 99.5 pct. Since the foregoing value is not based on any reported size of fume particles, it is felt that the numbers' approach given previously is more reliable. These calculations serve to indicate the desirability of thorough cleaning, preferably at the source, and with efficiencies well above 90 pct, preferably above 95 pct (dilution 1:20). One of the most important items in any control program is to reduce the concentrations as close to their sources as possible. The use of better furnace design, deeper coverage over the electrodes, and the prevention of blows or breaks in the surface all help to reduce dissemination; consequently, all of these improvements should be made, if possible, to cut down the effluent load. In addition, in order to minimize the volume of contaminated air that has to be cleaned, the furnace should be enclosed as much as possible. Test Arrangements Before fundamental studies with collectors were made, a furnace stack selected for the test program was sampled to determine the gas temperatures and

Jan 1, 1956

By B. F. Oliver, F. Garofalo

Gas-metal heterogeneous reactions and zone-lrelting were sinultarneously employed to produce several high-purity irons with low interstitial contents in a levitating- zone melter. Successive zone-tneltitzg pusses were made in carious sequences of atmospheves which included prepuvified tank hy-drogeta, water vapor hydrogen, palladiuril-purified hydrogen, and vacuunm of 2 x 10-6 Torr. Different irons ranging in purity from 99.89 to 99.996 pct with residual curbon contents of 17, 8 to 10, and 3 to 5 ppm have been Drepared. No measuvable gradient in the residual carbon content was observed along the entire zone-melted length (6-10 in.) in I-ilz.-diameter bars. The absence of a carbon-concentration gradient in the solid indicates an apparent distvihution coefficient of 1, an unusual condition. Internal friction, solid-state extraction, and hot-hardness results indicate that the level of mobile carbon in a iron depends on the gas-metal heterogeneous reactions employed. Purification under an oxidizing atmosphere resulted in the immobilization of nearly all of the carbon present at leuels of 10 ppm or less. Continuation of purification in a reducing atmosphere veturued the carbon to a state of mobility which was aguin reversed by further purification in all oxidizing atmosphere. The immobilization of curbon at "vesidual levels " is believed to be associated with a strong interaction between carbon and oxygen atoms. frons with low carbon and nitrogen contetzts which did not exhibit a hot-hardness peak were produced after zone ynelting in vacuum. CARBON, nitrogen, and oxygen have strong and well-known effects on many properties of iron. These effects persist even at concentrations of 5 to 20 ppm. The intent of the present investigation was to establish procedures for the preparation of high-purity iron with concentrations of these elements in the range of 5 to 20 ppm and lower. The results reported here deal with the procedures employed to prepare high-purity iron, and with observations on the behavior of certain elements at "residual levels": particularly carbon. The details of the (levitating) zone melter in which the final purification steps are performed and the necessary control of the pertinent solidification variables have been described previously.1,2 MATERIALS AND PROCEDURES Commercial electrolytic iron was induction vacuum-melted and cast into 30-lb ingots. Melt additions and ingot analyses for carbon, oxygen, and nitrogen are noted in Table I. All ingots were melted in stabilized zirconia crucibles conditioned with one iron wash heat. Middle sections of the ingots were forged to 1-1/4-in. rounds, machined to 1-in.-diameter bars, then cut to 36-in. lengths. The zone-melting operations were performed on six iron bars (A to F) at a freezing velocity of 2 in. per hr with the freezing interface rotating2 at 200, 300, or 400 rpm. Liquid zones were passed through the bars in various sequences of atmospheres, Table 11, including prepurified tank H2, palladium-purified Hz, wet H2, and system vacuum of 2 x 1018 Torr. Wet-Hz atmospheres were obtained by bubbling palladium-purified Hz through water exhibiting a resistance of 3 megohms. This water was heated with a platinum-immersion heater and was degassed prior to use. Zone melting in a wet-HZ atmosphere resulted in oxidation of the elements which are oxi-dizable with respect to iron. Fine oxide particles were observed on the surface of the liquid zone, and were encased in the bar surface with the passage of the molten zone. Between each zone pass, the surface of the bar was removed by filing and deep etching; this was continued until the oxide formation ceased. The filings were magnetically separated and the residues analyzed by optical spectroscopy. These were especially high in silicon and manganese. Samples were removed from the iron bars, with few exceptions, following each zone-melting operation. A 0.08-in.-thick disc was cut with an Al2O3 cut-off wheel at a point 1/2 in. above the beginning of freezing. Material from each disc was used for hot-hardness measurements, resistivity-ratio measurements, and carbon, nitrogen, and oxygen analyses. Analyses for most other elements were

Jan 1, 1965

By Joseph T. Singewald

AMONG the genetically interesting iron ores of the United States are those of the St. Francis Mountains near Ironton and Iron Mountain, Missouri. They are specular hematite in porphyry. The Iron Mountain and Shepherd Mountain deposits are generally spoken of as veins and those of Pilot Knob, Cedar Hill, and Russell Mountain as bedded deposits. Iron Mountain has produced nearly 4,000,000 tons of ore and Pilot Knob about 1,500,000 tons. The output of the other three localities has been insignificant. Pilot Knob is no longer worked as an iron mine, but the rock is now being crushed for use as road metal. Iron Mountain has continued as an active producer. In 1927, the property was acquired by the M. A. Hanna Co. and an extensive prospecting and exploration campaign was undertaken, so that the ultimate production of Iron Mountain will doubtless greatly exceed the figures mentioned. Previous Theories of Origin Descriptions of the deposits and theories of their origin have been concerned mainly with Iron Mountain and Pilot Knob, which represent the two contrasting types of occurrence. The Iron Mountain deposits have been considered of close magmatic origin by Whitney' in 18.54, Geijer2 in 1915, and Spurr3 in 1927. Whitney referred to them as of eruptive origin. Geijer considered them fissure fillings at magmatic temperatures. Spurr called them vein dikes formed from ore magma which was essentially fluid iron oxide. Schmidt4 in 1872 ascribed them to fissure filling by thermal chalybeate waters of meteoric origin. Nason5 in 1892 advanced essentially the same explanation. One of the best

Jan 1, 1929

By Wallace Thorneycroft

FOREWORD This paper by Mr. Thorneycroft, Past President of the Institution of Mining Engineers (Great Britain), and chairman of its Subsidence Committee, is a valuable contribution to the assemblage of data on ground movement and subsidence from coal mining. It deals with the effects of advancing longwall, a method almost universal in Europe but as vet little used in the United States outside of Northern Illinois and in a few scattered places elsewhere, in thin coal beds, as in the Lexington field, Missouri, Canon City field, Colorado, and the Birmingham field, Alabama. Although by advancing- longwall, a maximum recovery of coal is obtained and it has to be employed where there are weak shale roofs, especially in deep mines, it is a more expensive method of operation unless the mining conditions are favorable, which is unusual in the United States. On the other hand, there is a growing use in this country of what is essentially retreating long wall, with an approximately straight break-line as described by Rayburn.1 With this method, in which the pillars are substantial, it was shown that the ground movement effect is practically identical with that of advancing longwall, hence the value to mining engineers of the precise data given by Mr. Thorneycroft. His study is unusual in several respects; it deals with conditions connected with ,the mining of a coal bed 20 in. thick, about 490 ft. below the surface, over a mined-out area in a 5-ft. bed about 90 ft. below, which had been mined about 12 years earlier. Both mines passed under Plean House, a building of massive cut stone construction built over a century ago, in which Mr: Thorneycroft resided throughout the under-mining period. Slight cracks opened in the walls as the longwall face approached the house in mining the upper seam, and closed after the face passed and subsidence took place. In the northwest wall, the last wall the face passed under, some stone blocks were broken, which was attributed to a strike period when the advance of face came nearly to a standstill. Other than this there was no perceptible permanent damage, as indicated by the photographs taken by the undersigned in 1923 (Figs. 1 and 2). Mr. Thorneycroft used a novel means of studying the successive positions of the corners of the building: he hung plumb bobs from the eaves and traced the paths of the respective plumb bob points on level surfaces. The angles made by the house walls with the plumb bob lines gave measures of the slope of the subsidence wave at the respective points. A slight upward wave was indicated by the surveys ahead of the subsidence, which would appear to be due to a tilting over of the massive sandstone stratum in the roof measures near the surface, the edge of the subsidence area acting as the fulcrum.

Jan 1, 1931

By L. S. Darken

IT has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernst1 in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and Fuoss2 with results which have recently been confirmed experimentally by Harped and Nuttall.3 This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author 4.6 who pointed out4 that "for a system of more than two components it is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepticism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley11 in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion 0f acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 1050°C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1948

By M. Gell, G. R. Leveran

The high- and low-cycle fatigue properties of the nickel-base superalloy, Mar-MBOO, in columnar-grained and single-crystal forms were determined at room temperature. It was found that the fatigue lives of these materials were greatly affected by the size of preexisting cracks in MC-type carbides contained in the micro structure. Most of the data falls on two curves given by: (zN)'/A€= K, where Nf is the number of cycles to failure, Af is the total strain range, and K is a function of carbide size. No difference was observed in the fatigue behavior of the columnar-grained and single-crystal materials for the same MC carbide size. Matrix slip and crack initiation occurred at precracked MC carbides and, to a lesser extent, at micropores. Fatigue crack propagation was mainly in the Stage I mode, i.e., on cry stallo graPhic slip planes. The Stage I fracture in these materials was unusual in that distinct features were observed on the fracture surfaces. In high-cycle fatigue, these features resembled those commonly observed on the cleavage fracture surfaces of bcc and hcp materials. Yet, in this study, the cracks propagated slowly in a cyclic manner. In low-cycle fatigue, the Stage I facets contained equiaxed dimples, similar to those observed on the tensile fracture surfaces of ductile materials. These observations indicate that both local normal and shear stresses are involved in these Stage I fractures. A model is proposed to explain these results based on the weakening of the cohesive energy of the active slip planes by reversed shear deformation and the fracture of the bonds across the weakened planes by the local normal stress. RECENT developments in casting technology have produced cast nickel-base superalloys in columnar -grained and single-crystal forms.1'2 The tensile and creep properties of the nickel-base superalloy, Mar-M200, cast in these forms have been shown to be superior to the corresponding properties of the conventionally cast polycrystalline material.lp2 This improvement in properties results, in part, from the elimination of grain boundaries in the single crystals and the alignment of the grain boundaries parallel to the stress axis in the columnar-grained castings. As part of a program to evaluate the fatigue properties of nickel-base superalloys cast in single-crystal and columnar-grained forms, a study has been made of the cyclic deformation and fracture of Mar-M2OO at room temperature. M. fiFl I .hininr Mpmher AIMF ic ^pninr Rocoarrh Accn^iata anH I) EXPERIMENTAL PROCEDURE The composition range of Mar-Ma00 in weight percent is: 8 to 10 Cr, 9 to 11 Co, 11.5 to 13.5 W, 0.75 to 1.25 Cb, 1.75 to 2.25 Ti, 4.75 to 5.25 Al, 0.01 to 0.02 B, 0.03 to 0.08 Zr, 0.07 to 0.12 C, bal. Ni. All of the castings met the above specifications. The castings were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr which resulted in a 0.2 pct offset yield stress of 150,000 psi at room temperature. The microstructure of the material consisted of cuboidal, coherent particles of ordered, fcc Ni3(A1,Ti) (commonly designated y'), approximately 0.3 p on edge, distributed in an fcc y solid-solution matrix. MC carbides together with shrinkage and gas micropores were also distributed throughout the materials. The MC carbides and micropores were located preferentially in the interdendritic interstices, as well as in the grain boundaries in the columnar-grained castings. The (100) direction of all the single crystals and the common (100) axis of the grains in the columnar materials were aligned within about 5 deg of the specimen axis. Fatigue testing was carried out in the high-cycle (HCF) and low-cycle (LCF) fatigue regions, with the major difference being gross yielding of the specimen occurred during the first cycle in the LCF region. This division also corresponded with the more usual one in which the life of a specimen in LCF is less than lo4 cycles and that in HCF is greater than lo4 cycles. The designs of the high-cycle fatigue and low-cycle fatigue specimens are shown in Figs. l(a) and (c), respectively. The gage sections of both HCF and LCF specimens were electropolished prior to testing. The HCF specimens were tested in an MTS, closed-loop, hydraulic fatigue machine at 10 cps in air. The specimens were cycled between a tensile stress of 5000 psi and a maximum tensile stress which ranged from 35,000 to 125,000 psi, Fig. l(b). The LCF specimens were cycled under strain control from zero to a maximum tensile strain, Fig. l(d), in a Wiedemann-Baldwin testing machine. The experimental procedure has been described elsewhere.3'4 Both HCF and LCF tests were interrupted periodically in order to replicate the development of slip and cracking at the specimen surface. This was accomplished by placing plastic replicating tape around the gage section of the specimen while the specimen was in the mahine. The size of the MC carbides for all specimens was measured on a polished longitudinal section through the gage section after fatigue testing. The method of measurement consisted of carefully scanning the entire polished section in order to locate the largest MC carbides. Photographs were then taken of the six longest carbides oriented approximately normal to the

Jan 1, 1969

By Charles Clayton

CAST-STEEL runners, while not interesting from a commercial standpoint, furnish valuable material for microscopic study. Foley1 found not only the usual ingot structure, but zones of Widmannstattian structure, which he explains as due to differential crystallization. The writer, in examining nickel-steel runners, found a type of pro-eutectoid ferrite that is unusual and most probably new. The runner in question was 8.75 cm. (3.5 in.) in diameter and analyzed at its center 2.69 per cent, nickel and 0.350 per cent. carbon and at its edge 2.62 per cent. nickel and 0.359 per cent. carbon. The macrostructure, which is the usual type, is shown in Figs. 1 and 2, which are a cross-section and the longitudinal surface, respectively. Slight segregation of ferrite can be seen near the center of the segment and at other points near the edges of polyhedral grains. Stead's reagent brings out the dendritic structure within the grains as shown in Figs. 3 and 4. This texture is what would be expected of such a steel. Figs. 5 to 10 show the peculiar swirls of pro-eutectoid ferrite, the finding of which prompted this paper. These swirls, or eddies, if such a term can be applied, occur in all parts of- the runner and in all parts of the individual grains. I he tipper left-hand figure shows this ferrite at a grain boundary; the middle left-hand figure shows the inner portion of a grain; and the lower left-hand figure shows these swirls at the edge of a grain which is also the outer edge of the runner. Straight-lined ferrite associated with swirls is found in the areas of Figs. 11 and 12. The texture of the carbon-bearing constituent of the runner is shown to- some extent in Fig. 12, the pearlite being very fine or sorbitic. Higher magnification does not bring out any new features either in the peculiar ferrite or in the pearlite. Figs. 13 and 14, at 240 diameters, show the curved and straight-lined ferrite.

Jan 3, 1920

By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By Albert J. Phillips

As EARLY AS 1824, Haidinger1 described crystals of native copper that were, according to Dana,2 "probably twinned parallel to the octahedral plane and normal to this axis." In 1837, Rose3 very clearly demonstrated that native copper crystals were commonly twinned on the octahedral plane. Lasaulx,4 in 1882, described polysynthetic octahedral twins and stated that enclosed twinning lamellae were observed. Even on crystals formed artificially by electrolysis, twinning was observed as early as 1886, by Brown.5 Many other descriptions of twinning in native copper and in gold and silver are to be found in the literature, and in every case with which we are acquainted the twinning is conformable to the spinel law; i. e., the octahedral plane is both twinning and composition plane. Metallurgists have long been familiar with the straight-sided bars or bands that commonly occur within the irregularly outlined grains of metallic crystalline aggregates. They are certainly found in nearly all metals of the face-centered cubic type after cold working and annealing. If a specimen showing these bands is rotated, keeping the angle of incidence of the illuminating beam constant, they usually exchange color contrast periodically with their respective matrix crystals. Also slip lines, when produced in these specimens, nearly always show a change in direction upon passing through the bands, giving rise to the "stairway" effect often illustrated in metallurgical textbooks. Apparently the only quantitative observations on bands of this sort were made by Osmond and Cartaud6 on austenitic steel. They selected,

Jan 1, 1928

By Evans B. Mayo

As a result of studies distributed over the earth- including ocean basins as well as continents- some tectonists recognize four dominant structural trends: 1) northwest; 2) northeast; 3) nearly east- west, or equatorial; and 4) nearly north-south, or meridional. Baker' proposed a theory to account for these trends and Sonder5 called their world-wide arrangement the regmatic shear pattern. Moody and Hill6 proposed a much more complicated shear network which, although fascinating and perhaps ultimately useful, will not be followed here. In a recent review of deformation within the Cordillera, Wisser7 mentioned the four fundamental directions. The fact that many geologists deny the existence of the regmatic shear pattern implies that the fundamental structures are far from obvious. It may mean, also, that some geologists are not accustomed to examine regional and world maps analytically. The maps require much study, and certain features, should be isolated on overlays. Even so, with the present limited knowledge, uncertainties remain. The following analysis is a qualitative experiment, subject to change as information accumulates, and should be supplemented by the western sheet of the Tectonic Map of the United States.8

Jan 11, 1958

By J. G. Morlet, A. R. Troiano, H. H. Johnson

Delayed failure in steel occurs by controlled initiation and growth of a crack. The incubation period for crack initiation was measured. Crack initiation and Propagation are controlled by interaction between hydrogen concentration and triaxial stress state. The incubation period results from stress-induced diffusion of hydrogen to the point of crack initiation. THIS paper describes the phenomenon of delayed failureland the kinetics of crack initiation and propagation in uniformly hydrogenated steel. The investigation was prompted by service failures of high-strength-steel components at applied stresses far below the conventional yield strength, after the part had successfully sustained equal or higher stresses for an extended time interval. This delayed failure phenomenon, often termed static fatigue, is associated1 with the presence of hydrogen. This is not surprising, since the voluminous literature on flaking and hydrogen embrit-tlement demonstrates that hydrogen may exert a potent embrittling influence. Flakes, or internal hairline cracks in alloy-steel forgings, are related to the presence of hydrogen retained from the steel-making process.2 On the other hand, embrit-tlement arises from hydrogen introduced during surface treatments such as acid pickling or electroplating. Laboratory delayed failures have been induced in notch specimens of 4340 steel by electrolytic charging of the specimen surface with hydrogen and subsequent static stressing.l,4,5 Static fatigue was observed over a wide range of applied stresses; however, failure did not occur below a critical applied stress, designated as the static fatigue limit. In this instance the extended time for failure resulted primarily from the macroscopic redistribution of hydrogen. A crack formed to the depth of the hydrogen enriched "case* upon loading; further crack growth naturally awaited diffusion of hydrogen into the material ahead of the crack. The crack-propagation rate was therefore controlled primarily by the macroscopic diffusion of hydrogen into the specimen interior during the test. Thus, in this instance static fatigue was associated with the movement of a gross concentration gradient. However, delayed failure in steel of uniform hydrogen concentration is of greater fundamental interest, as well as commercial significance. With a homogeneous hydrogen distribution a different mode of delayed failure might be expected. As the heterogeneous hydrogen distribution became more uniform,4,5 the initial crack-propagation rate decreased markedly and, in fact, what appeared to be an incubation period for crack initiation was observed. However, the macroscopic concentration gradient precluded an accurate evaluation of these observations. Although the existence of an incubation period, up to this time, has not been established definitely, it is not amiss to point out some implications of the concept. It is of interest in all hydrogen-induced embrittlement phenomena, such as flaking, delayed failure, and hydrogen embrittlement. Much discussion has centered around the possibility of an

Jan 1, 1959

By R. R. Hart, B. C. Wonsiewicz, G. Y. Chin

In recent years there has been increased miniaturization of electromechanical devices to keep pace with current trends toward smaller electronic components. A major problem facing the designer, however, is the higher stresses encountered by the material as a result of shorter springs. Hence an improvement in the elastic limit, as approximated by the 0.01 pct offset yield strength, would be highly desirable. An increase of 25 pct in the yield strength, for example, will permit a 20 pct reduction in both the length and thickness of a cantilever-type spring while maintaining the same compliance. One technique of improving the yield strength that has received little commercial attention is crystal-lographic texture strengthening.1,2 Texture strengthening is expected to be most beneficial in materials of hcp structure, but considerable gain can also be expected in cubic materials. A wire with a (111) fiber texture, for example, is expected to be 20 pct stronger than randomly oriented material, and 50 pct stronger than wire with a (100) fiber texture.293 For sheet specimens with a {110}(112) texture, characteristic of many heavily rolled fcc alloys, the (111) transverse direction is expected to be the maximum yield strength direction, about 20 pct higher than that in the (112) rolling direction.' In addition, the (111) direction is the direction of maximum modulus of elasticity for most cubic alloys. A large value of the elastic modulus could be desirable in designs where stiffer springs are required. To test the above idea, a 0.090 in. (-2.3 mm) thick commercial grade A (5 pct Sn) phosphor bronze sheet, a widely-used material for relay springs, was rolled from the spring-tempered condition (60.5 pct reduction) to various additional reductions up to a total reduction of 95 pct. Subsequently, additional material was obtained with a total thickness reduction of 97.3 pct Standard tensile specimens were prepared from the sheet material with the tensile axis parallel to and at 90 deg to the rolling direction. Tests were run on an Instron testing machine at a strain rate of about 0.050 min-l. Textures were determined by the use of the reflection pole-figure technique. Data were obtained using nickel-filtered CuKa radiation and with the aid of a Siemens pole figure goniometer. The X-ray pole figure studies show an incrzasing development of the texture toward the {110}(112) ideal

Jan 1, 1970