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By Fred T. Agthe, Fred C. Bond

When some materials are ground dry in a ball mill, a stage of comminution is reached at which the finely divided particles begin to adhere to the balls and to the mill lining. As grinding progresses, a coating accumulates upon the grinding media, which tends to cushion the impacts and thus retard reduction of the material. and finally becomes so thick that all grinding ceases. At this stage, the characteristic noise produced by the grinding media during normal mill operation changes to a dull, muffled sound. In most instances, the formation of the coating marks the practical limit of size reduction. Industrial requirements for fine grinding frequently meet with this obstacle, and the tendency in many commercial operations to grind materials to a higher degree of fineness than formerly makes the solution of this problem an important one. The phenomenon is of far greater importance, therefore, than the limited amount of research and technical discussion devoted to it implies. In order to learn more about the coating of different materials when ground dry to a high degree of fineness, certain laboratory tests were made from which it was found that different materials form coatings at widely different size distributions. It is probable that most materials will coat if they are ground fine enough; the exceptions have inherent lubricating qualities, like coal and graphite. In general, the softer materials tend to coat at coarser sizes than the harder or more brittle materials. Limestone, as an example, will coat more readily than quartz, even though limestones of different- texture and composition exhibit great differences in coating potentialities. Various materials were tested in the laboratory to show the variation in coating qualities. It was found that in most tests quartz must be ground to a fineness that would permit it to pass through 325 mesh before coating became markedly detrimental to the grinding operation. Siliceous rocks, however, tend to coat more readily than quartz. Granite, which is composed essentially of feldspar, quartz and mica, has been found to start coating at about 92 per cent through 200 mesh, and feld-spathic minerals alone usually show a tendency to coat at the same fineness. Barite has been ground in the laboratory to a fineness of 99 per cent through 325 mesh without showing serious coating of the grinding media. Gypsum coats readily. Apatite and phosphate rock usually tend to coat. Hematite usually coats, although when mixed with charcoal it does not do so. In testing the carbonate rocks and minerals, it has been found that burned magnesite, dolomite, and dolomitic limestone coat, whereas calcite and calcined calcite do not coat so readily. It has been found that commercial glass, slate, talc, steatite and coke have little tendency to coat. The relative tendencies toward coating during grinding operations, exemplified by

Jan 1, 1943

By Fred C. Bond, Fred T. Agthe

When some materials are ground dry in a ball mill, a stage of comminution is reached at which the finely divided particles begin to adhere to the balls and to the mill lining. As grinding progresses, a coating accumulates upon the grinding media, which tends to cushion the impacts and thus retard reduction of the material. and finally becomes so thick that all grinding ceases. At this stage, the characteristic noise produced by the grinding media during normal mill operation changes to a dull, muffled sound. In most instances, the formation of the coating marks the practical limit of size reduction. Industrial requirements for fine grinding frequently meet with this obstacle, and the tendency in many commercial operations to grind materials to a higher degree of fineness than formerly makes the solution of this problem an important one. The phenomenon is of far greater importance, therefore, than the limited amount of research and technical discussion devoted to it implies. In order to learn more about the coating of different materials when ground dry to a high degree of fineness, certain laboratory tests were made from which it was found that different materials form coatings at widely different size distributions. It is probable that most materials will coat if they are ground fine enough; the exceptions have inherent lubricating qualities, like coal and graphite. In general, the softer materials tend to coat at coarser sizes than the harder or more brittle materials. Limestone, as an example, will coat more readily than quartz, even though limestones of different- texture and composition exhibit great differences in coating potentialities. Various materials were tested in the laboratory to show the variation in coating qualities. It was found that in most tests quartz must be ground to a fineness that would permit it to pass through 325 mesh before coating became markedly detrimental to the grinding operation. Siliceous rocks, however, tend to coat more readily than quartz. Granite, which is composed essentially of feldspar, quartz and mica, has been found to start coating at about 92 per cent through 200 mesh, and feld-spathic minerals alone usually show a tendency to coat at the same fineness. Barite has been ground in the laboratory to a fineness of 99 per cent through 325 mesh without showing serious coating of the grinding media. Gypsum coats readily. Apatite and phosphate rock usually tend to coat. Hematite usually coats, although when mixed with charcoal it does not do so. In testing the carbonate rocks and minerals, it has been found that burned magnesite, dolomite, and dolomitic limestone coat, whereas calcite and calcined calcite do not coat so readily. It has been found that commercial glass, slate, talc, steatite and coke have little tendency to coat. The relative tendencies toward coating during grinding operations, exemplified by

Jan 1, 1943

By R. E. Miner, J. K. Jackson, T. L. Wilson

A study has been made of the transformation kintetics and morphology in gas-quenched Fe-5 pct Ni alloys. Massive ferrite or nlurtensite was found to form at temperatures in agreement with earlier results. Surface Preparation appeared to have the greatest effect in determining the type of transformation Product formed. Grain size change, subgrain morphology, and dislocation densities of massive ferrite were essen-tinlly invariant functions of cooling rate. The mar-tens~tic structures were typical of transformation in austenite grains of the order of the sample thickness. BY introducing the idea of a massive transformation in dilute iron-base alloys, Gilbert and Owen in 1962 served to stimulate a closer inspection of phase transformations in ferrous systems.' A wealth of literature has followed concerned with the morphology,2-5 transformation mode,2'3'6-8 and thermodynamics of transformations.2,5,9 interesting controversies have resulted from the experimental observations; closer attention has been paid to the definition of massive transformations and still to be resolved is the Ms temperature of pure iron. The purpose of this note is to report some observations made in a detailed kinetic and metallographic examination of the transformations that occur in gas quenched Fe-5 pct Ni. The results are pertinent to the Ms extrapolations that have been made for pure iron and the observed substructure of massively transformed alloys. PROCEDURE The material used in this investigation was cast as a 5 lb vacuum induction melted, carbon deoxidized heat. The ingot was hot worked to a strip 0.10 in. thick, decarburized, and cold rolled to final thickness. Specimens were punched to sample shape and decarburized in wet hydrogen at 600°C. The chemistry of test specimens is indicated in Table I. Samples 1 by $ in., by thickness were resistance heated and rapidly cooled in an apparatus as illustrated in Fig. 1. Similar helium quenching apparatuses have been described previously;2,6'10 the distinguishing feature of this apparatus is the nozzle geometry. Twin nozzles with three convergent-divergent, sonic ports were mounted perpendicular to the specimen for quenching purposes. The specimen temperature was monitored with an intrinsic 3 mil chromel-alumel thermocouple spot welded to the specimen and con- nected to an oscilloscope. A single switch stopped the current flow through the specimen, opened a gas flow solenoid valve, and initiated an oscilloscope sweep. Cooling rates were read directly from a photograph of the oscilloscope trace and the quenching rates quoted later were made at a point immediately prior to transformation on the trace. All quenching studies were conducted either under a vacuum of 10"-5 torr or a helium atmosphere. The sample geometry was chosen large enough to permit optical and electron microscopy to be performed on samples. The samples were electropolished for both types of examination in a perchloric-acetic solution. Electron microscopy was conducted on a HU 11A microscope operated at 100 kv. Dislocation densities were determined at the same general operating reflection (110) on foils thick enough to produce Kikuchi patterns. RESULTS AND DISCUSSION Transformation Temperature Observations and OD-tical Microscopy. The quenching results of this study are illustrated in Fig. -2(a). Samples which were treated in the as-decarburized condition transformed in a manner similar to that reported previously—a decrease in transformation temperature occurred as the quenching rate increased until a plateau region was reached. Within the scatter of the results obtained here, there was no break in the transformation temperature-quenching rate plot. This suggests no change in transformation mode. Further metallographic examination confirmed this observation. A martensitic transformation was obtained for similarly treated samples except that the surface was first electropolished. The Ms temperature was approximately 85°C below the plateau determined for the unpolished samples and cooling rates as slow as 2000°C per sec were adequate for producing marten-site. The transformation temperatures are in gen- / STRIP SAMPLE / COPPER I SAX/-/}' / CONNECTOR-----A f, SON|C poRTS AC LEADS 3j ]j"I rofe[ \ Mf/yinK/iKj''^ THERMOCOUPLE X-(^—iie"s*c? ' LEADS 1 INCH Fig. 1-—Schematic scction of gas quenching apparatus

Jan 1, 1970

By F. W. Bradley

This chapter on the Alaska Juneau mill is intended to make clear that "choice of methods," or the selection of proper methods, is the first essential step in launching a new enterprise; and to illustrate that when entering into new country where local conditions and physical features are new or strange to an engineer, he should respect the practices already adopted and followed in meeting peculiar conditions in these new countries that may seem strange to a casual visitor. For example, Americans going into Malay Peninsula with their most up-to-date machinery for drilling placer prospect holes found their cost to total about $3 per foot; by adopting native methods, it was found the same work could be done for 50 cents per foot. Also, those not used to frozen road conditions in a country of arctic climate might scrape the snow off such a road and cause unending road troubles into the following spring and summer; while natives understanding local conditions would leave the snow on the road. So in the neighborhood of Juneau, Alaska, where successful gold-milling operations had been going on for

Jan 1, 1932

By R. Taggart, R. H. Ericksen, D. H. Polonis

Transmission electron microscopy techniques hare been used to study the spontaneous marfensite phase that forms during the thinning of Ti-Cr alloys. The structure of this phase has been found to differ. from the hcp martensite and has been identified as a clisforted fcc lattice. The spordaneous marlensile in this system is interpreted as a metastable isomorph of the equilibriunz TiCr, phase. WHEN thin-foil specimens for transmission electron microscopy were prepared from metastable alloys of the Ti-Cr system, a spontaneous transformation occurred' when the foils contained the untrans-formed 0 phase or two-phase mixtures of the 0 and w phases. The purpose of this paper is to examine the relationship that exists between the crystal structure of the spontaneous product and that of the matrix. The differences between the martensite transformation that occurs in the bulk material and the spontaneous reaction that occurs during the preparation of thin foils are compared with the observations that have been reported for similar phenomena in a commercial titanium alloy.' A spontaneous reaction that exhibits characteristics similar to a martensite transformation has been reported to occur in thin foils prepared from the retained metastable structures of several alloy systems.1'3"7 ~ull~ observed such a spontaneous reaction in 0 brass and attributed the apparent increase in the martensite transformation temperature to a decrease in the non-chemical free energy associated with bulk strain energy. He also showed that the spontaneous product did not have a specific habit plane, but that its orientation relationships to the parent matrix were dependen on the thickness of the transforming region. It has also been pointed out by Breedis6 that in thin films the absence of the constraints imposed by a bulk matrix can cause different requirements for the martensite plate interface and lattice distortion which is reflected bv a dependence of the transformation mechanism on the specimen geometry. In the case of the spontaneous reaction reported for Au-Zn alloys7 a definite habit plane was determined and shown to correspond with the habit plane calculated on the basis of the Bowles and Mackenzie crystallographic theory of the martensite transformation.'- lo EXPERIMENTAL PROCEDURE A series of titanium alloys containing 5.5, 5.9, 6.4: 7.6, 8.0, 11.3, and 18.7 at. pct Cr were prepared from high-purity (iochrome) chromium and iodide-grade titanium by levitation melting. The experimental procedure used for sectioning the alloys and for thin-foil preparation has been reported in an earlier paper.' X-ray diffraction patterns were obtained using a 114-mm Debye-Scherrer camera and Cu-Ka radiation. In order to minimize fluorescent radiation from the specimen, a strip of aluminum foil 0.002 in. thick was placed in contact with the X-ray film. After a specimen was removed from the camera: an additional X-ray experiment was performed, to insure that no spurious lines were obtained due to the presence of the aluminum foil. The interstitial impurity analysis for the alloys used in this study was as follows: oxygen, 100 ppm: hydrogen, 30 ppm: nitrogen, 28 ppm. EXPERIMENTAL RESULTS Electron diffraction patterns were obtained from several individual crystals of the spontaneous marten-

Jan 1, 1970

By Albert E. Wood, Edgar R Shepard

The interest of the Federal Government in improvement of waterways dates from 1820, when Congress appropriated $5000 for making a survey of the Mississippi and Ohio Rivers and assigned this work to the Corps of Engineers of the Army. Since that time the Government has gradually assumed increasing jurisdiction in the matter of improvement and control of inland waterways until, by the River and Harbor Act of Jan. 21, 1927, Congress assigned to the Secretary of War and to the Chief of Engineers the duly of making surveys, in accordance with House Document No. 308, 69th Congress, to formulate plans for the most effective improvement of the navigable streams of the United States and their tributaries, for navigation, development of water power, control of floods, and the needs of irrigation. Virtually all the preliminary investigations and surveys required by this act have been completed. The reports made to Congress have been published and often are referred to as ''308 Reports." The map shown in Fig. 1 is merely a skeleton distribution of the projects covered by these reports, but it serves to indicate the magnitude of the proposed undertaking. In many instances, a single character on the map stands for a major development involving several dams and reservoirs or many miles of canals or levees. The devastating floods of 1936, and the need for worthy public works to take up the slack in employment, gave further impetus to this program and in 1936 led to the enactment of a bill authorizing a large number of these projects. The National Flood Control Act of 1936 specifically authorizes some 270 flood-control projects in 31 states, and affecting nearly every state in the Union, with an estimated construction cost of about $300,000,000. In addition, the 1936 Act directs the Secretary of War to make preliminary examinations and surveys for flood control in some 230 additional localities, and to continue surveys and studies of 18 reservoir sites. The Corps of Engineers is proceeding rapidly with foundation investiga-

Jan 1, 1940

By Albert E. Wood, Edgar R. Shepard

The interest of the Federal Government in improvement of waterways dates from 1820, when Congress appropriated $5000 for making a survey of the Mississippi and Ohio Rivers and assigned this work to the Corps of Engineers of the Army. Since that time the Government has gradually assumed increasing jurisdiction in the matter of improvement and control of inland waterways until, by the River and Harbor Act of Jan. 21, 1927, Congress assigned to the Secretary of War and to the Chief of Engineers the duly of making surveys, in accordance with House Document No. 308, 69th Congress, to formulate plans for the most effective improvement of the navigable streams of the United States and their tributaries, for navigation, development of water power, control of floods, and the needs of irrigation. Virtually all the preliminary investigations and surveys required by this act have been completed. The reports made to Congress have been published and often are referred to as ''308 Reports." The map shown in Fig. 1 is merely a skeleton distribution of the projects covered by these reports, but it serves to indicate the magnitude of the proposed undertaking. In many instances, a single character on the map stands for a major development involving several dams and reservoirs or many miles of canals or levees. The devastating floods of 1936, and the need for worthy public works to take up the slack in employment, gave further impetus to this program and in 1936 led to the enactment of a bill authorizing a large number of these projects. The National Flood Control Act of 1936 specifically authorizes some 270 flood-control projects in 31 states, and affecting nearly every state in the Union, with an estimated construction cost of about $300,000,000. In addition, the 1936 Act directs the Secretary of War to make preliminary examinations and surveys for flood control in some 230 additional localities, and to continue surveys and studies of 18 reservoir sites. The Corps of Engineers is proceeding rapidly with foundation investiga-

Jan 1, 1940

By G. W. Healy, L. F. Sander

was investigated by reacting thin discs of calcium oxide with gas mixtures of CO2, CO, and Son. Its value was 19,300 * 300 cal independent of temperature in this range. No solid solubility of sulfur in calcium oxide was detected within the limits of the experimental method and it is estimated to be below 0.025 pct by weight. The importance of lime in desulfurization is well-established but complete information on the pure phase equilibrium: CaO + 1/2 s2 = CaS + +02 [11 is not yet available. The goal of this work was to evaluate solid solubility of CaS in CaO and to determine the free-energy change associated with Reaction [I] at temperatures of 1400" to 1650°C. The equilibrium constant for Reaction [1] can be written: It is convenient to rewrite Eq. [2] in the form: where A = {Ps /PqJ1'2 has been referred to' as the "sulfurizing power' of a gas mixture. In this work, thin discs of CaO were suspended in a vertical tube furnace and exposed to CO + CO2 + SOz gas mixtures having known values of A. The samples were then analyzed for sulfur. As expected, X-ray diffraction confirmed that CaS was the only sulfur-bearing phase formed at the relatively low oxygen pressures used. EXPERIMENTAL PROCEDURE Reagent-grade CaCO3 was pressed in a 3/8-in.-diam pill die and prefired in air to produce CaO discs weighing between 0.004 and 0.01 g. Several discs were used to provide a suitable weight for chemical analysis while maintaining a large surface area to react with gas mixtures. These were placed in a platinum mesh basket and suspended in the gas stream in the hot zone of a vertical tube furnace. Desired gas mixtures were prepared from cp grade CO and CO2 and anhydrous grade SO2. The method of soap bubble displacement was used to calibrate capillary flow meters. While this gave excellent results with CO and Con, some problems with bubble insta- bility and soap film "drag" arose with the use of SO2 at low flow rates. Hence, frequent sampling and analysis of gas mixtures was carried out to insure proper control of the ingoing SOZ. The furnace used for gas:solid equilibration was a vertical mullite tube externally wound with 60 pct Pt-40 pct Rh wire having a diameter of 0.028 in. An inner tube of $ in. ID served as the reaction chamber having Pyrex ground joints sealed to the mullite to provide gas-tight connections at top and bottom. A Pt-Pt 10 pct Rh thermocouple was inserted into a protection tube adjacent to the sample basket to measure sample temperature during a run. Constant-temperature control to 2C was observed at any desired set point within the range of this investigation. This was accomplished by a control thermocouple imbedded in the furnace windings which served to actuate an electronic controller wired for high-low operation. The sulfur analyses of the solid samples were carried out using a stoichiometric combustion technique based on the method of Fincham and Richardson. Some analyses were done using a modified evolution method3 but these were used primarily to check the results of the combustion method. The results were in good agreement but the combustion technique of-ferred an advantage in economy of time and material. CALCULATION OF GAS EQUILIBRIA Heating a given mixture of CO + CO + SO2 to high temperatures gives rise to a large number of product species. The details of calculating the partial pressures of these products of interaction and dissociation can be found in several references4,5 and need not be repeated here. The thermodynamic data selected for the major species in the gas mixtures are shown in Table I. Equilibrium constants from these reactions were combined with oxygen, carbon, and sulfur balances and a computer program written to facilitate the calculations. Some early difficulties in reproducing experimental results were finally traced to the effect of atmospheric pressure changes. No reference to consideration of this question had been found in the

Jan 1, 1969

By Edward Keller

In a paper, entitled A Uniform Method for the Assay of 'Copper Material for Gold and Silver,' A. R. Ledoux invited the assayers of this country to contribute to a symposium, in which the results of their assays of given samples of copper-matte and metallic copper would be made comparable. This symposiun 2 appeared about one year thereafter; and through it and its discussion, first became generally known the fact that the gold-yield by the all-fire method of assaying is usually higher than by the so-called combination (wet and dry) method, in which nitric acid is employed as a solvent for the copper. In the publication alluded to, the supposed cause of gold-losses in the latter method was declared to be the solvent action of copper nitrate, or of the reduction-products of the nitric acid, upon the gold. Up to a very recent date, gold has been held to be insoluble in pure nitric acid. (The solvent action of any chlorine present in the nitric acid must here properly be disregarded as belonging in the realm of carelessness.) Among later allusions to this topic, W. R. Van Liew3 ascribes the solution of the gold in the combination-assay entirely to the action of nitrous acid at the high reaction-temperature of copper and nitric acid; F. B. Flinn4 believes the low result in gold to be due exclusively to mechanical losses—finely-divided gold penetrating through the filter-paper—but presents no experimental data confirmative of this belief; and 0. Pufah]5 attributes the solubility of' the gold in some coppers to the presence of selenium—a view which appears to be shared by many as-

Jan 1, 1913

By S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of gold and copper in dilute Au-Cu-Sn alloys have been determined using a liquid metal solution calorimeter. The self-interaction coefficient, Au - has been calculated at constant copper concentrations and n cu has likewise been determined at constant gold contents. Good experimental agreement is obtained between the interaction coefficients and nAu Cc thus demonsbating the reliability of the measured heat values. The measured data are compared with the Predictions of certain solution models. In previous publications,1,2 the results of calori-metric investigations of dilute Ag-Au-Sn and Ag-Cu-Sn alloys have been presented. The present work on the Au-Cu-Sn system concludes a program of studies of enthalpy interaction coefficients in dilute alloys of the Group IB metals with tin. Since the definition and derivation of an enthalpy interaction coefficient has been discussed previously,1,2 no restatement of this theory will be presented here. From the determination of the partial heat of solution of gold and copper in ternary alloys of various copper and gold contents, values of the interaction coefficients can be calculated. These coefficients give an insight into the various solute interactions that occur in the liquid solutions since changes in their magnitude and sign reflect bonding changes that are taking place in alloys of varying solute contents. EXPERIMENTAL Details of the design and operation of the liquid metal solution calorimeter used in this work may be found in a paper by Poo1.3 For the present studies copper of 99.999 pct purity was supplied by American Smelting and Refining Co., gold of 99.999 pct purity by A. D. Mackay, Inc., and tin of 99.99 pct purity by Baker Chemical Co. At the commencement of each series of experimental drops, a tin solvent bath consisting of between 70 and 90 g of the pure metal was inserted in the calorimeter. The weight of the bath was accurately determined and to it were added appropriate amounts of gold or copper to give alloys of the desired composition. For determinations of approximately 0.0015 g-atom samples of Cu were used and for measurements of ?HAu approximately 0.0025 g-atom additions of Au. The heat capacity of the bath was determined at regular intervals during a series of drops using tin calibration samples. Measurements were made of the heat of solution of copper in alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of Au, respectively, in order to determine ?HCu in each alloy, and the same mole fractions of copper were used to determine equivalent values for nAu at constant copper concentrations. The composition of the bath was maintained at the desired constant gold or copper content by making calculated additions of the appropriate solute throughout the experiments. The limiting values ?HAu in alloys of constant copper content and of %c, in alloys of constant gold content were studied as a function of the mole fraction of copper or gold respectively in order to determine and nCu. Heat content and heat capacity data used in calculating values of ?ºHAu and ?HCu at the experimental temperature of 720°K were obtained from Hultgren et a1.4 ' RESULTS AND DISCUSSION Determinations of ?HAu. The partial heat of solution of gold in pure tin as a function of gold concentration was determined in the previous study of dilute Ag-Au-Sn alloys1 and can be represented by the least-squares expression: ?HAu(l) =-8075 + 2413xAu [l] which is valid between XAu= 0.00 and xAu = 0.05. The standard error in the constant term, which represents the partial heat of solution of gold at infinite dilution in tin,?HºAu(l)is 35 cal per g-atom, while the standard deviation of the slope, which represents n Au is ± 619 cal per- agtom. Corresponding expressions for ?HAu(l) in alloys containing constant mole fractions of 0.01, 0.02, 0.03, and 0.04 copper were obtained from the data listed in Table I and are themselves given in Table II. Fig. 1 illustrates the partial heat of solution of gold as a function of its concentration in each of the alloys. For the four alloys of constant copper concentration, the values obtained for ?HºAU(l) (in order of increasing copper content) are -8141 i 36 cal per g-atom, -8210 ± 42 cal per g-atom, -8202 ± 46 cal per g-atom and -8268 ± 51 cal per g-atom. The corresponding values of the self-interaction coefficient, n Au, for these alloys are 3103 * 644 cal per g-atom, 2425 ± 676 cal per g-atom, 2574 * 717 cal per g-atom and 2523 ± 899 cal per g-atom. In Fig. 2 these values of n Au are plotted as a function of the copper content of the alloys and are seen to remain approximately constant within the experimental limits. The addition of increasing, small amounts of copper to dilute binary Au-Sn alloys thus has no apparent effect on Au-Au interactions in these dilute liquid solutions, although more exothermic values of ?HºAu(l) do result from an increase in the copper content of the alloys. Analogous behavior was observed with additions of silver to dilute Au-Sn alloys.' By

Jan 1, 1970

By D. G. Westlake

The electrical resistance of a series of V-H alloys (0 to 3.5 at. pct H) has been measured over the temperature range G° to 360°. Interstitial impurities made contributions to the residual resistivity, but not the ideal resistivity. The contribution of hydrogen in solid solution is expressed by Ap = 1.12 microhm-cm per at. pct H; but the contribution of precipitated hydride was negligible. A portion of the so1vu.s for the V-H phase diagram is presented. The solubility limit is given by In N (at. pct H) = (5.828 i 0.009) - (2933 i 44)/RT. Comparison of critical temperatures joy hydride precipitation and published critical temperatures for hydrogen embrittlement suggests the two are related. ThiS study was initiated as part of an investigation of the mechanism by which small concentrations of hydrogen embrittle the hydride-forming metals at low temperatures. It has already been shown that, in the case of hcp zirconium, a reduction in ductility accompanies the strengthening resulting from precipitation of a finely dispersed hydride phase.''' Our attempts to detect a similar precipitation of a second phase at low temperatures in V-H alloys by transmission electron microscopy have been thwarted because we have been unable to prepare thin foils that are representative of the bulk material with respect to hydrogen concentrati~n.~'~ The present investigation establishes the solvus of the V-H system at subambient temperatures. Subsequently, we hope to be able to determine whether the embrittlement temperature is related to the critical temperature for precipitation of the hydride in a given V-H alloy. veleckis5 has proposed a partial phase diagram for the V-H system based on extrapolations of the pressure-composition relations he measured at higher temperatures. Kofstad and wallace' conducted a similar study of single-phase alloys but did not attempt to establish the phase diagram. Zanowick and wallace' and ~aeland' have studied a portion of the phase diagram by X-ray diffraction, but they investigated no alloys in the hydrogen concentration range 0 to 3 at. pct, the range of interest to us. EXPERIMENTAL PROCEDURE The vanadium was obtained from the Bureau of Mines, Boulder City, Nev., in the form of electrolytic crystals. The analyses supplied with them listed 230 ppm by weight metallic impurities, 20 ppm C, 100 ppm N, and 290 ppm 0. The crystals were electron-beam-melted into an ingot that was rolled to 0.64 mm. Strips, 60 mm long and 4.2 mm wide, were cut from the sheet, and both rolled surfaces were ground on wet 600-grit Sic paper to produce specimens 0.4 mm thick. They were wrapped in molybdenum foil, vacuum-encapsulated in quartz, and annealed 4 hr at 1273°K. The specimens were annealed in a dynamic vacuum of 2X lo-' Torr for 30 min at 1073°K for dehydrogenation, and charged with the desired quantity of hydrogen by allowing reaction with hydrogen gas at 1073°K for 2 hr and cooling at 100°K per hr. Purified hydrogen was obtained by thermal decomposition of UH3. Sixteen specimens were studied: two contained no hydrogen and the others had hydrogen concentrations between 0.5 and 3.5 at. pct (hydrogen analyses were done by vacuum extraction at 1073°K). Electrical resistances were measured by the four-terminal-resistor method on an apparatus similar to the one described by Horak.~ The specimen holder was designed so that both current and potential leads made spring-loaded mechanical contact with the specimen. The potential leads were 30 mm apart, and the current leads were 55 mm apart. The current was 0.10000 amp. We used the following baths for the indicated temperature ranges: liquid nitrogen, 77°K; Freon 12, 120" to 230°K; Freon 11, 230" to 290°K; and ethanol, 290" to 340°K. Temperatures lower than 77°K were achieved by allowing the specimen to warm up after removal from liquid helium. Temperatures above 77°K were measured by a calibrated copper-constantan thermocouple (soldered to the specimen holder) and below 77°K by a calibrated carbon resistor. The temperature of the bath changed less than 0.l0K between duplicate measurements of the resistance. RESULTS AND DISCUSSION Typical plots of resistivity p vs temperature T are shown in Fig. 1. In the interest of clarity, only five curves are presented and the data points have been

Jan 1, 1968

By Robert E. Green, Wolfgang Sachse

Simullaneous ultrasonic attenuation measurements of both quasishear waves propagating in single cryslals of aluminum indicate that, in the undeformed annealed state, the dislocation density is generally not uniform on all slip systems. Change oof attenuation measurements made during plastic defortnation of crystals , which possessed specific orientations ideal for studying the orientation dependence of dislocation damping, indicate that, for low strain levels, dislocation motion occurs on additional slip systems besides the primary one, even for crystals oriented for plastic deformation by single slip. THE sensitivity of internal friction measurements permits such measurements to be used successfully in studying the deformation characteristics of metal crystals. On the basis of experimental observations, T. A. Read1 was the first to associate internal friction losses with various dislocation mechanisms. Since that time further work2-' has been performed and a dislocation damping theory has been formulated by Granato and Lucke.6 In the amplitude independent region, this theory predicts the attenuation a to be dependent on an orientation factor O, a dislocation density A, and an average loop length L. if is a constant, independent of crystallographic orientation. For a given crystallographic orientation, changes in dislocation density and loop length give rise to the observed attenuation changes accompanying plastic deformation. The Granato-Liicke theory suggests the investigation of the orientation dependence of attenuation measurements in hopes of obtaining information to separate dislocation motion losses from other losses.7 An experimental study of the orientation dependence of attenuation in undeformed annealed single crystals should yield an insight into the uniformity of dislocation distribution throughout the entire specimen. A similar study on crystals plastically deformed in a prescribed fashion should give information about the alterations in the dislocation distribution on the slip systems activated during plastic deformation. The possible modes of elastic waves which can be propagated in aluminum,8 copper,9 zinc,10 and other hexagonal metals" have been calculated. Associated with each mode of wave propagation are dislocation damping orientation factors, which are based on the resolution of the stress field of that particular elastic wave onto the various operative slip systems in the material. These orientation factors have also been calculated as a function of crystallographic orientation in the papers cited above. Einspruch12 obtained agreement between predicted and observed attenuation values of longitudinal and shear waves in (100) and (110) directions of two undeformed aluminum crystal cubes. He ascribed the slight deviations between predicted and observed values to a nonuniform dislocation distribution, or to other loss mechanisms. In shear deformation of zinc crystals, Alers2 found that the attenuation of shear waves having their particle displacements in the slip plane was very sensitive to the deformation, while the longitudinal wave attenuation was affected only when the wave propagation direction was not normal to the slip plane. Using aluminum single crystals oriented for single slip, Hikata3 et al. found that during tensile deformation the change of attenuation of the shear wave (actually quasishear) having particle displacements nearly perpendicular to the primary slip direction exhibited the easy-glide phenomena, while longitudinal waves did not. Similar results were reported by Swanson and Green5 during compressive deformation of aluminum crystals. These results are in qualitative agreement with the calculated orientation factors for specimens of this orientation. In well-annealed, undeformed aluminum crystals, the damping is expected to be due to dislocations vibrating on all twelve slip systems. The orientation factors associated with this initial damping will be designated by O2 and O3, where a, represents the average orientation factor for the slow shear (or quasishear) wave and O3 represents the average orientation factor for the fast shear (or quasishear) wave. The calculation of these values for aluminum crystals by Hinton and Green8 shows that they vary very little as a function of crystallographic orientation—at most, by a factor of 2.47. If the dislocation density and loop length are uniform, then in the initial undeformed state, Here the subscript zero refers to the initial value of the attenuation. Also for aluminum, the calculations8 show that the orientation factors for primary slip only, associated with each shear wave, exhibit a sharp minimum for particular crystallographic orientations. A composite plot of the two shear wave orientation factors for primary slip only is shown in Fig. 1. Since these orientation factors are associated with dislocation motion occurring on the primary slip system only, the proper condition to check these factors might be attained by slightly deforming a single crystal oriented for primary slip. For dislocation motion on the primary slip system only,

Jan 1, 1969

By George F. Comstock

It seems a common opinion among metallographists that all light-gray inclusions seen with the microscope in polished sections of steel are manganese sulphide. Examples of this belief are continually appearing, as for instance in the paper by Dr. Henry Fay on manganese sulphide as a source of danger in steel railsll and in Lieutenant-Commander Cook's paper on Metallography of Steel for U. S. Naval Ordnance.² Slate- colored inclusions are considered to be silicates, and dove-gray inclusions, manganese sulphide. To show the danger in the latter unqualified assumption, it should be sufficient to examine the edge of any piece of steel that is covered with a fairly thick scale, and that has been polished in such a way as to prevent the scale from breaking away entirely below the polished surface. This can be done by protecting the scaled edge of

Jan 1, 1917

By Richard F. Miller

The investigations of large-grained specimens carried out by Polanyi and Schmid,l Sykes,2 Goucher,3 Yamaguchi,4 Gough, Cox, and Sopwith,5 Carpenter and Elam,6 Aston,7 and others have shown qualitatively that grain boundaries restrain the deformation of adjacent crystals. But whether or not the influence of the grain boundary is confined to the glide planes intersected by the boundary has not been demonstrated in any of these investigations, nor has there been carried out any quantitative analysis of the influence of a boundary on the deformation of a crystal. Indeed, the specimens employed in the previous work contained so many complicating factors that it would have been difficult to observe any variation of the extent of the influence of the grain boundaries in relation to their sizc. The specimens were small, the grain boundaries irregular and at no particular angle to the specimen axis or the

Jan 1, 1934

By R. A. Cummings, N. N. Moebs, M. M. Singh

Disintegration of the immediate shale roof in coal mines interferes with ventilation, production, and safety. The effect is seasonal and correlates with high levels of moisture in the intake ventilation air. Disintegration, though not completely understood, is caused by shale dilation and weakening upon exposure to atmospheric moisture. Fluctuating moisture conditions are particularly deleterious, but may be at least partially controlled by tempering the air before it is brought to the working places. Disintegration of shale roof is progressive loosening of chunks or slabs or roof shale, which fall to the floor. Bolts are left dangling or are connected to the roof by a column of loose rock. Posts are rendered ineffective. Passage of ventilation air and personnel is restricted by piles of fallen material on the floor. Shale disintegration as it occurs in mine roofs does not appear to have much in common with slaking, such as is measured in slake-durability tests, which results in the failure of certain shales when exposed in embankments or foundations. A two-year program was conducted on behalf of the US Bureau of Mines, incorporating field and laboratory analysis of deterioration. During this study, a. survey was conducted of underground mining operations in the Illinois Basin and Appalachia. In all, 47 mines in six different coal seams were identified as possibly having roof deterioration problems pertinent to the study. Of these, the No. 1 Mine of the Valley Camp Coal Co. near Triadelphia, WV was selected for detailed study. This mine uses conditioning entries, workings where raw intake air is routed before reaching the key haulageways. Deterioration is to be confined to the conditioning chambers. The approach adopted to study the deterioration problem was to measure atmospheric moisture in the mine, determine shale behavior in the laboratory under various moisture conditions, and measure mine roof behavior that could be correlated with atmospheric moisture observations. The following tasks were performed: • Atmospheric baseline data were collected, consisting of airflow measurements, continuous monitoring of the mine and surface atmospheric conditions using a sling psychrometer. • Roof deterioration was documented through measurement of roof convergence (sag), mapping of roof conditions, collection of fallen and rashed material and measurement of roof height increase and photographic logging. An infrared scanner was also tried, but not found useful. • The behavior of shale under various moisture conditions was determined in the lab through tests of shale expansion, natural moisture content, moisture uptake capacity at various humidities, and static (immersion) slaking.

Jan 1, 1984

By George Ross Green

[In discussion of the paper of Mr. J. C. Bayles, read at the New York meeting of September, 1890, Trans., xix., p. 18.1 It is often so difficult to locate the causes of failures of machinery and apparatus which can be examined and studied at leisure, that it is not surprising that the causes of explosions should escape detection. Usually the explosion is the first evidence that anything is amiss, and the time for observing the conditions is necessarily brief. An incident in a welding-works near Essen, Germany, might be cited as exemplifying what trifling causes may lead to disaster, and how difficult, under the most favorable conditions, it may be to discover them. A blowing-engine was arranged with two suction-pipes at each end of the blowing-cylinder—one leading to the air, and the other to the gas-holder. Each pipe was provided with a valve, and all were so adjusted that the cylinder drew in gas and air in the proportions found most advantageous. The gases from the cylinder were carried directly to the furnace through suitable pipes, and while the cylinder was provided with relief-valves, every effort was made to prevent explosions, principally by compressing the gases to a point where the rate of efflux of the mixture was greater than the velocity of combustion, if the expression is here allowable. It was found that the apparatus would work satisfactorily for some time, and then the relative proportions of the mixture would change, and an explosion might have been the result. Experiments consuming days were made to discover a method of averting this danger, but they were unsuccessful, until it was observed that the change in the composition of the mixture of gas and air took place when the gasometer began to rise or fall—the back-pressure due to friction when the holder was rising or its absence when falling being sufficient to change the conditions. As soon as this was discovered,

Jan 1, 1892

By R. E. Mazurak, E. L. Ealy

At the Beckley mine in southern West Virginia, forecasting unstable roof conditions in advance of mining is accomplished by wing a rating system that combines historical information on mine roof failures with known mine geology. Failure frequency rates are derived for each category of roof rock composition, unit thickness, structure, and extraction ratio. In this manner, known geological environments are rated according to instability based on actual experience. Drill hole control and geological interpretation provide the basis for forecasting unstable conditions beyond working faces. The forecasting technique has assisted mine management in reducing fall frequencies by 80% over the past two years compared to the first five years of operation. This reduction in fall frequency was accomplished by modifying the plan of advancing sections to minimize mining exposure to unstable roof conditions.

Jan 1, 1983

By R. L. Braun, D. L. Leach

Laboratory experiments simulating in-situ copper recovery from primary sulfide ores in sulfuric acid systems pressurized with oxygen are reported. Copper extraction and acid consumption data are correlated with temperature in the range 50 to 150°C and quenched pH in the range 0.25 to 2. Adverse changes in the chemical composition of the leach solution and the formation of gangue-mineral alteration products and secondary sulfides can severely limit the extraction of copper above 90°C. Keeping the pH below the self-buffered value of about 2 and the temperature below about 110°C produces the maximum extraction rates. Forcing the pH too low not only results in excessively high acid consumption but may also limit the extraction of copper at temperatures above 100°C.

Jan 1, 1977

By Arthur Phillips

The progress made in recent years in the art of dispersion-hardening has naturally led to an intensive study of alloy systems capable of yielding supersaturated solid solutions at ordinary temperatures. In general, the investigations have been confined to rather precise determinations of solubility limits and to experimental approaches designed to furnish more complete information regarding the rate and nature of precipitation under appropriate thermal conditions. Efforts are being made to focus more sharply on the atomic changes that are a direct consequence of the instability of the supersaturated solution. Here precision X-ray methods have come to be of considerable importance because lattice parameter measurements indicate very precisely the concentration of solute atoms in the solvent lattice. In spite of the general acceptance of parameter values as a criterion for the placing of solubility limits, it may be suggested that no thorough appraisal has been made of the several factors that conceivably may affect such measurements. More specifically, little attention has been devoted to the significance of surface energy conditions, specimen size and method of preparation, with particular regard to the genesis of the grains and the surface concentration changes as a consequence of heat treatment and etching. Stenzel and Weertsl recently published the results of a detailed study of precipitation reactions in aluminum-rich copper alloys. They found that, although copper lowers the lattice constant of aluminum, a 5 per cent copper alloy quenched from 150" and 225' C. had parameter values unquestionably higher than that of pure aluminum. Their results seem to substantiate, at least qualitatively, the earlier work of von Göler and Sachs,2 who indicated a parameter value, for the same alloy annealed for 24 hr. at 200° C., some 0.0008Å. larger than that of pure aluminum. Stenzel and Weerts attributed the abnormal lattice dimension to the effect of strain induced by the precipitation of CuA12. Weerts3 later

Jan 1, 1934

By J. L. Craig, C. L. Edwards, M. D. Harper, J. M. Ray

The Los Alamos National Laboratory executed 19 intermediate scale cratering experiments in oil shale at the Colony Mine in Garfield County, Colorado. These experiments have led to a better under- standing of fracture characteristics and fragmentation of & - oil shale by use of a conventional high explosive. Geologic site characterization included detailed mapping, coring, and sample analyses. Site-specific geology was observed to be a major influence on the resulting crater geometry. The joint patterns at the experimental site frequently defined the final crater symmetry. Secondary influences included vugs, lithology changes, and grade fluctuations in the local stratigraphy. Most experiments, in both the rib and floor, were conducted to obtain data to investigate the fragmentation results within the craters. The rubble was screened for fragment- size distributions. Geologic features in proximity to the explosive charge had minimal effect on the rubble due to the overpowering effect of the detonation. However, these same features became more influential on the fracture and rubble characteristics with greater distances from the shothole. Postshot cores revealed a direct relationship between the grade of the oil shale and its susceptibility to fracturing. The Colony Mine experiments have demonstrated the significant role of geology in high explosive/oil shale interaction. It is probable that this role will have to be considered for larger applications to blast patterns and potential problems in retort stability in the future of oil shale development.

Jan 1, 1983