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By Stanley Rajnak, John E. Dorn

The saddle-point activation energy for the nu-cleation of a pair of kinks is estimated as a function of the applied stress, the lattice constants, and the height and shape of the Peierls' hill by employing the line-energy model of a dislocation. The kinetics of disloration motion by the Peierls' mechanism are discussed and the microscopic dislocation velocities and macroscopic strain rates are formulated by the Arrkenius type of approach in terms of the activation energy for the formation of pairs of PEIERLS was the first to illustrate that a straight-dislocation line has its lowest energy when it lies in a potential valley parallel to lines of closest packing kinks. The log of the dislocation velocity is found to be approximately proportional to the log of the local applied stress. It is also shown that the low-temperature mechmical properties of several bcc metals might be explained in terms of the Peierls mechanism, good agreement being obtained between theory and experiment for the flow stress us ternperature, activation energy vs stress, and activation volume us stress curves for these metals. of atoms on the slip plane. When such a straight dislocation is moved rigidly from one valley toward the next, the atoms in the vicinity of the core of the dislocation change their positions and bond angles, causing the energy of the dislocation to increase. Midway between two adjacent valleys, the disloca-tion energy reaches a maximum value and any additional small displacement will cause the dislocation to fall down the hill into the next valley. The maximum shear stress necessary to promote such

Jan 1, 1964

By D. G. Westlake

Resistance was measured as a function of temperature, 77° to 350°K,for niobium with hydrogen concentrations up to 3.76 at. pct. Cooling curves exhibited a discontinuity in slope that was attributed to the initiation of hydride formation. A thermal hysteresis was explained in terms of diffusion and the effects of mechanical constraint on nucleation and growth. The heat of solution of hydrogen in saturated Nb-H solid solution was 2. 737 * 0.045 kcal per g-atom, including an unknown stress contribution. The critical ternperatures for hydride formation during cooling and for embrittlement are correlated but not coincident. This, too, has been explained in terms of mechanical constraint and stress-itlduced tratzsfomtation. Nb-H alloys undergo a ductile-brittle transition with decreasing temperature.'-3 Similar behavior has been noted for v-H.1,5 For the latter system, there is evi-dence6 suggesting coincidence of the temperature of minimum ductility and the critical temperature T, for initiation of metal hydride precipitation during cooling. A decrease in ductility due to the presence of brittle hydride particles is readily explainable. The fact that ductility begins to decrease at some temperature higher than T,4,5 has led us6 to suggest that precipitation may be strain-induced locally during tensile testing. Wood and Daniels' have reported that a plot of temperatures for 10 pct reduction in ductility vs hydrogen concentration in niobium is not coincident with, but parallels, the solvus.7,8 They believe this indicates a correlation of precipitation and embrittlement. Unfortunately, the two reported solvuses 7,8 to which Wood and Daniels refer are not in agreement with each other. Furthermore, neither solvus was determined experimentally: each was a plot of calculated solubilities. Thus. neither is highly dependable for determining whether embrittlement coincides with initiation of hydride precipitation. Longson 9 studied phase relations in the Nb-H system between 77° and 473°K by dilatometry. Comparison with metallographic observations convinced him that discontinuities in the slopes of his dilatometric plots were coincident with the initiation of hydride precipitation. Plotting the logarithm of the hydrogen concentration vs the reciprocal of the temperature at which precipitation was initiated during cooling, he obtained a straight line shown in Fig. 1. Walter and chandler,'' using X-ray techniques to detect the for mation of a second phase? have obtained three experimental points in the temperature range 295° to 338°K which fall within Longson's experimental error for this plot. A similar plotg of temperatures at which dissolution was completed during heating was a parallel line shifted toward higher temperatures. A straight-line plot was obtained, also, for the temperatures of the ductile-brittle transitions,9 but it was shifted toward still higher temperatures. Longson calculated an activation energy of 2.980 * 0.300 kcal per mole for the hydrogen embrittlement mechanism, compared with 3.180 * 0.400 kcal per mole for hydride formation. Despite this agreement, he concluded, "It seems unlikely that embrittlement results from hydride formation..." because hydrogen embrittlement was observed at temperatures above the solvus. It is our contention that embrittlement is correlated with precipitation of the hydride.6 Because only Longson has investigated Nb-H phase relations at sub-ambient temperatures, we deemed it advisable to re-determine the temperature dependence of the solubility using the resistometric technique already proven successful for the V-H system.6 Coincidence of our solvus with temperatures for embrittlement would

Jan 1, 1970

By C. H. Samans, G. F. Tisinai

HARDENING and embrittlement of the ferritic chromium stainless steels at temperatures near 885 °F have been known for a long time.' However, no satisfactory explanation has been given. Both ordering and precipitation hardening have been suggested. Fisher, Dulis, and Carroll2 discovered a chromium-rich body-centered-cubic precipitate in embrittled alloys. Subsequently, Williams' and Wright4 also have found evidence of this body-centered-cubic constituent. William's hardness, electrical resistance, and magnetic studies led to his proposal of a new constitutional diagram for the Fe-Cr alloys. The new feature of this diagram is the eutec-toidal decomposition, below about 970°F, of the s phase into two stable body-centered-cubic solid solutions, one rich in iron and the other rich in chromium. An observation of Heger5 that the amount of s phase has increased and the amount of chromium-rich body-centered-cubic phase decreased in the interval 5000 to 32,600 hr at 900°F, even though the alloy increased in hardness, casts some doubt on this diagram. If precipitation hardening causes the embrittlement, the precipitate probably is always coherent with the matrix, since no evidence of overaging has been reported. It cannot be stated positively, however, that Fisher's body-centered-cubic constituent is the embrittling phase. According to Preston's data,6 such a chromium-rich phase should have a parameter less than about 0.5 pct larger than that of the iron-rich matrix lattice. Moreover, the constitutional relationships whereby Fisher's constituent forms, and whether it is stable, metastable, or a transition phase, are not yet completely clear. The recent studies of Wright4 and of Lommel,7 as well as the earlier studies of Becket8 and of Hochmann,9 have shown that 885°F hardening occurs in relatively pure Fe-Cr alloys. No evidence of its occurrence or absence in chromium itself has been reported. The rate of hardening in high purity alloys seems appreciably slower than that in alloys containing larger amounts of impurities (chiefly carbon and nitrogen). This may be due merely to the absence of hardening and straining effects from precipitated carbides and/or nitrides. These observations on high purity alloys make it seem unlikely that 885 °F hardening is caused by a constituent containing other than iron and chromium atoms, e.g., carbides and/or nitrides. Wright,4 Lommel,7 and Lena and Hawkes10 emonstrated the accelerating effects of a finely dispersed precipitate of (probably) chromium nitride on the hardening reaction. This appears to be evidence that lattice straining increases the rate of nucleation of the hardening constituent. Some new observations on 885°F hardening are reported here. They show an effect of preheat treatment that should contribute to a better understanding of the 885°F hardening phenomenon. They also clarify a discrepancy which exists in the literature. Some investigators have reported most rapid hardening at 885", whereas others have reported it at 930°F. The present work also shows that 885°F hardening does not occur in electrolytic chromium, and that any long range ordering type of reaction affecting any sizeable part of the volume is unlikely. Materials Studied Table I shows the currlposition of the alloys used in this investigation. In these alloys carbon and nitrogen are present in roughly similar amounts. Presumably both elements precipitate, as carbides and/or nitrides, during the heat treatments given.

Jan 1, 1958

By L. S. Darken, H. A. Wriedt

An investigation has been made of nitrogen absorption by the lattice defects in a low-carbon steel afte~ Plastic deformation. Specimens in which defects were distributed by various combinations of cold rolling and vacuum heat treatment were equilibrated with controlled ammonia + hydrogen mixtures at 300° to 450°C to study the relation between the solubility and the thermodynamic activity of nitrogen. The results are interpreted in terms of nitrogen being absorbed upon two different types of defect sites, called A sites and B sites. The concentrations of these sites are calculated for specimens with various histories of straining and annealing; and the thermodynamic relations descrihing the equilibrium distribution of nitrogen among the A, B, and ordinary interstitial sites in ferrite are evaluated as follows: THE generalization that the solute atoms in a solid solution interact with imperfections in the solvent lattice is now universally recognized and the subject of an extensive literature. All types of imperfections—point, line, or surface—exhibit these interactions, but the relative importance of each type depends upon its concentration, the strength of its interaction with the particular solute atom, and whether the interaction is attractive or repulsive. The strength and sign of the interaction vary with the vectorial displacement of the solute atom from the imperfection in the crystal. The concentration of lattice defects increases during plastic deformation and the effect of the imperfections upon the solute atoms is usually perceived only after cold work or irradiation. Two experimental methods have previously been used to observe the effects of interaction between nitrogen atoms and lattice imperfections in a iron. Internal friction, which was first used for this purpose by Dijkstra,1 has been applied more often than the electrical-resistivity method of Cottrell and Churchman.2 The method of the present investigation has not been used before.* Uniform specimens of steel with a metastable defect structure are produced by cold rolling and subsequent heat treatment below the recrystallization temperature. Variations in the defect structure are obtained by varying the amount of strain and the heat-treatment conditions. The specimens are then saturated with nitrogen at moderately elevated temperatures in ammonia + hydrogen mixtures having various thermodynamic activities of nitrogen below saturation with Fe4N. From the nitrogen contents of analyzed samples, the metastable equilibria of interactions between the defects and nitrogen can be established and the concentration of sites for nitrogen atoms in the lattice defects calculated. A steel was used in the present experiments instead of purified iron or iron alloys because the amount of nitrogen absorbed at defects is larger in the steel over a much wider range of experimental conditions and could therefore be measured more accurately. The effect of alloy composition is discussed in Part II of this paper; it is sufficient to say here that impurities and phase heterogeneity in ferritic alloys favor the generation and/or retention of larger defect concentrations during plastic deformation and annealing at 300° to 500°C. MATERIALS AND EXPERIMENTAL PROCEDURE The experimental specimens were prepared from stock of a low-carbon steel, which will be called "X steel" here, with the composition: C, 0.12 pct; Mn, 0.43 pct; P, 0.010 pct; S, 0.034 pct; Si, 0.007 pct; As, 0.086 pct; Cu, 0.022 pct; Ni, 0.009 pct; Cr, 0.003 pct. The stock was all from a single ingot made by the basic open-hearth process, which was hot-rolled to strip 0.080 in. thick.. This hot-rolled strip, given the code designation "XH", was the starting material for preparing a series of cold-rolled sheets. The latter are designated "XC27",

Jan 1, 1965

By Donald L. Katz, Leslie J. Noaker

Experimental data are presented for hydrate formation conditions for mixtures of hydrogen sulfide and methane. Vapor-solid equilibrium constants for hydrogen sulfide are also presented. Equilibrium constants, defined here as the ratio of the mole fraction of hydrogen sulfide in the vapor phase (dry basis) to the mole fraction of hydrogen sulfide in the solid phase (dry basis), were calculated using the vapor-solid equilibrium constants for methane presented in an earlier paper. The conditions at which a natural gas will form gas hydrates with water may be computed from its composition, when hydrogen sulfide is present in addition to carbon dioxide and the paraffin hydrocarbons. INTRODUCTION Many gases are known to form solid hydrates in the presence of liquid water at temperatures above 32°F. This hydrate formation is of importance to the natural gas industry inasmuch as most of the constituents found in natural gases will form hydrates. The attention of the industry was called to hydrates by Hammer-schmidtl0 in 1934. A number of papers have been written giving the temperatures and pressures at which these hydrates will form3,4,5,6,7,8,9,10,13,14,15,18,19 and a bibliography on the subject has been compiled13. Deaton and Frost4,5,6,7,8 report work for various pure gases and for some natural gases. Katz and co-workers3,4,13,14,18,19 have reported data for various gases at high pressure. They developed a method of predicting conditions for hydrate formation from equilibrium constants3,19 and from gab gravity." The effects of anti-freeze agents on the formation of hydrogen sulfide hydrate were reported by Bond and Nelson.' The hydrogen sulfide-water system, including hydrate, has been the subject of recent investigation by Sage and co-workers." Mixtures of hydrates behave as solid solutions and an equilibrium exists between the vapor phase and the solid phase that appears to be comparable to the equilibrium between vapor and liquid phases.3,10 By means of the vapor-solid equilibrium constants which have been published for methane, ethane, propane, iso-butane, and carbon dioxidel6 it is possible to determine the temperature and pressure at which hydrates will form for a specific gas mixture when water is present. Hydrogen sulfide which is frequently found in natural gases has a very strong tendency to form hydrate and must enter the solid solution when present in a natural gas forming a hydrate. To determine the effect of hydrogen sulfide when computing the conditions for gas hydrate formation, it is necessary to have the equilibrium constant giving the ratio of the concentration of hydrogen sulfide in the gas phase to the concentration in the solid phase. This paper presents data on hydrate formation for mixtures of hydrogen sulfide and methane and presents the equilibrium constants which were calculated from these data. EXPERIMENTAL PROCEDURE The apparatus used to determine the conditions of hydrate formation for the methane-hydrogen sulfide system was similar to that employed by previous investigators.3,18,19 A charge gas cylinder was used to supply the hydrogen sulfide-methane mixtures, called the charge gas, and to supply the pressure up to 1.000 psia. This

Jan 1, 1955

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;'-' and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By O. P. Arora, M. Metzger, G. R. Ramagopal

The rates of grain boundary and general corrosion were surveyed by an approximate method. Quantitative differences between their variations with the strength or cupric ion content of the acid yielded large variations in their ratio, highly selective intergranular attack being observed only under specific chemical conditions. The boundary corrosion rate increased with the copper content of the aluminum; this was attributed to an autocatalytic effect similar to the one shown for general corrosion. High- purity aluminum in hydrochloric acid exhibits striking intergranular corrosion and other structure-dependent corrosion phenomena of fundamental interest. The behavior is highly sensitive to the metallurgical and chemical conditions, the significance of many of which has not been established. The features of the intergranular-corrosion phenomenon, first described by Rohrman,l are summarized in the remainder of this paragraph. Strong attack normally occurs only at high-angle grain boundaries.' Usually 15 to 25 pctHCl is used to obtain a high rate, but this has also been obtained with weaker (7 to 15 pct) acid either by adding cupric or ferric ion to the acid3-5 or by passing an anodic current (-0.1 ma per sq cm).2,3,5,6 The two latter corrosion conditions produce strong attack of low-angle boundaries after certain heat treatments 2-4,5,7 The susceptibility of high-angle boundaries is influenced by the grain-boundary segregation of iron atoms; this increases the slow (µ per month) attack in 10 pct HCl8 but diminishes the rapid (mm per month) attack in 20 pct Hc14 (the present and most previous investigations deal with rapid attack). That segregation of elements other than iron affects intergranular corrosion has not been demonstrated, although analysis of data for iron alloys indicated that at least one other element must be considered.9 Intergranular attack occurs over a wide range of purity although it begins to become obscured above several hundred parts per million (ppm) total im- purities by the severe general corrosion which accompanies the higher iron contents and which is associated with the presence of a second phase or an inhomogeneous distribution of the dissolved iron.4,6,10 The variation of intergranular-corrosion rate with heat treatment1'3-6'"10 can be explained in some cases in terms of the distribution of the iron impurity but is not in general adequately understood. The present work dealt with two questions not previously considered in detail. The first proceeded from the view that the extent to which a special behavior is associated with the boundaries is indicated not by the intergranular corrosion rate alone but by the ratio of the intergranular to the general corrosion rate. A comparison of the two rates was therefore made for one lot of aluminum in acids of varying strength and metallic ion content. The second question was the effect of the copper content of the aluminum. For general corrosion, it has long been known that copper ions introduced into the acid by corrosion of the solid solution are reduced on the aluminum as patches of elemental copper which enhance the corrosion rate by providing cathodes of lower hydrogen overvoltage than were originally present.''-'3 Since the copper patches remain themselves unchanged, their action is "catalytic", and since they are products of corrosion, the effect is "autocatalytic." This phenomenon is significant at copper levels much lower than previously suspected, even at those typical of high-purity aluminum, as the authors have shown in a previous paper.l4 The present work shows that copper content affects intergranular corrosion. With polycrystalline specimens, truly quantitative rate measurernents are not readily made for intergranular corrosion or for general corrosion in the presence of rapid intergranular attack, and previous work in this field has tended to be qualitative. The present study made use of a simple procedure which provided fair approximations to the quantitative corrosion rates and fitted the purpose of surveying the behavior over % wide range of conditions and displaying certain large effects. The approximations involved in this work were usually outweighed by the experimental scatter, which tends to be substantial in a system as sensitive as this one. I) EXPERIMENTAL A. Material. The material procured, Table I, represented three low copper (1 to 3 ppm) lots, two of "normal" copper content (21 and 22 ppm), and two

Jan 1, 1962

By P. R. Bradley

The property of the Alaska Juneau Gold Mining Co., covering the Juneau gold belt for over a mile in length, consists of 136 claims and 24 mill sites; these are near Juneau, Alaska, in what is known as the Harris mining district. Gold was discovered in the district in 1880, by Richard T. Harris and Joseph Juneau, who had been prompted to explore the section by rumors they had heard among the Indians. Gold was first found on the beach at the mouth of Gold Creek and further search revealed the lode deposits in the Silver Bow basin, about two miles inland. The lode locations made immediately thereafter constitute the principal area of the Alaska Juneau group of claims. Gradually news of the strike spread and, during the late eighties, Silver Bow basin became a substantial producer of gold, both from placer work and from quartz milling. Numerous small mills of various types were erected to crush high-grade float and stringers gouged to shallow depths. Placer mining gradually ceased and the pioneer milling operations gave way to larger and better mills, which in time were the predecessors of the two large mills built by the Alaska Gastineau Co. and the Alaska Juneau Co. on the shores of Gastineau Channel. This evolution from arrastres to small mechanical mills, thence to the two large-capacity mills on Gastineau Channel, although a natural sequence of events, had a most important bearing on the development of the district. Knowledge of the character, extent, and value of the ore deposits gained by these early operations could not have been acquired otherwise. Spencer shows1 that the early mills were: Arrastres in 1881-82-83-84-85-86-88; a 5-stamp mill in 1882; a "newly devised grinding mill" in 1884; two Huntington mills in 1886; a 10-stamp mill in 1889; a revolving Dodge mill in 1890; a 5-stamp mill in 1891; and a 20-stamp mill in 1893. He also estimates the gold production to the end of 1893 as $1,000,000 from lode mining and $1,250,000 from placer mining. No estimate can

Jan 1, 1925

By R. A. Graham, R. W. Rohde

The effect of hydrostatic pressure upon the austenite start temperature of a commercial Fe-28.4 at. pct Ni-0.5 at. pct C alloy has been determined. For pressures to 20 kbar, the austenite start temperature decreased from its atmospheric pressure value of 380°C at the rate of about 4°C per kbar. These data are analyzed by two different thermodynamic approaches; first, considering the transformation as an isothermal process, and second, considering the transformation as an isentropic process. It was found that both these approaches fit the experimental data equally well. The effect of hydrostatic pressure upon the austenite start temperature is best described by considering the mechanical work done during the transformation as that work obtained by multiplying the applied pressure with the gross volume change of the transformation. It is widely recognized1 that strain has an important effect on the initiation of martensitic transformations.* For example, the martensite start tempera- *In this paper, use of the term martensitic transformation implies the reversal of martensite to austenite as wen as the formation of martensite from austenite. ture, M,, may be increased by plastic deformation. Similarly, plastic deformation is observed to lower the austenite start temperature, A,. The effect of uniaxial stress on the M, of iron-nickel alloys has been studied by Kulin, Cohen, and Averbach.2 They found that the martensite start temperature was significantly changed by stresses well within the elastic region. Moreover, the effect of tensile and compres-sive stresses differed. These effects were explained in terms of the interaction of the applied stress with both the dilational and shear components of the transformation strain. The magnitudes of the influence of uniaxial tension, compression and hydrostatic pressure on Ms were measured in 30 pct Ni 70 pct Fe by Pate1 and Cohen.3 Their thermodynamic calculations and similar calculations by Fisher and Turnbull4 predicted the experimental results when the transformation was assumed to occur isothermally at some fixed driving force. This driving force was assumed to be supplied by a combination of the chemical free energy difference between the austenitic and martensitic phases and the work performed during transformation by the applied stress. More recently, Russell and winchel15 reported the effect of rapidly applied shear stress on the reversal of martensite to austenite in iron-nickel-carbon alloys. They performed a thermodynamic analysis of this transformation based upon the assumption that the re- versal occurred adiabatically. They concluded that the applied shear stress did not significantly interact with the transformation strain and thus did not assist in inducing the reversal. Rather they concluded that the reversal was effected by localized strain heating which resulted from the gross local shear deformation of the experiment. In either the adiabatic or isothermal analysis it is necessary to compute the work performed by the interaction of the applied stress and the transformation strains. In the case of hydrostatic pressure this interaction has been treated by two different methods. In either case the applied pressure is assumed to remain constant during the transformation. In one treatment the applied pressure is assumed to interact directly with the dilatational strain associated with the formation of an individual martensite plate.3'4 This local strain has been measured at atmospheric pressure in iron-nickel alloys by Machlin and Cohen.6 In the above treatment this local strain is assumed invariant with temperature and pressure changes. In the other treatment the applied pressure is assumed to interact with the gross volume change of the transformation.7,8 The usefulness of this latter treatment has been demonstrated by Kaufman, Leyenaar, and Harvey7 who calculated the effects of pressure upon the martensite and austenite start temperatures of Fe-10 at. pct Ni and Fe-25 at. pct Ni alloys. Excellent agreement was obtained between their calculations and their experimental data on an Fe-9.5 at. pct Ni alloy. However, this treatment suffers from the fact that the data required to calculate the volume change of the transformation (i.e., the initial specific volumes, the thermal expansion and compressibility data for both the austenitic and martensitic phases) is, in general, not available for any material except pure iron. Thus the calculations of Kaufman et al.7 were necessarily performed by assuming that the volume change of the martensitic transformation in the iron-nickel alloys was that same volume change occurring during the a-? transformation in pure iron. While this approximation may suffice for very dilute alloys it is likely to be inaccurate in high nickel alloys. We have performed measurements of the effect of hydrostatic pressure to 20 kbar on the A, temperature of an Fe-28.4 at. pct Ni-0.5 at. pct C alloy. The composition is similar to the alloy used by Pate1 and Cohen3 to determine the effect of pressure upon the M, temperature. The present measurements permit calculation of the interaction between the applied pressure and the transformation strain. Additionally, measurements have been made which allow precise determination of the gross volume change of the transformation. The data allow direct comparison between the alternate hypotheses of the interaction between the applied pressure and a dilatational transformation strain characterized by either the formation

Jan 1, 1970

By C. K. Leith

THE purpose of these conferences has been to find some basic principles to guide us in the chaos which confronts us, to arrive at elements of a national policy. None such exists, nor, as a matter of fact, have there been any concerted efforts by the public or the mineral industry to evolve one. In the absence of such a policy the administrative agencies of the government can hardly be expected to be consistent or really effective in their handling of mineral problems, domestic or foreign. Basic Facts MINERAL reserves are unequally distributed among the nations. The principal world supplies are grouped around the north Atlantic, and nearly three-fourths of the world's total is controlled politically and commercially by English-speaking people. No one nation has a complete supply of the minerals necessary for modern industry; specialization, reciprocity, and large-scale movements between the nations are inherent in nature's unequal distribution of them. The principal sources of supply are relatively few compared with the nations to be served-a fact which determines broadly certain natural outlines of the world flow. National isolation with regard to minerals can be accomplished only through backward steps in industry and lower standards of living even in the nations possessing the most of the mineral supplies. A certain measure of unified commercial control, international in scope, is a natural consequence of the limited number of the large sources of supply. Mineral supplies for the world as a whole are so large that there is little need for concern about early exhaustion, but every nation has important problems of early exhaustion of particular minerals, which must affect their policies.

Jan 1, 1933

By W. O. Philbrook, L. D. Kirkbride

IN the normal operation of the iron blast furnace, reduction of the iron oxides is accomplished almost entirely above the tuyeres.' Blast furnace slags usually contain less than 0.5 pct FeO, although higher values may occur with abnormal operation. There is reason to conjecture, however, that incompletely reduced ore may sometimes reach the hearth and enter the slag as a result of heavy slips or, perhaps, even from cores of excessively large lumps of a charge material of poor reducibility. The possibility of reoxidation of iron droplets falling in front of the tuyeres has been considered by several writers. It would be of interest, to know how rapidly iron oxides reaching the slag for any of these reasons could be reduced by reaction with coke or with the high carbon liquid iron in the hearth. In comparison with the hundreds of papers that have appeared on various aspects of the reduction of solid iron oxides by gases and in the presence of several forms of carbon, little work has been published on the reductioin of liquid oxides or slags. Dancey measured rates of reaction of the pure liquid oxides, both FeO and Fe,O,, with molten iron containing about 4.3 pct C. The oxide was dropped into the cup formed in the upper surface of the iron by rotating the crucible and melt. Under these conditions, reduction of either FeO or Fe,O., was completed in less than 10 sec. The present study was concerned with the reduction of FeO from blast furnace-type slags containing less than 5 pct FeO and melted over carbon-saturated iron in stationary graphite crucibles. The results were considerably different from those found by Dancey, as will be discussed later. Although this work is of interest in relation to hearth reactions in the blast furnace, interpretations must be made with caution because the experimental conditions do not duplicate those within a furnace and may not even lead to the same reaction mechanism. The authors were motivated in undertaking this work by an additional interest—the part played by FeO reduction in the mechanism of de-sulphurization of iron by slags under similar experimental conditions. Derge, Philbrook, and Goldman eveloped detailed experimental evidence to support a three-step mechanism for desulphurization like that originally proposed by Holbrook and Joseph' (These reactions are written in molecular form for convenience, but this is not intended to imply the existence of molecules of FeS in the bulk metal phase nor to deny the likelihood of ionic reactions in the slag.) Earlier work by Chang and Goldman" had shown that the overall reaction follows first-order kinetics with respect to sulphur and that the rate of reaction is proportional to the slag-metal interface area, which observations have been confirmed by subsequent work. Later studiese,' have established the influence of al.loying elements on the first and last steps of the reaction. This paper reports a study of step 3 alone, uncomplicated by the simultaneous process of sulphur transfer. Apparatus and Procedure The experiments were made in a conventional high frequency induction furnace powered by a 35 kva Hg spark gap converter. The graphite crucibles used for most of the runs were 14 cm (5.5 in.) deep and 4.8 cm (1.9 in.) ID with 0.75 cm (0.3 in.) wall. An insulating cover with a small opening for withdrawing samples was used to minimize heat loss and infiltration of air into the furnace. The crucible was charged with 300 g of carbon-saturated iron and either 65 or 100 g of prefused slag analyzing 38.0 pct SiO,, 15.4 pct A10 and 47.1 pct CaO. To obtain the cleanest possible interface at the start of the reaction, the metal and slag were brought to temperature together to prevent the rejection of kish graphite that would have been caused by the chilling effect of a large addition of cold slag to carbon-saturated iron. After temperature control had been established, the desired amount of iron oxide was added in the form of a prefused slag of composition 73.6 pct FeO, 7.7 pct AWX and 19.0 pct SiOl. This slag addition was observed to be molten in somewhat less than 1 min, and a very vigorous reaction proceeded for 1 to 2 min after its introduction. Zero time was taken as 2 min after the ferrous silicate slag addition. Slag samples weighing about 0.5 g each were taken periodically by a copper chill sampler." The weight of the initial slag was large relative to the weight of samples removed, so that the slag weight never varied by more than 5 pct during any run. Temperature was measured by a calibrated W/Mo thermocouple immersed in the metal, with a graphite tip cemented over the fused silica protection tube to prevent attack by slag and metal. After some difficulties with uncertain temperatures during the first two runs, the practice adopted to position the thermocouple for reproducible results was to lower the protection tube to touch the bottom of the crucible and then raise it 0.5 cm. The apparent temperature gradient between the bottom of the crucible and the top of the slag was found to be 15°C (27°F). but much of this spread was probably the result of inadequate immersion of the protection tube to off-set conduction losses along the graphite tip when the thermocouple was inserted only into the slag. The temperature of the bath was controlled within 25°C (9°F) during a run.

Jan 1, 1957

By Charles T. Holland, David A. Olsen

Considerable work has resulted in the development of a formula by which the strength of coal pillars for an L to T ratio of up to 12 may be estimated. One of the factors involved in this formula is the coefficient of friction between the coal pillar and the adjacent rock with which it is in contact. This paper presents the results of studies on sandstone, limestone, shale and coal and the coefficient of friction between coal and the other three under wet and dry conditions. With the coefficients of friction thus determined and the use of results obtained earlier by Meikle and Holland, it seems probable that coal pillar strength may be more closely estimated. Several investigators1-3 have found that the com-pressive strength of cubical coal specimens can be correlated by an equation such as

Jan 1, 1969

By Walter S. Lutz, J. T. Griffith

The rainfall during the last six months of 1942 in Scranton and vicinity was 24.06 in.—only 4.35 in more than the average for this district in any equivalent period—yet that rain forced The Hudson Coal Co. to handle 38.8 tons of water for every ton of coal mined. It filled to overflowing, or to a higher level, 14 flooded mine areas holding, in total volume, 8.3 billion gallons of water in storage; brought about a pumpage of 11.4 billion gallons in the months of December 1942 and January, February and March 1943 Half of the total energy generated or purchased (44,322,980 kw-hr.) was required to keep the mines sufficiently free of water to permit the mining of coal during a period of much needed output. Fig. I shows the extent to which this flooding of exhausted and idle properties has proceeded, and is known to be proceeding further, at the upper end of the Northern field. This rainfall (24.06 in.) means 80,559,444 tons of water on approximately 46.2 sq. miles of area tributary to the pumping plants. During the high rainfall period, 72,687,661 tons went underground, being pumped at the stations in this territory. This means an inflow of 88per cent, a runoff of 12 per cent compared with 64 per cent during normal conditions in a normal region. During this period no floods, either surface or underground, had to be dealt with, although the streams and rivers were high on several occasions. In general, the rainfall for the first three months of 1943 can be described as heavy but not abnormal.9 These figures not only indicate the large volumes of water to be handled but, by their very size, they also emphasize that the mine-water problem is not to be conquered, at least from an economical standpoint, by merely buying and installing more and more pumps. Into the solving of this water problem must go much planning, adhering to the principle of keeping the highest percentage of water at the highest possible level for the longest period of time; the storage of huge volumes in sumps capable of being reduced after the flood inflow and at rates less than the inflow; plans for prevention of surface inflow; provision of the minimum of pumping capacity arranged to as nearly 100 per cent pumping load factor as is possible; intercompany joint pumping plants; the conducting of water from one plant to another and from one property to another over distances measured in miles; priorities in power to the threatening situations; and. balance of the necessities and dangers existent in one colliery over another, day by day, when quantities of water are running high. Despite these astronomical figures of water volumes, their disposal to the surface is accomplished reasonably cheaply because, although the annual cost of $575,020 is a large sum, the cost per ton is about 0.1168 cents. Credit for this goes

Jan 1, 1947

By J. T. Griffith, Walter S. Lutz

The rainfall during the last six months of 1942 in Scranton and vicinity was 24.06 in.—only 4.35 in more than the average for this district in any equivalent period—yet that rain forced The Hudson Coal Co. to handle 38.8 tons of water for every ton of coal mined. It filled to overflowing, or to a higher level, 14 flooded mine areas holding, in total volume, 8.3 billion gallons of water in storage; brought about a pumpage of 11.4 billion gallons in the months of December 1942 and January, February and March 1943 Half of the total energy generated or purchased (44,322,980 kw-hr.) was required to keep the mines sufficiently free of water to permit the mining of coal during a period of much needed output. Fig. I shows the extent to which this flooding of exhausted and idle properties has proceeded, and is known to be proceeding further, at the upper end of the Northern field. This rainfall (24.06 in.) means 80,559,444 tons of water on approximately 46.2 sq. miles of area tributary to the pumping plants. During the high rainfall period, 72,687,661 tons went underground, being pumped at the stations in this territory. This means an inflow of 88per cent, a runoff of 12 per cent compared with 64 per cent during normal conditions in a normal region. During this period no floods, either surface or underground, had to be dealt with, although the streams and rivers were high on several occasions. In general, the rainfall for the first three months of 1943 can be described as heavy but not abnormal.9 These figures not only indicate the large volumes of water to be handled but, by their very size, they also emphasize that the mine-water problem is not to be conquered, at least from an economical standpoint, by merely buying and installing more and more pumps. Into the solving of this water problem must go much planning, adhering to the principle of keeping the highest percentage of water at the highest possible level for the longest period of time; the storage of huge volumes in sumps capable of being reduced after the flood inflow and at rates less than the inflow; plans for prevention of surface inflow; provision of the minimum of pumping capacity arranged to as nearly 100 per cent pumping load factor as is possible; intercompany joint pumping plants; the conducting of water from one plant to another and from one property to another over distances measured in miles; priorities in power to the threatening situations; and. balance of the necessities and dangers existent in one colliery over another, day by day, when quantities of water are running high. Despite these astronomical figures of water volumes, their disposal to the surface is accomplished reasonably cheaply because, although the annual cost of $575,020 is a large sum, the cost per ton is about 0.1168 cents. Credit for this goes

Jan 1, 1947

By J. T. Norton, J. G. McMullin

An 1820°C isothermal cross section of the Ti-Ta-C ternary diagram was prepared from X-ray diffraction and metallographic data. No phases other than those appearing in the three binary diagrams were observed. At temperatures above the titanium transition temperature titanium and tantalum form a complete series of solid solutions containing up to 2 atomic pct C. The phases Tic and TaC also form a continuous series of solid solutions extending across the diagram. PREVIOUS work on this alloy system was very limited. Of the three binary constitution diagrams involved, only one, the Ta-C system was available in the literature. Preliminary data on the other two systems was received from the investigators during the course of the investigation and both have been published in recent months. It had been shown that Tic and TaC formed a continuous series of solid solutions, but the range of carbon content in this phase was not known. While Ta2C had been described, its solubility for or reactions with other carbides had not been reported. It was not known whether or not any ternary compounds occurred in the system. The present program was undertaken to determine experimentally the general form of the ternary diagram. It is hoped that the results will be of value in furthering the development of sintered carbide cutting materials and high temperature ceramets, many of which contain combinations of Tic and TaC. The Binary Systems Of the three binary diagrams involved only that of Ta-C was available at the time this project was started. The diagram of Ellinger¹ redrawn in Fig. 1, shows a hexagonal phase Ta2C having a very small composition range and a cubic TaC phase having a composition range of from 40 to 50 atomic pct C. The authors made a separate determination of the composition range of TaC using lattice constant values and found the range to extend from 40 to 49.7 atomic pct C in good agreement with Ellinger's diagram. Two determinations of the Ti-Ta system have appeared recently.2,3 These two diagrams are in good agreement and show that ß titanium and tantalum form a complete series of solid solutions. The Ti-C diagram by Cadoff and Nielsen4 shows a very limited solubility of carbon in both a and ß titanium. The single carbide formed persists over a wide range of carbon contents. Several values for the upper limit of carbon content of this phase have been reported."' The highest value obtained in the M.I.T. Laboratory was 47.5 atomic pct C with a lattice constant of 4.328?.5 Fattinger7 describes a gas carburization method which he claims produces stoichiometric Tic although he does not present any data showing that he actually had 50 atomic pct combined carbon. Several complete analyses on

Jan 1, 1954

By E. M. Cox, T. Rosenqvist

IN a recent investigation, carried out at the Institute for the Study of Metals, the affinity of sul-phur for iron, copper, and manganese was studied over the temperature range 700" to 1300°C.' It was found that copper exhibits a rather high affinity for sulphur, especially at higher temperatures; and attention was called to the possibility that copper when present together with sulphur in liquid steel would tend to lower the chemical activity of sulphur and thus interfere with the desulphurization process. It was clear, however, that the data for the equilibrium between pure copper and pure copper sulphide (Cu2S) could not give any quantitative information about the effect of copper when dissolved in liquid steel. The present work is concerned with the activity of sulphur in the diluted range of the binary iron-sulphur system, and with the influence of small amounts of copper on this sulphur activity. This investigation is in principle based on the same method previously described for the binary metal-sulphur studies;1,2 namely, reaction with hydrogen to form hydrogen sulphide. The equilibrium ratio PH2s/Ph2 in the equilibrium gas mixture is, for a given temperature, directly proportional to the sulphur activity. The activity of sulphur in liquid iron has previously been studied by Chipman and Ta Li,3 White and Skelly,4 and recently by Sherman, Elvander, and Chipman.5 Morris and Williams6 have studied the effect of added silicon, and Kitchener, Bockris and Liberman,7 and recently Morris and Buehl,8 the effect of added carbon on the sulphur activity. In present day steelmaking processes the steel bath contains between 0.01 and 0.1 pct sulphur, and the copper content may be as high as 0.5 pct. The equi-librium gas ratio (H2S/H2) would, for such a low-sulphur content, be too low to be measured with the experimental technique we use. It has been shown by previous investigators that the H2S/H2 ratio is closely proportional to the sulphur content up to about 1 pct sulphur. The sulphur activity at very low-sulphur content can therefore be calculated by linear interpolation between 0 and 1 pct sulphur. In order to show the general trend with increasing sulphur content, the present work has been carried out to about 3.5 pct sulphur. As the effect of copper was assumed to be more a function of the Cu/S ratio than of the absolute copper content, the runs with copper were made for certain constant values for this ratio.

Jan 1, 1951

By W. R. Johnson, M. Hansen, John M. Parks

AS part of a research project sponsored by the Signal Corps Engineering Laboratories, which had the objective of obtaining a magnet wire of good conductivity and low temperature coefficient of resistance, a comprehensive literature survey, supplemented by experimental work, revealed that a linear relationship exists for solid-solution alloys between the electrical conductivity, K, and the temperature coefficient, a, as expressed by the equation: k = a/ß where ß is constant for the solvent metal and a - per°C. tR0 It has long been known that the electrical conductivity at a given temperature and the temperature coefficient of resistance of binary alloys are related to their constitution by the LeChatelier-Guertler rules, as illustrated by Figs. 1 and 2: Rule 1—In alloy systems consisting of a heterogeneous mixture of two phases, the electrical conductivity and temperature coefficient vary as a straight line, if the composition of the alloys is given in volume percentage, Fig. 1. Rule 2—In solid solutions, the electrical conductivity and temperature coefficient are always lower than those of the solvent metal, and usually a considerable decrease occurs with the first small percentage additions of the solute metal, Fig. 2b. If the two components form a continuous series of solid solutions, the electrical conductivity and temperature coefficient curves take the form of a U-curve, Fig. 2a. That some kind of proportionality exists between electrical conductivity and temperature coefficient of resistance is implied by the LeChatelier-Guertler rules and by study of data such as those given by Smith and Palmer,' Fig. 3. Dellinger2 in 1910 first recognized this relationship in a number of commercial copper wires, ranging in conductivity from 94 to 100.7 pct I.A.C.S. He gave the ratio of temperature coefficient to the percentage of conductivity as a constant, C = 0.003939. A year later, Lindeck observed that the linear relationship was valid for a wider range of conductivity in "various sorts of copper," and concluded that the product of resistivity and temperature coefficient was 6.78x10-5 1.5 pct. Since then, this relationship seems to have been entirely ignored. Conductivity-Temperature Coefficient Relationship If the electrical conductivity of copper solid-solution alloys with phosphorus, silicon, arsenic, antimony, aluminum, nickel, manganese, and iron is plotted against the temperature coefficient of these alloys, the diagrams in Figs. 4 and 5 are obtained. Similar data were found with copper-rich solid solutions containing magnesium, cobalt, and titanium,'" as shown in Fig. 6. In all cases, a linear relationship exists. The point representing the highest

Jan 1, 1952

THERE is at least one concrete indication that Soviet Russia's two most important iron ore producing centers are seriously depleted. While keeping in mind Russia's penchant for reverse propaganda, one piece of evidence indicates that Magnitugorsk in the southern Urals and Krivoi Rog in the Ukraine have been mined to a point where lower grade ores are being recovered. An article in Pravda, Soviet newspaper, by I. P. Bardin. a Russian metallurgist, says that ore presently mined must undergo an expensive enriching cycle before it can be used in blast furnaces. Com- pounding Russian metallurgical troubles is the low quality of coking coals. High ash and sulphur content typifies the coal Badin talks about. Coal from the Ukraine, Eastern Siberia, Kazakhstan, and the Far East requires extensive treatment before it can be used, according to the article in Pravda.

Jan 7, 1953

By D. B. Williams

For the first time in the history of the Venezuelan petroleum industry production exceeded 200 million barrels. The total production for all fields amounted to 205,430,869 bbl., which is more than 9 per cent of the world's 1939 total. This is an increase of over 15 million barrels or 8.0 per cent above the 1938 figure, which, compared with the slightly less than 2 per cent increase of the 1938 figure over 1937, shows the marked activity in Venezuela during the past year. The Maracaibo Lake fields are still the predominating factor in Venezuelan production, showing an increase of approximately 9½ million barrels over last year's figure and accounting for 71.8 per cent of Venezuela's total. Lagunillas continues to hold precedence as a single field, having yielded 47.1 per cent of the accumulative total and 39.4 per cent of 1939's total. This field showed an increase of slightly more than 3½ million barrels over 1938. Tia Juana, the second largest field, attained a record production, increasing its percentage of the Venezuelan total from 23.4 in 1938 to 23.7 in 1939. The La Rosa field, which includes Punta Benitez and Ambrosio, declined from 13.7 to 12.0 per cent; Bachaquero, the southernmost Lake field, which came into regular production at the end of 1938, contributed over 31/3 million barrels. Quiriquire, in eastern Venezuela, ousted La Rosa as the third largest producing field, and, although production increased by 11/3 milliorl barrels, percentage of the total declined from 13.2 to 12.9. Mene Grande, the oldest field, declined from 6.6 per cent in 1938 to 5.9 in 1939. Tem-blador produced for a whole year for the first time and yielded 3,647,867 bbl. The Colon district, in the Maracaibo Lake area, comprising the Tarra-Los Manueles fields, showed slight increases, as also did Cumarebo and Pedernales. Construction of the 16-in. pipe line from Oficina to Puerto La Cruz (Guanta), the longest line of this size in the world, was completed toward the end of the year and this new field in eastern Venezuela started shipping oil in December. This field is operated by the Mene Grande Oil Co. and was credited with a production of 2,347,625 bbl. in 1939. Jusepin field, some 25 miles southwest of Quiriquire in eastern Venezuela,

Jan 1, 1940

By D. B. Williams

For the first time in the history of the Venezuelan petroleum industry production exceeded 200 million barrels. The total production for all fields amounted to 205,430,869 bbl., which is more than 9 per cent of the world's 1939 total. This is an increase of over 15 million barrels or 8.0 per cent above the 1938 figure, which, compared with the slightly less than 2 per cent increase of the 1938 figure over 1937, shows the marked activity in Venezuela during the past year. The Maracaibo Lake fields are still the predominating factor in Venezuelan production, showing an increase of approximately 9½ million barrels over last year's figure and accounting for 71.8 per cent of Venezuela's total. Lagunillas continues to hold precedence as a single field, having yielded 47.1 per cent of the accumulative total and 39.4 per cent of 1939's total. This field showed an increase of slightly more than 3½ million barrels over 1938. Tia Juana, the second largest field, attained a record production, increasing its percentage of the Venezuelan total from 23.4 in 1938 to 23.7 in 1939. The La Rosa field, which includes Punta Benitez and Ambrosio, declined from 13.7 to 12.0 per cent; Bachaquero, the southernmost Lake field, which came into regular production at the end of 1938, contributed over 31/3 million barrels. Quiriquire, in eastern Venezuela, ousted La Rosa as the third largest producing field, and, although production increased by 11/3 milliorl barrels, percentage of the total declined from 13.2 to 12.9. Mene Grande, the oldest field, declined from 6.6 per cent in 1938 to 5.9 in 1939. Tem-blador produced for a whole year for the first time and yielded 3,647,867 bbl. The Colon district, in the Maracaibo Lake area, comprising the Tarra-Los Manueles fields, showed slight increases, as also did Cumarebo and Pedernales. Construction of the 16-in. pipe line from Oficina to Puerto La Cruz (Guanta), the longest line of this size in the world, was completed toward the end of the year and this new field in eastern Venezuela started shipping oil in December. This field is operated by the Mene Grande Oil Co. and was credited with a production of 2,347,625 bbl. in 1939. Jusepin field, some 25 miles southwest of Quiriquire in eastern Venezuela,

Jan 1, 1940