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By Zay Jeffries

This paper will include a brief discussion of Prof. Howe's paper on The Supposed Reversal of Inheritance of Ferrite Grain Size from that of Austenite.l The general subject of grain refining in steel and iron will also be treated. The conclusions reached are stated in the following hypotheses which are discussed more in detail below. 1. The ferrite grain size in pure iron, the ferrite and pearlite grain size in hypoeutectoid steel, the pearlite grain size in eutectoid steel and the cementite and pearlite grain size of hypereutectoid steel are not inherited from the grain size of the mother austenite. 2. The only structural feature that is generally inherited from the austenite of hypo- and hypereutectoid steels on cooling through their transformation ranges is the position of the excess ferrite or cementite at the austenite grain boundaries, sometimes causing complete and sometimes incomplete networks which outline the old austenite grain boundaries. Rapid cooling through the transformation range will cause the non-inheritance of this structural (network) feature. 3. The austenite grain boundaries themselves are nearly always effaced in all steels and also in pure iron during the At transformations. 4. The grain-size refining of steel and iron is brought about by the combined effect of non-inheritance of the transformation products on either heating or cooling, i.e., the austenite transformation products do cst inherit their grain size from the austenite on cooling through the transformation range nor does austenite inherit its grain size from the products which form austenite on heating. 5. In general, in both iron and carbon steel the larger the austenite grain size, the larger will be the grain size of the transformation products on cooling. This, of course, assumes all other conditions constant except the austenite grain size. An exception is found to this general rule in very pure iron such as electrolytic iron. In this instance small austenite grains may form very large ferrite grains on cooling through Arg.

Jan 1, 1918

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young's modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young's modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman' noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig' observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity' or the paramagnetic susceptibility.' Likewise, no one has noted a change in crystal symmetry. In the present investigation Young's modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,' and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.' The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder' the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young's Modulus: For measurement of Young's modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young's modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young's modulus at 25°C, Fig. la, is 28.2~10" dynes per cm' (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;' the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By Owen F. Jensen

CONSTRUCTION of a ground-water supply includes many operations, which do not end with completion of facilities. Evaluations must be made of the quality of water in various areas and the history of production. Following an analysis of geologic, hydrologic, and chemical data there must be an exploratory drilling program and a study of resulting information. When the well is completed a continuous survey of operating records and basic data is necessary, since designs for future wells are varied as more data becomes available for those already completed. As the following discussion must be limited to a single undertaking, the customary procedure will be outlined for development and construction of a ground-water supply in which more than three wells are involved. Parts of this procedure are applicable for all ground-water supplies. Three possible sites were selected for construction of a paper mill. The problem was that the industry daily required approximately 15 million gallons of water of the best quality available; however, if water of the best quality were not available in the desired amount, water of a poorer quality could be used up to half the required amount, about 7 million gallons. In the preliminary survey approximately 1500 to 2000 square miles were covered for each site. Collected data consisted of several hundred electric logs of oil and gas wells; reports by the U. S. Geological Survey on ground-water resources of localities in and near the area; unpublished records of several hundred water wells including chemical analyses of the water produced and drillers' logs of the wells; records of periodic water-level measurements made in observation wells by the USGS; topographic maps drawn up by USGS and by army engineers; and highway and county road maps. A preliminary report based on study and evaluation of these data was presented to the client, recommending the site with the most favorable and economical ground-water conditions. The study indicated that water of the quality and quantity desired could be developed. In this particular area there were indications that the aquifer could be separated into two zones con- taining water of different chemical character. This chemical character varied somewhat with area, but principally with depth, a factor which later proved an economic advantage in design of the well field. After studying the preliminary report, the client weighed other economic factors as well as ground-water advantages and selected a plant site. Authority was given to proceed with detailed study of the chosen area. Evaluation of preliminary data concerning the area indicated that it should be supplemented with additional information derived from actual exploratory drilling and testing. A flexible plan of exploratory drilling was devised so that data obtained as each test hole was drilled could be correlated with existing data and additional test holes could be located and drilled accordingly. Specific data to be obtained from each test hole were: samples of all formations penetrated; the driller's descriptive log of formations; electric logging surveys; one or more samples of water from selected water-bearing formations; temperature; and water levels and their recovery after periods of production. The area studied in such detail was approximately 400 square miles. Choice of location for the original test holes was based on the preliminary study. The pattern for these test holes was designed to require a minimum number of holes and to allow for interpolation of data between two, three, and four holes. Geologic, hydrologic, and chemical data gathered after completion of the first four test holes showed that the north section was the most desirable in the area, which was then reduced from the original 400 square miles to about 150 square miles for more detailed and intensive study. On the basis of findings from the current test a tentative well field was laid out and a drilling program devised. One test hole was located on the actual plant site and later developed into a small pilot production well equipped with a deep well turbine pump. Water from this well was used for general construction requirements. Another test hole drilled near the pilot production well and adjacent to the proposed route of the well-collection system was used during the pumping test of the pilot production well to determine the degree of interference. From the data thus obtained, calculations were made to determine the coefficients of transmissibility and storage. Three additional holes

Jan 1, 1955

By C. S. Barrett, O. R. Trautz

PREVIOUS investigations have shown that lithium is body-centered cubic from near its melting point to the temperature of liquid air1,2,3 Nevertheless there was an incentive to search again for a transformation at low temperatures: C. Zener4,5 has remarked that the low value of the elastic modulus (11 - C12)/2 of body-centered cubic metals and alloys implies a rapid increase in free energy with decreasing temperature, which would favor the occurrence of a transformation; also the shear movement to which this modulus applies is one that can transform a body-centered cubic structure into a slightly distorted face-centered cubic structure. It was confirmed that lithium does not transform spontaneously at liquid nitrogen temperature, but it was found that a transformation can be induced at this temperature by cold working the metal,6 and at slightly lower temperatures a different transformation occurs spontaneously. Transformations were also found in solid solutions of magnesium in lithium. THE NATURE OF THE TRANSFORMATIONS Before presenting a detailed treatment of the technique used and the specific data obtained, it would be well to give a brief survey of the general characteristics of the transformations. A new crystal structure begins to form spontaneously in a specimen when it is cooled below a critical temperature. In lithium the structure appears to be close-packed hexagonal; in the Li-Mg alloys most of the diffraction lines (but not all) are near those for hexagonal lithium. The transformation proceeds as the temperature is lowered and soon stops if the temperature is held constant or raised. The course of the transformation on cooling is indicated by the curve at the lower left of Fig I. This curve is drawn in stepped fashion because the transformation goes by discrete steps with audible clicks. Because of the similarity to the decomposition of austenite into martensite in steels, it seems appropriate to designate the beginning of the spontaneous transformation on cooling as the Ms point. On heating to room temperature after the low temperature treatment only the usual BCC structure is found. On heating, the low temperature modification begins to disappear at a temperature which will be designated as Ac. The transformation on heating is halted when the rise in temperature is halted. The temperature must be raised 40 to 50°C above Ac before the reversion is complete-an interval which is sensitive to the rate of heating and to the time of holding at temperatures above Ac. This behavior on heating thus has similarities also to the formation of martensite in the cooling of steels.

Jan 1, 1948

By G. P. Connell, R. E. Gilmore, J. H. H. Nicolls

The purpose of this paper is to suggest a procedure for indicating the dividing line between noncaking coals and those that have weakly caking properties. A laboratory agglomerating test as an aid in classifying weakly caking coals is outlined and its merits in comparison with the standard agglutinating method advanced by the U. S. Bureau of Mines are discussed. No attempt, however, is made to discuss in detail either the different methods for determining "caking" and "agglutinating" indices or the various systems of classification. Two methods, differing somewhat in procedure, have been employed and recognized as suitable for determining the caking or agglutinating values of coals; namely, those in which an inert material such as sand, electrode carbon, etc., has been mixed with the coal before being heated, and those in which the coal is carbonized alone. In all such methods, the coal with or without the inert material is in the finely divided state and the index or value sought is derived from the examination of the residue after heating in a closed crucible or other container. The procedure outlined by Selvig, Beattie and Clellandl is the most recent representative of the method using sand as inert material, while the agglomerating test described below is representative of the method in which the coal is carbonized alone. The standard volatile-matter determination affords a means for observing the coking properties of a coal, and this has been described by Rose2 as the simplest of all coking tests. According to him, "the resulting coke button will indicate whether the coal is noncoking, feebly coking or strongly coking," despite the fact that "almost every condition in this test is at variance with large-scale carbonizing practice." Lessing,3 the

Jan 1, 1934

By W. N. Miner, R. O. Elliott

Electrical-resistivity )measurments were made be-trueetz room temperatrive and 1.5 oK on five different stocks of cerium metal, and the results were correlated with the types, amounts, and distribution of the impurities present. Magnesium, which appeared to be distributed as a solute throughout the cerium matrix, was found to have a large effect on the residual resistivity, 1 at. pct Mg being sufficient to increase the residual resistivity by about 10 microhm-cm. The formation of ß by repeated thermal cycling between room temperature and liquid-helium temperature is attributed to the deformation and faulting that occurs during the ? D a transformation. In preparation for starting a proposed study of cerium-rich alloys, we examined samples from severa1 stocks of cerium metal in order to choose the purest stock for future use in making the alloys. Low-temperature electrical-resistivity data were used to gain initial information about the purities of the stocks. Additional information was subsequently obtained from chemical analyses, density measurements, optical metallography, and electron-micro-probe analyses. Cerium that has been annealed at high temperature and cooled to room temperature has the fee crystal structure (? phase) with a = 5.16Å. When cooled further, in the region between about 250" and 150°K, some of the fee phase transforms to the double hcp form (ß phase) with a = 3.68 and c = 11.92Å. The remainder of the room-temperature fee form (and perhaps some of the hexagonal phase) transforms electronically in the vicinity of 100° K to the more dense or "collapsed" fee form (a phase), a - 4.85A, by transferring about 0.5 electron per atom from the 4f level to the valence band. Very little work related specifically to the effects of impurities on the physical properties of cerium has been reported in the literature. Gaume-Mahn1, 2 has studied the effects of calcium, magnesium. iron, silicon, and tantalum on the electrical resistivity and magnetic susceptibility of cerium between 60o and 300°K. Gschneidner, Elliott, and McDonald3 have discussed the effects of total impurity content on the hysteresis of the a —? (reversible) transformation and on the formation of the 4 and "a-? intermediate" phases. Smith and Morrice* have reported the effect of total impurity content on the resistivity of cerium at 4 and 293°K. In none of these reports, however, is it apparent that the distributions of the impurities were determined, L.r., whether the impurities were present in inclusions or in solid solution in the matrix is not mentioned; nor does it appear that the phase purity of the cerium was always considered. In the present study, five different stocks of cerium were involved. One was represented by a single sample of electrowon cerium, which was all that had remained from a stock of high-purity material obtained from the U.S. Bureau of Mines, Reno, Nev., in 1959. The other four stocks were recently purchased from commercial sources and were specified to be 99.9 wt pct pure. EXPERIMENTAL Cerium stocks designated as #1, #2, #4, and #5 were obtained from commercial suppliers for the specific purpose of finding a reliable source of high-purity cerium. Although the purity level of the cerium was specified to be 99.9 pet, the specifications did not include limits as to the amounts of various impurities that would be acceptable. Consequently the chemical analyses of the different stocks varied widely. Stock #3, which had been obtained from the U.S. Bureau of Mines and which was the purest on the basis of chemical analyses, consisted of a single specimen of electrowon cerium. It was included in the examination for purposes of comparison. Table I contains the chemical and spectrographic-

Jan 1, 1968

By V. Koump, R. H. Tien, W. J. Kim

This paper presents an approximate solution of the problem of freezing of a binary alloy. he alloy is in the form of a one-dimensional slab of finite thickness. The surface temperature of the slab is assumed to be constant and lower than the solidus (or eutectic) temperature. The densities of the liquid and the solid are assumed to be equal. For a given binary alloy system, initial concentration of solute and surface temperature, the solution yields a) the temperature distribution in the solid skin, b) the temperature, concentration, and solid fraction distribution within the solid-liquid region, and c) the positions of the liquidus and the solidus (or eutectic) fronts as a function of time. The results of calculation for Fe-C and Fe-P systems are presented. In this investigation we are considering the problem of solidification of a binary alloy. The alloy is in the form of a one-dimensional slab of finite thickness. The molten alloy is initially at liquidus temperature. At time zero the surface of the slab is reduced to a temperature T, < Te,, where Te, is the solidus (or eutectic) temperature and T, is a constant. The densities of solid and liquid alloys are assumed to be equal and independent of temperature and composition. A qualitative picture of solidification of an alloy, under these conditions, is illustrated in Fig. 1. During the initial stage of solidification, before liquidus front reaches the center of the slab, freezing proceeds by propagation of two isothermal fronts, the liquidus front and the solidus (or eutectic) front. The fraction of solid at the liquidus front is zero; the fraction of solid at the solidus front is unity, The solid fraction and the temperature distribution between the two fronts and the width of the solid-liquid region change with time. During the later stage of freezing, after the liquidus front reaches the center of the slab, the liquidus front disappears. The solid fraction and the temperature at the center of the slab, as well as throughout the solid-liquid region, are now changing with time. The solidification is completed when the fraction of solid at the center of the slab reaches unity. In solution of this problem we seek to determine a) the temperature distribution in the solid, b) temperature, concentration,

Jan 1, 1968

By J. W. Spretnak, R. Speiser

IT has been suggested that boron in steel may form a film entirely around the austenite grain and that this film is responsible for the boron hardenability effect. In this connection, it is of interest to examine some of the ramifications of the concentration range of boron usually employed in hardenable steels, namely 0.0005 to 0.003 pct in a grain size range of ASTM grain size No. 1 through No. 10. The ratio of the iron to boron atoms and the number of unit cells of y iron per boron atom are listed in Table I. Even at the highest concentration considered, there are 1600 unit cells of y iron per boron atom, assuming a uniform distribution of boron. To investigate the possibility of the boron film formation, the number of boron atoms required to cover the grain surface completely must be calculated. With some transition elements, boron crystallizes in sheets composed of equilateral hexagons very much like graphite.&apos; The selected value for the length of a side is 1.80Å. A simple calculation shows that two boron atoms cover an area of 8.4x l0 -16 sq cm. Table II lists the number of atoms of boron required for the formation of the monatomic film and Table III lists the number of boron atoms per grain. The hypothetical cases of 100 pct and 10 pct adsorption are calculated (all boron atoms in a grain and 10 pct of all boron atoms in a grain are located at the grain surface respectively). In Table 111, all combinations of grain size and composition below and to the left of the solid line (100 pct adsorption) and the dashed line (10 pct adsorption) are excluded as to the possibility of covering the grain surface with a continuous boron film. Thus, even for 100 pct adsorption, the smaller grains can form the film only at the higher concentrations. For the best case, grain size No. 1 and 0.0030 pct B, the required degree of adsorption is 3.9 pct. The above calculations deal only with the number of boron atoms required to form a monatomic film and do not take into account the mechanism of concentration of boron at the grain surface and the possible limitations to the extent of this concentration at a constant temperature, as for example in the austenitizing process. The question next arises as to how this surface concentration can occur during an isothermal treatment. Such surface enrichment of boron must occur through the phenomenon of surface adsorption, i.e., the concentration of solute atoms in solid solution in the vicinity of the surface without precipitation. A solute atom will tend to concentrate at the grain boundary if it reduces the interfacial tension. The possibility of adsorption effects involving both boron and carbon in iron has been discussed.&apos; In general, the tendency for a sol-

Jan 1, 1954

By D. C. Seidel, M. C. Fuerstenau, R. J. Roman

The role of surface charge in soluble salt flotation, which was developed in Part I, is extended to relate the theory to the specific phenomena of KCI-NaC1 separations. Temperature-collector solubility relationships, metal ion activation, and particle size effects are discussed. The initial paper in this series developed and presented the hypothesis that one of the mechanisms of soluble salt flotation may involve electrical attraction between the collector and mineral surface. This hypothesis was developed from a combination of experimental data and free energy calculations, and details of the logic are presented in this first paper.* The studies have indicated that KC1 has a positive surface charge and NaCl a negative charge. KC1 can therefore be floated with sulfonate ion (RSO;) or with an aqueous polar species such as the aqueous amine chloride, RNH3C1(,,). The chloride end of the RNH3C1(,,) molecular dipole is probably negative and will be attracted to the positive surface of the KC1 particles and absorb (actually probably fit into a vacant chloride site) on the mineral surface. The amine end of the collector molecule would extend into the solution phase and provide the air avid surface required for flotation. NaCl particles are floated by such collectors as aqueous molecules of fatty acid salt, RCOONa(,,), in which the positive inorganic end of the dipole is attracted to the negatively charged surface of the NaCl and, in this case, adsorb and probably fit into a vacant sodium site on the surface. The aminium cation, RNH~, should also be a collector for NaC1. For certain collectors, actual precipitates of the collector must be formed before a sufficient amount of the polar aqueous molecule is present to effect flotation. In a system of this type there is a three-way equilibrium between: Aqeous Molecular Solid Precipitate - A of the Collector (Not Dissociated) . Ionic Species (Dissociated). The controlling equilibrium is probably between the precipitated form of the reagent and the aqueous

Jan 1, 1969

By C. R. Kuzell

INTRODUCTION KNOWLEDGE of the thermal capacity of gases is of great importance in making metallurgical calculations. The metallurgist is, frequently called upon to investigate and determine furnace efficiencies in which the heat carried into or out of the furnace by gases is a large item in the heat balance. Not only do such problems present themselves in the determination of furnace efficiency, but also in the study of the application of heat is accessory apparatus, such as stoves, regenerators, waste-heat boilers, driers,.etc. The thermal effect of the use of excess air in the combustion of fuel, the theoretical temperatures of combustion, the quantity of heat in hot blast at various temperatures, the effect of hot blast on furnace temperatures, are a few more examples of frequently occurring calorific problems involving gases. So many are the applications of the data on the heat capacity of gases that the subject merits careful study. The heat in a gas maybe due to its heat of combustion, if it is a combustible gas, and to its temperature. The latter is called its sensible heat and is the heat absorbed or evolved by a gas as its temperature is raised or lowered. The heat of combustion of gases is well established and is commonly known. The values can be found in almost any mcdern treatise on metallurgy. The sensible heat of gases has not been so well established because it is in most cases a function of the temperature, and the values of specific heats of gases over a wide range of temperatures have only recently been determined. It is the purpose of this paper to deal with the sensible heat of gases.

Jan 8, 1914

By Henry D. Hibbard

FoR the purpose of this paper all steels will be divided into two divisions: effervescing and non-effervescing. This classification must be borne in mind as many statements true of one class are not true of the other. Effervescing steels are those that effervesce in the molds, evolving large volumes of gases, which, in escaping, throw up a spray of molten particles of steel and give the molten metal in the mold a rapid stirring or churning motion until it freezes, or, at least, becomes pasty. This effervescing is intended and proper. The non-effervescing steels, which are more or less completely killed, should not evolve any gas in the molds. Many years ago the writer proposed to call the two classes of steels evolution and solution steels, depending on whether the gases in the molds are evolved or kept in solution, but the present designations seem to be better. In America, at least, effervescing steels are in a class by themselves and include steels made for boiler, tank, and ship plates, steel pipe, soft steel wire, wire nails, soft machincry, and structural steels. These are all low-carbon steels with less than 0.40 per cent. carbon. Low-carbon steels that do not effervesce but are killed are also made; these are put into ingots and castings but they are outside the limits of this paper. Effervescing steel is cast into square or slab molds, either top or bottom poured. Most of the effervescing steel is made in the basic open-hearth furnace, though much is made by the acid Bessemer process and a little is made in the acid open-hearth. It is not made by the crucible or electric-furnace process, in which the volume of gas required cannot be produced in the steel and evolved from it in the mold to give the effervescence desired. Any steel ingot, when teeming is finished, is of a certain size or volume. Leaving out of consideration for the moment the lessening of the over-all dimensions of the ingot through contraction due to loss of heat, the ingot may be placed in one of three classes: It may settle, losing in volume; it may stand, that is, remain constant in volume; it may rise, that is, increase in volume. Into which class an ingot will fall depends on the gases of the steel,

Jan 1, 1920

By H. K. Birnbaum, H. B. Aaron

he authors suggest that a number of the types of yield phenomena which have been observed in high-purity fcc metals are due to dislocation interactions bccurring at the surface of the crystals rather than due to volume effects. Since rather different inter-pretationS2,7,12,14,15,21-23 of these effects have been suggested, it is of some importance to ascertain the role of the surface in these yield phenomena. It should be first noted that the high-purity fcc metals appear to exhibit several distinct types of yield phenomena. The "unloading yield point" which is observed on reloading the specimen after removing the applied load has been found to be independent of the time of holding in the unloaded condition. If however the specimen is aged while under load and re-tested without removing the load, a yield point is observed which does depend on the aging time and tem-perature. Feng and Kramer suggest that the removal of the unloading yield point on removing sufficient material from the surface of the specimen indicates that the effect is associated with dislocation interactions at the specimen surface. Their observations are counter to those of Haasen and Kelly5 and Birnbaum.12 Since the unloading yield points are extremely small (-2 pct of the flow stress) the results of the surface removal will depend on whether the material is removed uniformly over the gage length. The introduction of small etch pits or the removal of more material from one portion of the specimen than from another will result in preferential yielding and obliteration of the yield point. With the normal electropolishing techniques it would be difficult to avoid these effects. The data obtained by Aaron and Birnbaum, Fig. 10, on aluminum polycrystalline specimens indicate that, although the unloading yield point and the strain-aging yield point are not simply additive, a time- and temperature-dependent yield point is observed under conditions where no creep is observed. This does not agree with the results of Feng and Kramer but does agree with the results on copper15 and gold.7~23 The source of the discrepancy may be the procedure used by Feng and Kramer to correct their time-dependent yield points for the effect of creep. Since the strain-aging yield point is not independent of the pre-aging strain rate, Fig. 11, the effects of creep cannot

Jan 1, 1967

By O. W. Ellis

Before entering upon a general discussion of the fascinating, but at present rather controversial, subject of gases in copper, the author feels that some attention should be directed to the work which has been carried out on the solubility of gases in metals. The outstanding contributions to our knowledge of this subject have been made by Sieverts and his collaborators(1) † and by Iwasé.(2) Both the German and the Japanese investigators employed apparatus of the same general design in their investigations. Full reference need only be made, therefore, to the German scheme, which is diagrammati-cally illustrated in Fig. 1. This, to use the words of Sieverts, which he employed in describing his arrangement of apparatus at the 1928 meeting of der Deutschen Gesellschaft für Metallkunde(10): shows a diagram of the usual mode of procedure. A quartz flask contains the metal (for high temperatures a highly refractory porcelain tube is used) and is connected with the rest of the apparatus by means of a stopcock. The other parts consist of a burette divided into 1/10 c.c., a leveling tube, and an adjustable mercury reservoir. The burette is connected on one side with the gas inlet and on the other side with the absorption flask; the connection can be interrupted by means of suitable taps. Another tap permits the connection of the flask and the Töpler pump. In an experiment the quartz flask is first exhausted and then a measured quantity of gas is let in from the burette. In the first place the volume of the flask when empty is found by calibration with an inert gas. The pressure is read off on the level tube of the burette, and the temperature measured by means of a thermocouple whose welded junction lies close to the outside of the quartz flask, which is heated in an electric furnace. In several experiments the quantity of absorbed gas was transferred to a burette by means of a pump and measured. Care was taken by Sieverts to cool the ground-in joint between the reaction flask (or tube) and the rest of the system. Suitable precautions

Jan 1, 1934

By Hertha R. Freche

The diffusion of magnesium and silicon from the core into the high-purity coating of Alclad sheet is important commercially, and led to the use of a duplex product for the study of diffusion by means of spectro-graphic analysis of successive layers. It has been found that in the duplex materials the diffusion of magncsium from an undersaturated aluminum-magnesium alloy into its high-purity aluminum coating is approximately of the same order of magnitude as the diffusion of silicon from a saturated aluminum-silicon alloy into its high-purity aluminum coating. However, if magnesium and silicon are both present in the alloy in the ratio of Mg2Si, they appear to diffuse in the approximate ratio of this compound. Finally, if the alloy contains silicon in excess of the amount required by magnesium silicide, the amount of diffused silicon in the high-purity aluminum coating will also be in excess. The interdiffusion of metals in the solid state is of both scientific and technical interest, because it is helpful in the study of the alloy structure and in the solution of problems pertaining to the strength and surface condition of the fabricated product. W. C. Roberts-Austenlt carried out the first quantitative determination of the coefficient of diffusion of gold into lead. This classical experiment was followed by a series of investigations on the diffusion of metals and nonmetals in iron and steel and in nonferrous metals and alloys. Recently the diffusion of copper in coated strong aluminum alloys was investigated by A. Burkhardt2. This appeared to be the first published investigation on the diffusion of metals into aluminum. The present investigation was the direct result of a technical question in connection with alloy fabrication and is a summary of some preliminary work pertaining to the diffusion of magnesium and silicon into aluminum. The results necessarily will be subject to some variations, since this is the first attempt to evaluate the coefficients of diffusion of magnesium and silicon into aluminum according to this method of procedure. This

Jan 1, 1936

By G. B. Craig, B. Ramaswami

The temperature and strain rate dependence of the flow stress ratio and the stvain rate dependence qi the flow stress of annealed polycrystalline a zirconiur were determined over the temperature range 30 0" to 1000°K. Some evidence was found for strain aging and discontinuous flow in the temperature ranges 520" to 650°Kand650" to 760°K, respectively. The Cottvell-Stokes relationship was obtained when deformation occurred by twinning as well as slip. The flow stress ratio showed a strong dependence on temperature and strain rate above 800°K. The expevirnental evidence indicated that the rate-controllitzg mechanism for the deformation of a zirconium above 800°K was dislocation climb, and that the deformation was not thermally activated in the range 520" to 800°K. The stacking-fault energy of a zirconium was estimated to be about 250 ergs per sq cm. A knowledge of the temperature and strain rate dependence of the applied stress necessary to deform a crystalline solid is essential for understanding the thermally activated processes occurring during deformation.&apos; Several experimental techniques have been developed for studying these processes.273 One of the techniques is the deter mi nation of the strain rate dependence of the flow stress at constant temperature. In close-packed crystals, it has often been observed that the change in stress due to a change in the strain rate varies linearly with the flow stress, (~1,&apos; This relationship, known as the Cottre ll-Stokes law, is obeyed when deformation occurs by glide alone. However, when deformation occurs by twinning as well as glide, there is disagreement among different investigators on whether the Cottrell-Stokes law is observed. Whereas Thornton et ~1.~find departures from Cottrell-Stokes law when twinning occurs in copper, ~avis~ and sasinski? find that Cottrell-Stokes law is obeyed when deformation occurs by twinning as well as slip in cadmium and magnesium, respectively. One of the main objectives of this study is to determine whether the Cottrell-Stokes law is obeyed when deformation occurs by twinning as well as slip. The second technique that has been used extensively to study the thermally activated deformation of crystals is the determination of the ratio of the flow stresses, at identical dislocation structures and con-

Jan 1, 1968

By M. H. Forester, John D. Cooner

ALTHOUGH the unmined anthracite will last for approximately A 150 years, most of the thicker and cleaner coal beds have been almost entirely first-mined and pretty well robbed, leaving much of the present and future production to come from thin and dirtier beds. Herewith is a section of one of the dirty beds being mined in the Wyoming region This section shows that 45.8 per cent of the bed is made up of impurities and that the 45 in. of coal in the bed is in five benches, the thickest of which is 19 inches. In some localities of the anthracite region there are 14 beds of minable coal. Orderly and proper mining of the coal makes it necessary to rob or second-mine-almost all beds have already been first-mined-in sequence from the top downward. Therefore the robbing of the few remaining portions of the thicker and cleaner beds is in many instances being held up by the mining of the overlying thin and dirtier coal beds. Impurities Impurities consist of fire clay, slate, rock, and bone. The latter, which is black, contains 40 to 60 per cent carbon and often resembles good coal. In some beds there are also bands of "blue" coal, which, as the name implies, is of a bluish slaty color. Although much of this "blue" coal has a carban content almost as high as the good anthracite, it is not

Jan 1, 1943

By Walter Kauzmann

ALL viscous or plastic flow of incompressible matter is the result of shear strain; the changing shape of any body that is being plastically deformed can be completely described in terms of the shear strain occurring at each point in the body.[t] Furthermore, the relative amounts of shear strain occurring in different parts of a body under stress depend upon the relative rates of shear strain at those different points, so that if the dependence of the shear rate of any material on the temperature, shear stress, previous history, etc., were understood, the principles of plastic deformation would be known, and we could calculate how a body made of a given material, having a given shape, and subject to a specified system of forces, would change its shape with time. It may be said, then, that the problem of plasticity resolves itself into, first, the problem of the rates of pure shear processes, and second, the application of what is known about pure shear to actual cases. It is the purpose of this work to investigate the former problem -i.e., the dependence of shear rates on temperature, stress, etc.-from the standpoint of recent developments in the field of chemical-rate theory and with particular reference to the phenomena occurring in the creep of metals and in the plastic flow of crystalline solids in general. It is left for the mechanical engineer, and perhaps the expert in hydrodynamics, to deal with the problem of applications1 RESOLUTION OF MACROSCOPIC SHEAR INTO MICROSCOPIC MOVEMENTS; RESEMBLANCE TO CHEMICAL REACTIONS Just as any large body is made up of many small units, or atoms, so macroscopically observable shear is the result of many microscopic unit shear processes; just as the understanding of the behavior of large bodies demands the understanding of the atoms of which it is made, so the understanding of macroscopic shear demands the understanding of these fundamental unit processes. The study of shear from this "atomistic" point of view has made considerable progress. There has been fairly complete understanding of shear processes in gases for a long time, at least for nonturbulent flow, as a chapter on gaseous viscosity in any text on the kinetic theory of gases will prove. In recent years Andrade2 and Eyring3 have presented important theories for the flow of liquids and amorphous solids. Becker,4 Orowan,5 Taylor,6 Burgers,7 and Kanter8 have considered the

Jan 1, 1941

By D. R. Uhlmann, T. P. Seward, K. A. Jackson, J. D. Hunt

microscopic ohservations on alloys of organic trzaterials show that dendrite arms can melt off under normal conditiorzs of growth. This occurs because of the interactiorz of&apos; heat and matter fluxes during dendritic growth. The re melting occurs where the den-drite arms are joined onto the main deizclrite sterrz. Many detached crystals can be produced in this fashion. It is postulated that this remelting phenornenon occurs in metal alloys, giving rise to the equi-axed region in castings. Experiments peyformed orr castings of transparent materials support remelting as a primary source of detached crystals. Ob~ervations an equiaxed tones in metal castings are discussed in terms of this and other mechanisms. It is concluded that the partial remelting of dendrites is on important mechanisnl for producing the equiaxed regions in castings. THE freezing of a casting can be divided into three regions: a chill zone formed near the mold wall, a columnar region, and a third region, at the center of the casting, which is called the equiaxed zone. The origin of the grains that comprise the equiaxed region is the subject of this paper. We will first outline the mechanisms which have been proposed to account for the origin of the equiaxed region and discuss some recent experiments which cannot be explained by these theories. We will then present some microscopic observations of dendritic growth which have led us to conclude that the equiaxed zone in castings can arise from partial remelting of dendrites. This proposal is supported by observations on transparent castings. Finally, we will discuss several observations on metal castings which could not be explained previously, and which can be accounted for by the present proposal. Previous Mechanisms. Winegard and Chalmers3 pointed out that the molten central region of an ingot could be constitutionally supercooled, because of the solute layer at the growing interface. In this supercooled region, nucleation on particles could occur, giving rise to the equiaxed crystals. Another mechanism has also been suggested,4y5 that the nuclei originate in the chill zone then float or are carried by convection to the center of the casting, where they grow to produce equiaxed crystals. In this case, all the crystals nucleate immediately on casting, so this mechanism will be termed "big-bang" nucleation. Walker&apos;s Experiments. J. L. Walker has made observations on the solidification of nickel and Ni-Cu alloys which cannot be accounted for by either of the above mechanisms. In studying the grain size resulting from freezing of nickel at various undercoolings, walker6 found that at large undercoolings the grain size was small, due to mechanical nucleation, as discussed by walker7 and Horvay.&apos; At small undercoolings, the grain size was large, and the growth dendritic. In Ni-Cu alloys, however, for initial undercoolings starting from just below the melting point and extending for a hundred or so degrees of undercooling, fine grains were also observed. Samples were undercooled 200 Centigrade degrees without nucleating, and were then heated 130 Centigrade degrees so that the undercooling was 70 Centigrade degrees, and nucleated. The samples had a small grain size, indicating multiple nucleation. There were no heterogeneous nuclei in the liquid which could operate at the temperature of growth. Constitutional supercooling could not have been greater than the supercooling of the initial melt, since the temperature rose as the freezing continued. walker -as also shown that a Ni-Cu alloy which can be undercooled to below its solidus will produce typical columnar and equiaxed regions when cast into a cold mold. This alloy could not reach a temperature below its solidus by constitutional supercooling. It could not, therefore, have nucleated heterogeneously. Neither the big-bang mechanism nor the Winegard-Chalmers mechanism can account for the fine grain

Jan 1, 1967

By Reuel A. Cochrane, Harry H. Angst

The successful exploitation by opencut methods of the low-grade porphyry copper deposits is due to the economical handling of large tonnages. Large tonnages are possible only if the rock material is broken so that the large power shovels can operate with minimum delays. This is particularly true at the New Cornelia mine, where the dense, hard, tough rock material creates problems not encountered in most of the porphyry copper mines. The introduction of churn drills at the New Cornelia for primary drilling, in 1936, necessitated a complete change in the methods of breaking ground as formerly air drills had been used. The blasting operations are of particular interest because of the handling of great quantities of high explosives in safely and efficiently fragmenting the hard rock material. Rock Formations At the New Cornelia mine the rocks are quartz monzonite with a diorite border facies intruding a rhyolitic series. Overlying these formations is a fanglomerate formation composed of boulders of monzonite, diorite, rhyolite, and other types of rock of unknown derivation. (The word "fanglomerate" is used in this paper in referring to the local conglomerate type of rock formations.) The ore body is approximately 4800 ft. long and 2800 ft. wide, and is of the disseminated type. Mineralization occurs principally in the quartz monzonite and to some extent in the adjacent diorite and rhyolite. The principal ore minerals are chalcopyrite, bornite, and a small amount of chalcocite. Over a considerable area the quartz monzonite is extremely hard and siliceous in character, owing to pegmatitic zones of alteration. The hardness of the ground depends on the intensity of the silicification. In a small area in the pit, the monzonite contains an abundance of pyrite accompanied by sericitization and is soft and easily fragmented. This is true also in the remaining oxidized portion of the ore body. The diorite and rhyolite formations, like the monzonite, vary from extremely hard to very soft material, but on the whole are easier to fragment than the monzonite. Jointing is prevalent in all the rock formations and plays an important role in the blasting efficiencies. In the fanglomerate formation, numerous well-defined joints, widely spaced, tend to make the ground blocky when blasted. This is a deterrent to good fragmentation. In the other rocks the joints are more numerous and are closely spaced, except in localized areas where the formations are extremely hard. These descriptions indicate that the lowest blasting efficiency will be obtained in the harder formations, from which the major portion of the mine production is obtained; namely, the monzonite and rhyolite. All rock formations mined at the New Cornelia pit are so hard that excavation

Jan 1, 1943