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By W. D. Robertson, J. -P. Briant, M. Gell

The distribulion of dislocatiorls genevnted during the propagalion of hydrogen-induced cracks in Fe-Si cryslcrls was studied as a funclion of temperature f-110o lo 243°C) and silicorz conlenl (3.1 and 4.2 pct). It zoas found that the clislocntiotl densily and the size of the plctslic zone increased with increasing tempevalnre and decreasing silicon conlent. Furtheruvzove, there was a correlcrtion in the dislocalion patterns formed around cracks that propagated at different tempevattrt-es in cvyslals of diffevent silicon contents such that a 1 pcl itlcverise in silicon content was equivalent to a lemperaluore redziclion of approximately 120°C. The experimenlal YeSnllS were compaved with the results of an elastic-plastic wodel that relates the size of the pluslic .zone to the cvack length, internal pressure, and yield stress. it was found that the clzunges in the dislocctlion cryrays with lemperature and combosition can be e-kplaincd by the lemperatrnre and composilion dependence of the yield stress. An wmtsual feature of this study was the observation of low -temperature noncrystrrllogruphic cracks. PLASTIC relaxation can occur at the edge of a moving crack by the operation of pre-existing dislocation sources or by the creation of new sources in a region of perfect 1attice.l'2 The amount of relaxation in a given crystal depends on the crack velocity and the temperature, and can determine whether a crack propagates in a brittle or a ductile manner.1-3 Tetelman and Robertson4 observed microcracks m Fe-3 pct Si single crystals that formed on (100) planes by the precipitation of hydrogen gas during electrolytic charging at 23°C. The plastic deformation accompanying crack propagation was observed in the form of dislocation etch pits and an extensive analysis has been made of the size, shape, and crystallography of the dislocation arrays5-7 This paper describes the effect of temperature on the plastic deformation generated around hydrogen-induced cracks in Fe-3.1 pct Si and Fe-4.2 pct Si single crystals. The observations are compared with the results of an elastic-plastic model for yielding around a crack containing an internal pressure. 1) EXPERIMENTAL PROCEDURES The composition of the materials used in this study are given in Table I. Single crystals of alloy A and the 4.2 pct Si alloy were grown by the strain-anneal method; crystals of alloy B and the 5.1 pct Si alloy were cut from an ingot grown from the liquid. he ~ingle-cr~stal metallographic specimens had a Cross section of 0.100 by 0.050 in. with a length of at least 3/8 in. Specimens were annealed for 3 hr at

Jan 1, 1968

By A. J. Opinsky

ThE superior performance of nonsag tungsten wire in lamps has been ascribed to the large-grained micro-structure that can be developed in it. The orientations of these large grains have been studied several times; most published data1-' appear to be similar to those plotted in Fig. 1. These new data were obtained by X-ray back-reflection Laue technique from all of the large grains occurring in thirteen different wires that had been heated at the lowest possible temperature for the formation of large grains. Here the wire axis is plotted in terms of the principal directions of the cube. Rosi decided that the preferred orientation of the large crystals could be described by a single ideal orientation, (531), being parallel to the wire axis.' Rieck2,3 and Mannerkoski' have essentially confirmed this finding. Opinsky, Orehotsky, and Seigle argued that the data suggest that (211) is parallel to the wire axis instead of a single ideal orientation.5 This {211} contains the (531) ideal orientation and would appear to be a more general case. Ahlborn and Wassermann report that their orientation data stretch from ( 110) through (531) to (311) 8 This is part of the locus of (211). All these investigators have determined the orientations of the large grains by back-reflection Laue techniques. They have all obtained essentially similar results. On the other hand, Swalin and Geisler, who obtained their data by neutron diffraction, indicated that the preferred orientation of the large grains in doped wire is (110) .7 These findings cannot presently be reconciled with the pole density data described in the previous paragraph. Rosi1 and Rieck2 have advanced arguments about how their orientations could occur. Nevertheless, the crystallographic link between the (110) (cold-worked) fiber texture and the preferred orientation of the large grains has remained missing. This link can be provided through the concept of coincidence-type boundaries. Such boundaries separate two grains that have a certain number of common lattice sites. Coincidence relationships that result from rotations about low index directions are given by Brandon et a1 .' What is desired is a calculation of those orientations that bear a coincidence relationship with the (110) fibers of the cold-worked matrix. This situation arises in the following fashion. Heating the tungsten wire for a combination of time and temperature falling short of the formation of the nonsag structure yields a structure that is still fibrous in nature and the preferred orientation remains (110). During grain growth, the growing grain is in contact with these fibers. It is hence possible that the entire process may begin by the passage of a coincidence boundary into a (110) fiber. The calculations were carried out analytically and checked graphically. Following Brandon et a1.,8 coincidence relationships from 1 in 5 to 1 in 19 have been considered. The results of the calculations are given in Fig. 2. Of the coincidences examined, some of those occurring upon rotation about ( 110) come closest to the experimental points in Fig. 1. Nineteen of the twenty-three data points in Fig. 1 can be attributed to the ideal orientations A, B, C, and D in Fig. 2. As determined analytically, three crystals lie within 4 deg of point A, four lie within 21/2 deg of point B, eleven lie within 5 deg of point C, and one lies within 1 deg of point D-a total of nineteen. The off-lying points are near the |110| point of the triangle.

Jan 1, 1968

By Lawrence P. Bonicatto

The steel industry's increased demand for higher grade pellets has caused the pellet producers to investigate methods of upgrading their product. The Hanna Mining Company's Groveland plant is no exception. The Groveland Mine is located in Dickinson County on the Upper Peninsula of Michigan. The low grade iron deposit is a complex mixture of magnetite and hematite with chert, quartz, jasper, and various iron silicates. (1) Beneficiation is by Humphrey spirals and anionic flotation of the iron minerals. (2) A general flowsheet is shown in Figure 1. Flotation of the spiral tailings makes up about 75% of the concentrate. A minor amount of concentrate, less than 3%, is produced in magnetic circuits. The concentrate is pelletized at the rate of 1.6 million tons per year.

Jan 1, 1968

By N. A. D. Parlee

THE gas-liquid metal diffusion cell technique1-3 has been used to study the diffusion of nitrogen in Fe-C alloys. The actual apparatus and technique were the same as employed by the authors to study the diffusion of hydrogen in liquid iron.' The diffusion cell' was formed by immersing an alumina tube in a stagnant melt contained in an alumina crucible. The tube (hereafter called absorption tube) contained nitrogen gas at 1 atm and was connected to a sensitive gas-measuring system. The change in the average concentration of nitrogen in the melt in the absorption tube was determined by measuring the rate of absorption of nitrogen in the diffusion cell. Eq. [I], 1-3 derived from the appropriate solution of Fick's second law, was used to examine the data and to calculate chemical diffusion coefficients (D) in situations where the absorption appeared to be controlled by diffusion in the liquid: where V is the stp volume in cu cm, d is the diffusion cell diameter in cm, p, is the density of the melt in g per cu cm, pg is the stp density of nitrogen in g per cu cm, C, is expressed in wt pct, D is in sq cm per sec, and t is in min. According to Eq. [I], a plot of v vs vt should yield a straight line passing through the origin if absorption is controlled by diffusion in the liquid. The slope of this line could be used to determine the value of D under appropriate conditions. As discussed in earlier reports,1,2 the initial thermal expansion of the gas upon immersing the absorption tube distorts the line in the initial stages of a diffusion experiment. However, this is not a serious problem since the slope of V vs 6 plots can be determined from the data points obtained after the initial expansion ceases. The volumes reported on the data plot presented here represent absorption after this thermal expansion ceased. Several preliminary diffusion experiments were attempted with melts of pure iron and with Fe-C alloys containing up to 0.6 pct C. In these cases, no or very little absorption was observed. The only data obtained were for an Fe-C melt which was in addition thoroughly deoxidized by successive hydrogen and vacuum-degassing treatments. These treatments introduced an appreciable amount of aluminum into the melt and reduced its omgen content. The original charge material for this melt contained 0.23 pct s and approximately 0.001 pct &. After repeated hydrogen and vacuum-degassing treatments two diffusion experiments were performed. The analysis of the melt

Jan 1, 1968

By R. C. Gifkins, K. U. Snowden

The value of the index n in power ktivs for the stress sensitivity of minimum creep rale at lead is derived front results drawn from lite literature and from previously unpublished nork on commercial (99.99 pel) and high-purity (99.999 pel) lead polycryslalline and hi crystal specimens. In tests al 0.5Tm (22 to 50'C) for slvesses below 250 psi, n fulls to mily for poly-cr,yslullirle specimens, single crystals, and bicrystals, and toy grain boundary sliding in bicrystals. Between 250 and 500 psi there is a tyansilion range and, for the polycrystalline specimens al least, u high-stress regime for 500 to 1500 psi where n is 5 or 6. These results are such that none of the suggested stress taws can he used to extrapolate to very loir stresses. Meclianisms for deformation in Ike grains and toy grain boundary sliding in the low-strcss regime are outlined. In particular, the mechanism for grain boundary sliding involves sliding controlled by diffusion from tensile to compressire Ledges. predictions based on this model give promising numerical agree-nicul with experiment. II is suggested that the mechanism for grain boundary sliding may he important in other circumstances, e.g., in creep of ceramic materials or superplaslicity, because it can operate with lille or no dislocation aclirity. WhEN the stress dependence of secondary creep rate is represented by a power law the values taken by the stress exponent n are found to vary between 1 and 7, see, c.g., Garofalo.' In Eq. 1 11 u is the applied stress and A a constant. The case for accepting values of v = 1 rests principally upon tests at high temperatures (>0.9Tm) and there have only been isolated tests at lower temperatures (rather than plots of creep rate against stress) for which the creep rates are such that some form of Nabarro-Herring creep with n = 1 is applicable. Hanson5 and Greenwood and cole6 plotted creep rate against stress for tests made in the vicinity of 0.5Tw, and found a "creep yield", so that below a certain low stress the creep rate was linearly related to stress: these observations appear to have been subsequently ignored. Various models have been proposed which agree with a large body of experimental results in which n equals -5 at high stresses (e.g., weertman7 and McLean8). Various alternatives to Eq. [1] have been proposed principally as a means of unifying creep data, but sometimes, it seems, in order to obviate the necessity for assuming a series of regimes of deformation associated with the various values of n; further refer- ence to these will be made in the section on stress laws. This paper calls attention to extensive results which show n = 1 for the creep of lead at room temperature (0.5 T,). RESULTS Fig. 1 is a composite diagram based on figures in the literature6,9,10 with additional results obtained by the present authors and their colleagues11,12 in the course of a number of investigations not directly concerned with stress sensitivity. In Fig. 1 In creep rate is plotted against In stress. The curves show results for two kinds of material. Lead I is of commercial purity (99.99 pct Pb) and lead IT a specially refined material, hydrogen-purified to remove oxygen; it contains 99.999 pct Pb. Curve A is for lead I in polycrystalline form (grain diameter 0.02 to 0.05 cm) at room temperature (22' to 26°C). Curve B1 is for lead I, polycrystalline, tested at 50C. Curve B2 is for lead 11, polycrystalline (grain diameter 0.02 cm), tested at room temperature (22 O- Curves C to F relate to tests made of bicrystals of lead 11: all of the same nominal orientation ("Y" in Ref. 12). Curves C and V are for creep within the component crystals of the bi crystals at 22°C (AB and CD in Fig. 2). Curve E is for creep measured in a gage straddling the boundary, approximately 0.15 mm either side (BC in Fig. 2). Curve F shows rates of grain boundary sliding (as distinct from strain rates in the other curves), obtained by averaging the offsets of six marker lines on the bi-crystal boundaries. The principal feature of the results is that the stress sensitivity falls into two distinct regimes, according to whether the stress is below approximately 250 or above 500 psi (there is a transitional range between 250 and 500 psi). The new result is that below -250 psi two of the curves (A and BI) give a value of n 1, and the other curves also drop below n - 2 to -1.5 but do not extend to low enough stresses to show clear evidence of n 1. At very high stresses the curves tend to give values of n - 6, as previously determined in other investigations. Curve R2 for the high-purity lead in polycrystalline form at room tenlperature almost merges with B, and thus gives new significance to the values for stresses of 150 and 200 psi; previously'3 these points had seemed to fall away from the curve of slope -3, but they now can be seen as almost completing a transition to n = 1. It should be noted that there was originally considerable apparent scatter in the results for the high-purity lead. However, this was found to be associated with annealing conditions or variations in residual content of oxygen and curve B2 was constructed using the highest rate (i .e., the rate for the purest lead) determined for each stress during the course of various investigations over the years: altogether, some forty tests were used in constructing curve R2.

Jan 1, 1968

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na' and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°'K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°'K and

Jan 1, 1968

By G. Y. Chin, M. T. Dolan, W. L. Mammel

In the case of plastic deformation by slip, von Mises&apos; showed that an arbitrary shape change of a crystal generally requires the activation of five independent slip systems. The selection of the five active systems was worked out by Taylor ,&apos; who hypothesized that, among all combinations of equivalent slip systems which are capable of accommodating a given imposed strain, the active combination is that one for which the sum of the absolute values of the glide shears is a minimum. Taylor analyzed the case of {lll}( 110) slip for fcc metals and applied the analysis to crystals undergoing axisymmetric flow, which approximates the shape change of an embedded grain in a polycrystalline aggregate deformed in tension (or compression). For the twelve equivalent (111) (110) slip systems, there are 384 independent combinations of five slip systems that satisfy the imposed strain.&apos; Taylor laboriously calculated the value of M = ZjIyj /E for each combination (although some were missed) and obtained the minimum M, hence the active combination, for a number of axial orientations distributed throughout the stereographic triangle. (yj is shear from slip on the th system and e is the tensile strain). Detailed contours of constant minimum M were recently obtained by Hosford and Backofen using a simplified but equivalent Bishop and ill&apos; analysis. Due to the numerous combinations of slip systems involved in the calculations, however, the full potential of the powerful Taylor analysis has not been exploited. For this reason, we have recently utilized techniques of linear programming to obtain solutions of the Taylor analysis for axisymmetric flow, for slip on {110)(< 111), {112)(111), and {123)(111) systems as well as mixed slip composed of these three systems. These slip modes are of obvious importance in the deformation of bcc crystals. Some of the salient results are summarized below. 1) Stress-Strain Data for Polycrystal. The value of M averaged over all axial orientations is the ratio of the tensile flow strength of a randomly oriented aggregate to the critical resolved shear stress for slip. This value enters importantly in theoretical deductions of the polycrystalline stress-strain curve from single-crystal data.2&apos;3&apos;5 Table I lists the values of Ma,, for the several cases of slip, as obtained by the present computer work. 2) Texture Hardening. Since the value of M depends on the axial orientation, the (tensile) flow strength of a specimen may be increased through texture control.&apos; An example of the computer results is shown in Fig. 1, where contours of minimum M have been computer-plotted for the case of mixed slip on {110}(111), {112)(111),and {123}(11 1) systems. It may be seen that, under axisymmetric flow, wires of (111) and (110) axial orientations are 50 pct stronger than those oriented at (100) .

Jan 1, 1968

By E. A. Rychkun

With the aid of modern computer automation, certain mathematical techniques are easily adapted to geophysical, geochemical and geological data analysis. First and second derivative filtering (or transformation) of raw data, in many cases, gives a better indication of anomalous conditions than conventional methods of analysis. The calculations involved, which are tedious manually, are simple, accurate and fast with the assistance of Fourier analysis and modern computers.

Jan 1, 1968

By C. B. Manula

The Crushed Stone Industry plays an important role in Pennsylvania&apos;s mineral economy. During 1965, the total production of crushed and broken stone in the United States reached 780 million tons from which 57 million tons were produced in Pennsylvania (Mineral Industries Surveys, 1966). It is further significant that Pennsylvania is the nation&apos;s leading crushed stone producer. Future trends in stone production will quite likely parallel those in the construction industry. Stone and stone products are finding greater and more varied uses each year. Continued record expenditures for structures such as dams, highways and buildings are the prime reasons for this accelerated growth in demand. Completion of the interstate road system and the maintenance of Pennsylvania&apos;s already expanded highway system form the essentials for this expanding market.

Jan 1, 1968

By V. W. Buys, R. E. Havener

11.3-1. Basic Principles. Communications systems available for application to surface mining operations can be divided into basic categories. These are: 1. Wired systems requiring some type of metallic conductor 2. Nonwired systems, or those commonly referred to as space-radio systems. Under the heading of wired systems, telephones of the ringer type utilizing magnetos were used in the early pit operations. These are still being used in underground mining operations where calling is accomplished by ringing a code made up of short and long rings. While the standard Bell Telephone Systems have not been applied extensively in underground mining, they have been used in open pit operations but have the disadvantage of using multiple pair cables which must be installed and maintained as the mining operations proceed. They have the advantage however, that when a Bell System is installed in a surface mining operation, communication is available not only within the operation but to any point in the world through the facilities of the world-wide Bell Systems. A second type of communication available is the audio system or public address system requiring the use of a special audio cable made up of shielded pairs for the loudspeaker and microphone circuits. Audio systems have one outstanding advantage over most telephone systems in that, with a high-powered amplifier, a paging call can be heard over and above the high ambient noise conditions usually found at a surface mining operation. However, they have the disadvantage of requiring special cable which must be installed and maintained. Another type of wired communication system available for surface mining is that of carrier frequency equipment similar to that used in underground mining operations. In this system, transmission is accomplished by means of a frequency modulated carrier that travels over the underground trolley wire, the rail on which locomotives travel, and adjacent telephone wires.

Jan 1, 1968

By R. H. Maes, R. E. de Strycker, J. J. Jacobs

A simple method, based upow density measurements, has been perfected in order to determine the critical temperature of liquid miscibility gaps. Applied to the Pb-Cu system, it yielded a value of 980"C for the critical tempevature of the miscibility gap in this system. In the Pb-Cu-As system, the immiscibility between lead and coppev evolves towards a miscibility gap be-tween lead and copper arsenides; the liquation temperatures were determined joy different avsenic contents and values up to 1065°C were found. Combining these results with those given by the clzemical analysis of liquid samples taken at dqj.event temperatures, it has been possible to make a cowzplete determination of the liquid miscibility gap in this ternary system. In the Pb-Cu-Fe-As system, a ternary miscibility gap has been discovered; for some compositions, the molten and slowly cooled alloys separated into three layers: an Fe-As alloy, a Cu-As alloy, and a lead-rich layer. ThE Pb-Cu-Fe-As system is of interest for the study of the behavior of speiss or arsenical alloys in the lead blast furnace. The speisses produced in lead metallurgy generally have complex compositions, but they may be considered, in a simplified way, as a mixture of copper, iron, nickel, and cobalt arsenides; there is often an excess of metallic constituants, and lead is also present. Speisses liquate from lead at various temperatures according to their composition; according to industrial experience, iron speisses are already distinctly separated from lead bullion at temperatures of the order of 1100°C, whereas copper speisses only begin to liquate from lead at much lower temperatures, near their solidification points, which were never accurately determined until now. Besides these considerations of practical interest, the present study is of importance for the knowledge of liquid miscibility gaps. Particularly the data of the literature about critical temperatures of liquation are incomplete and present sometimes considerable disparities; a method has been perfected in the present work to determine these temperatures with accuracy. MISCIBILITY GAP OF THE LEAD-COPPER SYSTEM Review of Literature. The generally admitted outline of the Pb-Cu equilibrium diagram is shown by Fig. 1. This figure, with its numerical indications, is taken from the review of Hansen and ~nderko;&apos; compositions are given in weight percent, as will be the case in the remainder of this paper. Between 36 and 87 pct Pb, Pb-Cu alloys separate into two layers, in the liquid state. The critical temperature of liquation has been much disputed in earlier studies, where values up to 1500°C were claimed; but a reliable study of ~ohnen,&apos; based upon differential thermal analysis, gave a value of 990°C; this rather low value was verified by a recent study of Schiirmann and Kaune? based upon thermodynamical properties of the Pb-Cu alloys, which predicted a value of 1002°C. Liquid miscibility gaps were also studied by means of chemical analyses. Satisfactory results were generally obtained with the method consisting in taking samples of the two liquid layers in equilibrium and submitting them to chemical analysis; however, this method becomes delicate near the critical temperature. With this technique, Friedrich and waehlerts ob-

Jan 1, 1968

By E. L. Singleton

The electrochemical reduction of aluminum chloride to aluminum was investigated in a closed, two-compartment cell utilizing a molten chloride electrolyte. The externally heated cell was divided into a reduction compartment and a combination AICl3 feed and metal removal compartment. Aluminum was deposited at 700° C on a molten aluminum catbode from a KCI-NaCI-AICI3 electrolyte. The AICl3 content of the electrolyte was replenished by either vapor or solid additions. The chlorine evolved was collected and measured to give a quantitative evaluation of AICl3 reduction. The effects of anode and cathode current densities and AIC13 concentration on anode current efficiencies were studiedo A range of 64 to 84 percent anode current efficiency was obtained with the 25-pound electrolyte capacity cell and related auxiliary equipment.

Jan 1, 1968

Jan 1, 1968

By J. Hudy

The performance of six dense-medium washers was evaluated in five preparation plants. Three of the plants were making a two-product separation that produced a clean coal and a refuse; one plant employed dense-medium vessels in series to effect a primary and a secondary separation; and one plant was equipped with a two-compartment washer effecting two separations in one vessel. The separate secondary drum-type washer produced a low-ash metallurgical coal and an intermediate-ash product suitable for plant fuel or steam generation. The two-compartment washer produced a premium anthracite product and a middlings product. The sharpness-of-separation values ranged from good to excellent for the five primary separations and for the secondary separation.

Jan 1, 1968

By Horace Pops

THE martensitic transformation occurring at cryogenic temperatures in the bcc ß-phase Cu-Zn binary alloys has been discussed in a number of publication~.1-3 Addition of a second solute element to the binary Cu-Zn alloys enables the ternary martensitic phase to be stable at temperatures above room temperature, and the variation of the MS temperature with third element content has been determined recently4 for a series of Cu-Zn based alloys in which either the zinc content or the electron concentration was maintained at a constant value. The present paper describes some characteristic growth features of martensite observed in ternary alloys. Alloys were prepared by adding small amounts of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, or Sb to a a -brass Cu-Zn master alloy. Details of the melting and casting technique, homogenization, examination by cold-stage microscopy, and the determination of the

Jan 1, 1968

By William Lodding

Muscovite was the crystalline material used in the experiments discussed in this paper. It was both wet and dry ground for various periods of time. The effects (physical and chemical changes) produced in grinding are analyzed by use of thermal analysis. That grinding may change a crystalline material both in a physical and in a chemical sense has been shown by a number of authors in recent years. Mackenziel and Bartha2 reported the effects of careful grinding on muscovite, quartz, gypsum, dolomite, etc. Increase in specific surface produced by grinding implies increase in total energy of a system. Newly produced surfaces are chemically more reactive; dislocations may be introduced during grinding and, on the other hand, existing strain may be released by the same process, as shown by Holt, et a1.3 All these changes are easily detected by thermal analysis, but it is not easy to separate the multiplicity of effects registered and to arrive at quantitative interpretations. This paper is an attempt to analyze, by the use of thermal analysis, some effects produced in grinding. In differential thermal analysis (DTA) one measures the sum of all thermal changes occurring in a substance during heating or cooling; e.g., chemical changes, such as decompositions, synthesis, oxidation, reduction, etc., and physical changes such as phase transformations, changes in specific surface and thermal conductivity, strain release, etc. By thermogravimetric analysis (TGA), on the other hand, only chemical changes involving weight loss or gain are recorded. Similarly, gas evolution analysis (GEA) will register only reactions involving gas evolution. By performing two or all three of these methods of thermal analysis simultaneously and on the same specimen, one can separate the different effects registered and, by difference, evaluate their magnitude. The results of TGA are usually plotted as percent weight against furnace temp. When one differentiates weight against furnace temp, a rate of weight-change curve is obtained, and the resulting differential thermogravimetric (DTG) plots are similar in appearance to DTA thermograms for the same reaction. While the integrated area under a DTA peak represents enthalpy and can be expressed in calories per gram the area under the corresponding DTG peak represents the weight change which took place during a reaction. The similarity of DTA and DTG thermograms obtained from one material can be seen in Figs. 1 and 2. EXPERIMENTAL A Fisher mortar grinder and a porcelain mill with burundum balls were used for both dry and wet grinding. Muscovite was first carefully hand-filed and screened on 20 and 100 mesh. The middle fraction was considered essentially unaltered muscovite.

Jan 1, 1968

This paper outlines mining practice in the South Alligator valley between 1954 and 1964. The valley is situated in the Northern Territory 130 miles south east of Darwin and trends north west. The centrally located El Sherana camp is 219 miles by road from Darwin via Pine Creek on the Stuart Highway. 64 miles of gravelled road with low level bridges and culverts which were completed in 1959, connect Pine Creek with El Sherana. This road is often impassable during severe wet season conditions. Earliest recorded production was during the years 1956-57 from the El Sherana and Palette miles, by shallow open cut and cut and fill stoping from small shafts. 4600 tons of high grade ore was processed by hand sorting of massive pitchblende followed by gravity concentra- tion. At the same time 627 tons of ore was won from a small open cut at Sliesbeck 35 miles SE of El Sherana. The second and most important phase of production was to fill two small contracts with the United Kingdom Atomic Energy Authority (U.K.A.E.A.) totalling 700 tons of U 08. About 144,000 tons of ore was mined from widely separated smal&apos; orebodies and mining practice varied from small open cuts to gloryholes, open stoping and cut and fill stoping. In some orebodies a combination of several methods was employed to complete production. Final deliveries were made to the U.K.A.E.A. In 1964.

Jan 1, 1968

By E. T. Turkdogan, J. H. Swisher

The solubility of oxygen in zone-refined iron was determined in the temperature range.from 881" to 1350°C. The solubility in a iron at 881°C ms found to be about 2 to 3 ppm; in y iron, the solubility was found to increase from about 2 to 3 ppm at 950°C to about 25 ppm at 1350°C. The permeability of oxygen in an iron -0.1 pct Al alloy was determined in the y iron range, using an internal oxidation technique. By combining the permeability and solubility data, the diffzisivity of oxygen in y and a iron was calculated. The oxygen diffusivity in solid iron may be s~immarized as follows: 8820 For 6 iron and IN a recent paper, Hepworth, Smith, and Turkdogan1 reported on the solubility, permeability, and diffusivity of oxygen in 6 iron, together with permeability data for oxygen in a iron. In the present investigation, similar measurements were made in the ? phase region. In addition, a solubility measurement was performed in the a phase region to permit calculation of the diffusivity of oxygen in a, iron. References to early work on this subject are given in the previous publication.&apos; EXPERIMENTAL Solubility Measurements. The oxygen solubility was determined by equilibrating cylindrical samples 0.3 in. diam by 14 in. long of zone-refined iron in water vapor-hydrogen gas mixtures. The zone-refined iron was prepared by B. F. Oliver of this laboratory, using an apparatus and technique described elsewhere.2&apos;3 Six zone-melting passes were used to achieve a total impurity level of about 30 ppm. Of this 30 ppm, the combined nickel and cobalt content was about 20 ppm, oxygen was 4 ppm, and all oxidizable impurities less than 1 pprn each. A vertical resistance furnace wound with molybdenum wire was used for the experiments. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. In the gas train, flow rates of hydrogen and argon were measured with capillary flow meters, and the resulting mixtures were passed through a column containing 90 pct oxalic acid dihydrate and 10 pct anhydrous oxalic acid to obtain predetermined ratios of H2O to H2. The vapor pressure of H2O above this mixture as a function of temperature is well-known.4 The exit gas was ana- lyzed periodically for H2O, and good agreement (+3 pct) with the calculated composition was obtained. The zone-refined iron specimens were held in the furnace for a sufficient length of time for equilibration, e.g., 18 hr at 1350°C and 1 week at 881°C, then quenched in a brine solution. After removing the surface oxide from the samples by machining, duplicate analyses were obtained by a combined vacuum fusion-infrared method; oxygen analysis was reproducible within 2 ppm. Permeability Measurements. The permeability of oxygen in alloys containing about 0.1 pct A1 was determined by internal oxidation and measurement of the subscale thickness as a function of time. The experimental alloys were prepared by adding aluminum to electrolytic iron (grade 104A plastiron) that had previously been vacuum-carbon deoxidized. The resulting ingots contained about 20 ppm O, 100 pprn C, 40 pprn Si, 50 ppm Mo, 20 ppm P, 20 ppm S, and 20 pprn Zr as the principal impurities. After hot rolling the ingots to 1-in.-thick slabs, specimens were machined from the stock in the form of rectangular plates, 4 by 5 by 2 in. The general procedure for the permeability experiments was the same as those for the solubility measurements. The specimens were cooled in a reducing atmosphere rather than quenched, however, in order to maintain a clean surface for measurement of the sub-scale thickness. This measurement was made on a polished cross section of each specimen, using a microscope with a micrometer stage. The inclusions formed at the lowest temperature 1033°C were too small to be seen with an optical microscope. An electron micrograph showing the size and shape of individual particles is shown in Fig. 1. The dark band in the picture is a boundary between two subgrains. The subscale thickness in these samples was measured with an optical microscope after heavily etching in 2 pct nital, which gave contrast between the subscale and the unoxidized zone.

Jan 1, 1968

By W. S. Landers

This bulletin is a detailed study of low-temperature, entrained-bed carbonization of a Texas lignite. The lignite studied was from the Sandow strip mine and is representative of the Rockdale formation of the Wilcox formational group. Carbonization was conducted in a continuous entrained-bed reactor at several temperatures in the 8801 to 1,52°C F range, and at air-coal ratios it the 0 to 10.30 scf/lb range (moisture- and ash-free basis). Carbonization rates ranged from 97.1 to 410.0 lb/hr (as-received basis), At the higher air-to-coal ratios employed, all or most of the carbonization heat was provided by internal combustion with air in the reactor. At the lower air-to-coal ratios, parts of the heat for carbonization was supplied externally. It was demonstrated that the entrained-bed carbonization of lignite is a complex reaction and that several variables, of which carbonization temperature, air-to-lignite ratio, and the average size of lignite are important, act together to influence both the carbonization yields and the properties of the resultant products, Process variables established by pant tests were used to design the industrial scale carbonizer operated at Rockdale, Texas, by the Texas Power & Light Company as agents for the Aluminum Company of America. Properties of the carbonization product obtained from the industrial scale reactor were essentially the same as those obtained from the pilot plant reactor operated under the same conditions.

Jan 1, 1968

By A. J. Stosick, J. R. Hoffman, E. Rudy, St. Windisch

The binary alloy system Mo-C zoas investigated by means of X-ray, metallog/aphic, thermoanalytical, and melting-point techniques on chemically analyzed specimens. The system, Fig. 39, is characterized by three congruently melting, intermediate phases, Mo2C, n MoCi-x, and aMoC1-,, of which only Mo,C is stable at temperatures below 1650°C. Substoichio-metrzc (~32.5 at. pct C) dimolybdenum carbide undergoes a homogeneous sublattice order-disorder transformation at temperatures of approximately 1400°C, whereas hyperstoichiorrletric compositions undergo a discontinuous Phase change. The order-disorder transitions in the Me, C phases are discussed in terms of the structural changes involved in the transformation processes and the absence of long-range sublattice coherency in stoichiometric or hyperstoiclziomet-ric compositions attributed to the impossibility of obtaining long-range order in a linear chain of alternating carbon atoms and vacancies. From the experimental phase relutionships and the known thermody-namic data for Mo2 C, limits for the free energies of formation for the high-temperature phases r) MoC1-, and aMoC1-, are deriued and found to be in good agreement with data previously obtained from phase equilibria in ternary metal-carbon systems. IN the course of studies of the high-temperature phase relationships in ternary systems of refractory transition metals with carbon,&apos; a number of inconsistencies found in previous work necessitated a reex-amination of some of the related metal-carbon binaries. A reassessment of the binary system data also seemed

Jan 1, 1968