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By W. G. Pfann

Formation and slow solidification of a molten zone in a homogeneous ingot produces a discontinuity in solute concentration at the boundary of the zone and a gradient of concentration within the zone. By using two solutes, one a donor, the other an acceptor, step or graded pn barriers can be produced. EXPLOITATION of the difference in concentration between a molten solution and the solid which freezes from it is continued in this paper. The normal segregation which results from this difference has been used for purification'.'2 and for pn barrier-formation in semiconductors."4 By means of traveling molten zones this difference has been used to effect multistage separations and to eliminate segregation in ingots." a It will be shown here that by means of stationary molten zones this difference can be used to produce discontinuities in concentration. In particular it will be shown that a pn or npn barrier can be made by the simple act of melting and refreezing a portion of a block of semiconductor, provided that the block contains proper concentrations of a donor and an acceptor in solid solution. Assumptions The operation of melting and slow refreezing will be called remelting and the interface between liquid and solid at the start of refreezing will be called the remelt bormdary. While remelting may be done for various shapes of starting crystal and remelt zone it will be assumed that the remelt zone is cylindrical, its length being measured in the direction of freezing, which is normal to the remelt boundary, and

Jan 1, 1955

By M. Kaufman, D. Rosenthal

IT would be of great importance to our understanding of the phenomena of fracture in metals if a unique relationship could be established between stress and some easily measurable parameter of deformation up to the fracture. It is known that no such relationshir, has been found when the parameter was the mechanically measured strain,' the major part of which is plastic. The present investigation was initiated to determine, among other things, if the X-ray or lattice strain" might be a • For the definition of lattice strain see ref. 2. more suitable parameter. To this end, annealed stress free*' specimens of 61s aluminum alloy were ** Freedom of stress in this particular case means absence of those stresses which can be checked by the technique employed. tested at room temperature and liquid nitrogen temperature (—195OC), by first maintaining the same temperature from the beginning until the end of the test, and then with crossovers from one temperature to the other. Three major factors had to be taken into consideration in designing the specimens and testing equipment. The test setup must allow X-ray pictures to be taken while the specimen is under load (for as much as 2 hr at a given load). Provision must be made for maintaining the test specimen at the temperature of liquid nitrogen as well as at room temperature. In addition, the specimen must be able to rotate to allow the X,ray beam to take in as large a sample of grains as possible, to maintain centering, and to correct for effects of large grains. The final design of the specimen and equipment is shown in Figs. 1 and 2. The specimen and grips are hollow, enabling liquid nitrogen to be poured in through a funnel-container arrangement while the specimen is rotating. The diameter of the specimens at the 2 in. gage section is 5/16 in. with a 3/16 in. diameter hole through the center. A small pilot valve in the lower grip allows a very small stream of liquid nitrogen to escape, thus assuring circulation of the liquid at all times. A low temperature silicone grease-tissue paper packing is used to seal all joints. The specimen is held in the grips by a pin. Spherical socket joints at top and bottom are used to allow for proper alignment. The grips are connected to the thrust bearings by means of plastic couplings to decrease the heat flow. Rotation is accomplished by means of a motor which drives a plastic gear (integral with the lower coupling) through a semiuniversal joint to allow for deforma- tion of the specimen. The torque applied to the specimen is very small. The maximum stress caused by this torque at the highest loads reached was found to be less than 200 psi, The whole unit was mounted in a 10,000 Ib testing machine. An insulation cage was placed around the specimen to cut down air circulation, and consequent frosting of the specimen, and also to reduce radiation and convection heat losses. A narrow window, covered on both sides with a thin plastic materiai allows the X-ray beam to reach the specimen. Thermocouples placed just outside the pilot hole at the lower grip, in the bottom of the funnel container and near the top of the funnel container permitted checks of the

Jan 1, 1955

By O. G. Lellep

Modern shaft kilns in Europe are fully mechanized and burn cement of acceptable quality at 700,000 Btu per bbl and lime at 3.2 million Btu per net ton. Rotary kilns for cement have increased in thermal efficiency by using exit gas heat for preheating incoming raw material and by recovering heat from outgoing clinker in air-quench coolers. The dry process Lepol or ACL kiln has the lowest fuel consumption, 580,000 to 630,000 Btu per bbl, and very low dust loss, about 1 pct weight of clinker. The Holdebank-Gygi system reaches 720,000 Btu per bbl. The calcinator kiln for the wet process consumes 1.1 million Btu per bbl. IN every country economic circumstances prescribe the method used to produce a commodity at lowest cost. In Pennsvlvania a man's wages for working 4 hr buys a ton of coal wholesale; in Germany a laborer must work 40 hr, or ten times as long. In western Europe, therefore, conservation of fuel is of primary importance, and recent practices of burning lime and cement differ from those employed in the United States. 'This Paper presents data collected during a trip through western Europe in 1953. Considered uneconomical, shaft kilns for burning

Jan 1, 1955

By Thomas A. Simpson

THE Birmingham red iron ore district in Jefferson County, north central Alabama, Fig. 1, is bounded on the northwest by the Warrior and Plateau coal fields and on the southeast by the Cahaba and Coosa coal fields. The area of study includes the ridge and valley between Red Mountain and Shades Mountain, Fig. 2, approximately 70 square miles extending from Homewood in the northeast to Greenwood in the southwest. The district is one of the most important producers of hematite in the United States, with an annual production of about 7 million tons. The amount of hematite mined between 1870 and 1950 ranged from 6 to 16 pct of the nation's total annual production, and the iron and steel products from blast furnaces in the Birmingham district supply the entire southeastern section of the country.

Jan 1, 1955

By F. R. Cattoir, R. W. Kimball, C. T. Anderson, V. V. Donaldson

THIS paper is the second of a series on the effect of various elements on hot-working characteristics of Fe-C alloys to be issued by this laboratory. The investigations being conducted at the Ferroalloy Research Branch of the U.S. Bureau of Mines, Redding, Calif., involve fundamental research on the effects of various alloying materials and impurities on the physical properties of high purity Fe-C alloys. This paper deals with the determination of the limit of forgeability of steels containing varying amounts of manganese and sulphur. A paper discussing the hot-working characteristics and the physical properties of the forgeable alloys is being prepared. One of the principal impurities in all steels is sulphur.. The phenomenon, hot-shortness, commonly attributed to sulphur, has long been a source of expense and inconvenience to both the maker and user of steels. In steelmaking practice, this effect of sulphur has been overcome by the addition of manganese which, apparently, acts as a desulphurizer. Manganese is also used as a deoxidizer and alloying material. The critical and strategic position of man- ganese gives added importance to research which may contribute to its conservation and more effective utilization. It is not the purpose or intention in the present paper to give any explanation of the mechanism of either hot-shortness or its prevention but rather to report the results of forging high purity Fe-C alloys of the range of compositions near the limit of hot-forgeability. Temperatures for each phase of reduction were duplicated within 20" to 30°F for all tests. The starting material was sponge iron, which, after melting and purification, gave a high purity iron containing about 0.001 pct each of silicon and phosphorus. Scrap iron was not considered suitable because of its high percentage of contaminants and wide variation in analyses. The sponge iron was melted and refined for melting stock in a three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating as described in the preceding paper. Additives were carefully selected to avoid addition of contaminants. The sulphur was added as resublimed flowers of sulphur or purified roll sulphur of analytical grade. The manganese used was dehydrogenated high purity electrolytic material produced by the Bureau of Mines plant at Boulder City, Nev. High purity aluminum in the form of wire was used for deoxidation. The limestone was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2,3.0; and P2O5, 0.014.

Jan 1, 1955

By A. J. Opinsky

THE purpose of this note is to indicate the locations and sizes of various interstitial holes in the orthorhombic uranium lattice based on a hard-sphere model. First, plane configurations of three and four atoms will be examined, and then the true interstices surrounded by four atoms in space and by five atoms in space will be obtained. The data and notation contained in a report by Tucker' will be used. Plane Configurations Fig. 1 presents the orthorhombic uranium lattice made of spheres touching at the closest interatomic distance. The three light-colored spheres in the ab plane are illustrative of the first type of configuration to be examined. If one edge of the unit cell is taken as the origin, the three atoms can be represented by the vectors [Oi + Oj + Ok], [ai + Oj + Ok] and [(a/2)i + (b/2)j + Ok] where i, j, and k are respectively parallel to a, b, and c. In the future, this notation will be shortened to [000], [a00] and [a/2 b/2 0], respectively. A vector R = [r s t] de-scribes the position of the hole surrounded by the atoms. Since the center of the hole must be equidistant from the three atoms R2 = r2 + s2 + t2 = (r-a)2 + s2 + t2 = (r-a/2)2 + (s-b/2)2 + t2. R = [a/2 (b/4) - (a2/4b) 0] is the solution of these

Jan 1, 1955

By D. J. DeLazaro, D. W. Levinson

Observations were made of the isothermal transformation and quench and reheat transformation characteristics of binary titanium alloys containing nominally 6 wt pct and 10 wt pct Mn at temperatures of 700°, 600°, 500°, and 400°C. A large change in electrical resistivity attends the beta to alpha transformation in these alloys. The correlation between the resistivity and microstructure provides a very sensitive means of following the transformation. IN a recent paper, Wyatt' determined the electrical resistivity of several grades of unalloyed titanium metal as a function of temperature. In addition to the expected discontinuity accompanying the a-B transformation, it was shown that s-Ti has a much larger temperature coefficient of resistance than 8. The result would be a very large change in resistivity attending ß?a: transformation if it were possible to retain the ß structure at room temperature in pure titanium. From these data, it was reasoned that this very large resistance change should accompany the decomposition of the ß phase in alloys in which the ß phase can be retained by quenching to room temperature from the ß field. This effect is illustrated schematically in Fig. 1. Binary Ti-Mn alloys containing more than 5 wt pct Mn can be quenched to retain ß from the ß field. While the ß phase would be expected to transform in these alloys to a + TiMn via a eutectoid reaction,' it has been observed that the eutectoid decomposition does not occur readily in hypoeutectoid alloys, but rather the decomposition of the ß occurs by rejection of proeutectoid a only." Thus, the resistivity should show a marked decrease, as the a: phase is rejected from ß and a study of the resistivity of solution treated and isothermally transformed or quenched and reheated alloys should provide an excellent means of establishing the transformation kinetics of these alloys at various temperatures. The usual metallographic method of determining the transformation temperature-time characteristics of alloys of this type is very satisfactory for deter- mining the time required to initiate the rejection of the a phase at temperatures relatively close to the ß/a: + ß boundary when the rejected a is coarse, and a typical Widmanstaetten structure is produced. The metallographic method is less satisfactory for this purpose at lower temperatures where a fine nodular decomposition product is observed and is very unsatisfactory for the determination of the time required to complete the transformation at any temperature. Accordingly, specimens were prepared for resistivity measurements in order to determine the transformation characteristics of the alloys.

Jan 1, 1955

By J. Leja, J. H. Schulman

FROTH flotation is usually effected by the addition of a collector agent and a frothing agent to an aqueous suspension of suitably comminuted mineral ores. The action of collectors is to adsorb onto the surfaces of minerals to be separated, sensitizing them to bubble adherence. The action of frothers has, in the past, been accepted as that of froth formation only, brought about by a lowering of the air/water interfacial tension. Substances capable of producing froth are classed1a,b according to their relative capacities for production of froth-volume and froth stability in the simple frother-water system. The purpose of this paper is to show that the surface active agents acting as frothers become effective only when there is a suitable degree of molecular interaction taking place between collector molecules and frother molecules at the air/water and solid/ water interfaces. Further, the discussion will demonstrate that the actual mechanism of adherence of an air bubble to a suitably collector-coated particle is due to the molecular interaction collector-frother. This leads to the formation of a continuous interfacial film of associated molecules, anchored to the mineral by polar groups of the collector, and enveloping the whole bubble. The tenacity of adhesion mineral-to-bubble results from the strength and the visco-elasticity of this mixed film. Some 20 years ago Christman2 postulated mutual dependence of collector and frother in effecting flotation. This view was, however, strongly opposed by Wark,3 who pointed out that an addition of frother had no effect on the value of contact angle once this was established in the solution of collector. More recent work by Taggart and Hassialis' indicated that the presence of frother, namely, cresol, leads to the immediate establishment of a contact angle on sphalerite, partially coated with xanthate, whereas an air bubble fails to make contact in potassium ethyl xanthate solution alone, even after 60 min induction time. Wrobel5 raws attention to the selectivity of frothers in flotation. Many instances of antagonistic effects of certain mixtures of frothers (or collectors and frothers) on flotation froth have been known to flotation operators and have been reported in literature. Taggart6 and Cooke7 give several examples of incompatibility of certain ratios of frothers and collectors, e.g., oleate and long-chain sulphates, pine oil and soaps. Monolayer Penetration. Properties of insoluble films produced by molecules of surface active agents orientated at the air/liquid interface are conveniently studied by the Langmuir trough technique, described fully by Adam.' Using the trough technique Schulman and Hughes" and Schulman et al.10a. b, c, d,e established the existence of molecular interactions occur- ring between certain types of surface active agents. Their experiments revealed the phenomenon of penetration of an insoluble monolayer (e.g., a film of a long-chain alcohol) by a soluble agent (e.g., sodium alkyl sulphate) injected into the substrate (water or salt solution). The degree of molecular interaction taking place on penetration is determined by changes in the surface pressure of the resulting film, changes of its surface potential and its mechanical properties (viscosity and rigidity). When the interaction takes place between both polar groups and both hydrophobic groups of the two participating amphipathic molecules a molecular complex is formed. Complexes formed on penetration of the monolayer at interfaces are not necessarily true chemical compounds: they are labile in solution, the activity and reactivity of individual components are greatly different from those of the molecularly associated complex, and on crystallization they usually separate out into components. However, when formed in the orientated state at interfaces they are found to be very stable, although some mixed films spread as monolayers of stoichiometric complexes can show further penetration by subsequent additions of the soluble component injected into the substrate.'" The degree of association between two or more types of surface active agents is very sensitive even to small changes in electric (dipole) moment of the polar groups of the amphipathic molecules as influenced by magnitude and position of neighboring ions or dipoles, their size, concentration, and stereochemistry. In addition, the molecular association is greatly influenced by concentration and type of inorganic salts in the substrate, by its pH, and by temperature. The nonpolar groups of interacting molecules greatly affect the stability of molecular complexes. Progressive shortening of the aliphatic chain of one of the reacting molecules weakens (at an increasing rate) its tendency to form stable complexes. Similarly, introduction of a double bond of cis-form into one of the reacting chains, which changes the straight hydrocarbon chain into a kinked one, or introduction of a branched chain, reduces the stability of the associated complex. Monolayer Adsorption. Using the trough technique and injecting metal ions into the substrate (water or salt solution) underlying insoluble films of fatty acids, alkyl amines, and sulphates, Wolsten-holme and Schulman11a,b,e. ' and Thomas and Schulman" have established conditions, namely, pH, concentration. and steric factors, under which molecular interactions take place between the polar groups of the surface active agents and the metal ions. These interactions are marked by great changes in the solubility and mechanical properties of the monolayer of the agent; no surface pressure increases are observed as in monolayer penetration experiments. The results of these adsorption studies, correlated with flotation experiments, indicated that in the case of fatty acids and alkyl sulphates their adsorption onto minerals of base-metals takes place by a similar

Jan 1, 1955

By R. F. Domagala, D. J. McPherson

Iodide zirconium was combined with calculated amounts of ZrO2 or master alloys and arc-melted. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat treated specimens permitted construction of the binary phase diagram from zirconium to ZrO2. Oxygen additions to zirconium raise the transformation temperature as well as the melting point. Features of the diagram include the peritectic formation of beta, the formation of alpha directly from the melt, an intermediate phase ZrOB with a' range of homogeneity, and a eutectic between alpha and Zr02. PHASE relationships in the Zr-0 system were determined in the range 0 to 66. 7 atomic pct 0 (ZrO,). Arc-melted alloys were annealed at temperature levels between 600" and 2000°C. Determination of the phase boundaries was accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to determine solidus curves, and X-ray diffraction work was employed to study the lattice parameters of the a solid solution and the phase ZrO,. Experimental Procedures Westinghouse "Grade 1" iodide zirconium crystal bar (approximately 99.8 pct pure) was employed for the investigation. This material is substantially free of the impurity inclusions characteristic of most zirconium metal. Previous work has shown it to be the most satisfactory grade for phase diagram studies. The zirconium crystal bar, as-received, was coated with corrosion product from autoclave tests by which its grade designation is determined. The bars were sand blasted lightly, pickled for 1 min in a 20 pct HN0,-5 pct HF aqueous solution, rinsed in water and acetone, and dried. The bars were rolled to about 1/32 in. strip, cut into 10 in. lengths, and pickled again. The material was sheared to approximately Y4 in. squares, cleaned with acetone, and stored for use. Two pounds of specially prepared "chemically pure," and 100 grams of spectrographic grade ZrO, were obtained for the preparation of alloys. The "Specpure" ZrO, was obtained from Johnson, Mat-they Co.. Ltd.. and Titanium Alloy Manufacturing Div. of National Lead Co. supplied the other grade of oxide. The "chemically pure" material (henceforth referred to as C.P. ZrO,) was used for the preparation of all alloys employed in the determination of phase relationships. A limited number of alloys were prepared with the "Specpure" oxide to recheck certain phase boundaries. Analyses of the two grades of oxide are given in Table I. The C.P. ZrOI was received in powder form, not suitable for arc melting. Therefore, this material was compressed to wafers 1 in. in diameter and about Vn in. thick. These were segmented and stored for use. The "Specpure" material, in the form of small granules, was suitable for use in the as-received condition. A nonconsumable electrode arc-melting furnace was used to prepare alloys. A water-cooled copper crucible and tungsten-tipped electrode were employed. The material was placed in the crucible and rapidly melted under a protective atmosphere of helium gas by striking the arc on a tungsten stud and directing it upon the charge material. Details of operation, including drawings of this type furnace, have been published.'

Jan 1, 1955

By N. J. Grant, A. W. Mullendore

Three aluminum alloys of 0.94, 1.92, and 5.10 pct Mg, prepared from very high purity metals, were tested at 500°, 700°, and 900°F in creep rupture. The degree of strengthening through solid-solu-tion alloying and the effects on the deformation characteristics and fracture were examined. The ductility of the alloys as a function of stress and temperature was closely followed. STUDIES of the creep process in pure metals in recent years have done much to expand the understanding of the fundamental deformation and recovery processes that contribute to overall creep behavior. In order that this knowledge may be applied to commercial alloys, it is necessary to know the principles governing the effect of alloying on the mechanisms of creep. A limited amount of work has been performed in this field, but few investigators have attempted to follow the changes in particular creep mechanisms with alloying. Recently, studies of the effects of solid-solution alloying on the plastic properties of aluminum have been conducted by Dorn, Pietrokowsky, and Tietz,1 Sherby, Anderson, and Dorn,2 and Sherby and Dorn.3 This paper presents the results of an investigation of the effect of solid-solution alloying of high purity aluminum with magnesium on the creep-rupture properties, and correlates these observations with changes in the creep mechanisms. This work is thus an extension of the creep-rupture observations of Servi and Grant4,5 and the deformation studies of Chang and Grant.6,7 Experimental Procedure Three alloys of aluminum containing approximately 1, 2, and 5 pct Mg were tested. These alloying additions are all within the solid-solubility limit at the testing temperatures.' The analysis of the materials is presented in Table I. The tests fall into two categories: l—creep-rup-ture tests at 500°, 700°, and 900°F, and 2—structure study tests performed primarily at 700°F. Speci-mens of 0.160 in. diameter with milled flats for metallographic observations" ' were utilized for the structure studies. All specimens were annealed in one step to give the desired grain size for the tests. Table II presents the annealing data and final grain sizes. The specimens were polished electrolytically before testing with Jacquet solution (2/3 acetic anhydride, 1/3 perchloric acid) at 25" to 30°C, and 15 to 20 v. Creep-rupture testing was performed under constant load with the apparatus previously described." Results and Discussion Creep-Rupture Properties: The log-log plots of creep-rupture data are presented in Figs. 1 and 2. For these very pure single-phase alloys, the minimum creep rate and the rupture life both exhibit straight-line dependence on stress in this method of plotting as they have for commercial alloys0,10 and for pure aluminum." Curve breaks, based on the use of straight-line segments, at 500°F have been found by metallographic study to correspond to a transition from low to high temperature behavior and so represent zones of equicohesion. Specimens on the high creep-rate side of the break showed normal granular deformation processes whereas those on the low creep-rate side showed rapidly increasing grain-boundary sliding and migration with extensive evidence of intercrystalline cracking at 500°F. Two micrographs of the 0.94 pct Mg alloy, Fig. 3, show the increased participation of the grain boundary in the deformation process at 500°F with decreasing stress. In Fig. 3a is shown the structure of a specimen which exhibits little deformation along the grain boundaries and failed transgranularly; in Fig. 3b is shown the increased deformation along the grain boundaries at a lower stress for a specimen which showed appreciable intercrystalline cracking. The severity of intercrystalline cracking increased with increasing magnesium content at 500°F. Intercrystalline cracking disappeared in most of the specimens at 700°F and persisted only in the 5 pct Mg alloy at high creep rates. At 900°F all of the specimens deformed with extensive grain-boundary participation, including extensive grain-boundary migration. None of the alloys at 900°F showed intercrystalline cracking.

Jan 1, 1955

By R. H. Frazier, F. W. Boulger

THE performance of welded structures is closely associated with the ductile-to-brittle transition temperature of the steel from which they are made. A low transition temperature is desirable because it indicates that the steel is less likely to fail suddenly at low ambient temperatures. Structures such as bridges, ships, storage tanks, and pipelines are usually made from hot rolled semikilled steel. Changes in rolling practice or chemical composition appear to be the most practical methods for improving the toughness of such materials. This results from the fact that production is likely to be seriously curtailed if improvements were obtained by recourse to heat treatment or complete deoxidation. This paper discusses the effect of variations in carbon and manganese contents on the properties of semikilled steels. The transition temperature, a property to which considerable importance is attached, varies with specimen configuration, testing method, and criterion of performance. Both the Navy tear test' and the keyhole Charpy test were used in the investigation. According to the terms used by Vanderbeck and Gensamer,V he tear test was used to measure a fracture transition and the Charpy test to measure a ductility transition. In either case the specimens absorb considerably less breaking energy in tests below the transition temperature than in tests above the transition temperature. Decreasing the testing temperature of notched-bar specimens seems to be equivalent in its effect to increasing the severity of loading on fabricated structures. Therefore, structures built from steels exhibiting lower transition temperatures in laboratory tests are expected to be less susceptible to sudden brittle fractures in service. Consequently, changes in composition which lowered the transition temperature of the experimental steels were judged desirable. Materials and Methods The steels for this study were made in a laboratory induction furnace and rolled to 3/4 in. plate, using a finishing temperature of 1850°F. Precautions taken to insure reproducible melting and testing practices are discussed in detail elsewhere.' All tests were made on hot rolled steels. The analyses of the experimental steels are given in Table I. The list includes steels with manganese contents ranging from 0.21 to 1.46 pct, at each of five carbon levels. The phosphorus, silicon, sulphur, and nitrogen contents of the steels are reasonably constant. The tensile and notched-bar properties of the experimental steels are presented in Table 11. Both upper and lower yield points are listed, and all values are averages for duplicate specimens. Transition temperatures based on three criteria are given. The keyhole Charpy transition temperatures are the temperatures at which the energy-temperature curves based on averages of four specimens cross the 20 and 12 ft-lb levels. Both definitions of Charpy transition temperatures have been used by other investigators. Charpy tests were made at intervals of 10°F, using a pendulum with an available striking energy of 220 ft-lb and a velocity of 18.1 ft per sec. The specimens were oriented parallel to the rolling direction and notched normal to the surface of the plates. The tear test transition temperatures are based on the usual' criterion of the highest temperature at which at least one of four specimens exhibits brittle behavior. The dimensions of the tear test specimens are shown in Fig. 1. The specimen is loaded eccentrically in tension, with pin and shackle fixtures, through the large holes while submerged in a liquid bath at the proper temperature. A specimen developing a fracture area with less than 50 pct shear or ductile texture is classed as brittle. Tear tests were made at intervals of 10°F.

Jan 1, 1955

By L. D. Jaffe

THE data recently published1-" on heat treatment of titanium alloys have not been readily systematized into an overall picture. When the ß titanium phase transforms isothermally at low temperatures, the hardness follows a typical age-hardening pattern, going through a peak as schematized by the "hardness" vs "time of isothermal transformation" coordinates of Fig. 1. As the temperature is raised, the peak will decrease in height and occur at shorter times; slowing must however take place as the /3 transus is approached. The brittle microconstituent in the region of peak hardness has been termed /3'. Its structure is still undetermined but it is clearly a transition stage from soft /3 to the £ + a that is found at the right of the peak. On continuous cooling, high cooling rates correspond to short times on Fig. 1; abscissa labeling has been added accordingly. Extremely rapid cooling will retain soft /3; very slow cooling will precipitate soft a; intermediate rates give hard 8'. Increasing distance from the water-quenched end of a Jominy hardenability bar corresponds to slower cooling (right on Fig. I), but the range of cooling rates covered by a Jominy bar is only a small portion of that shown in the figure. The p-stabilizing alloying elements retard the transformation process, moving the material to the left on Fig. 1. A lean alloy is harder water-quenched (P') than air-cooled (/3 +a); a rich alloy is harder air-cooled (/3') than water-quenched (/3). Examples of the position of various compositions with respect to the curve, based on limited data in the literature, are given at the top of the figure. Oxygen and carbon accelerate the transformation process, moving the material to the right on Fig. 1. If an alloy quenched quickly enough to retain soft /3 is reheated below the £ transus (tempered), it ages, going through a hardness maximum as time increases (moving right on Fig. 1). Material which after cooling from the /3 range lies on or right of the hardness peak, will move still further right on tempering, and so soften. Since the rate of the tempering (aging) reaction increases with temperature, the figure also may be used to represent the variation in properties with tempering temperature, at short tempering times. The simple picture given here neglects martensite transformation, as well as differences between decomposition products of /3 formed by direct isothermal transformation and those formed by quenching and tempering. It may nevertheless be of use as a guide for practical heat treatment and for further research.

Jan 1, 1955

By W. A. Olds, H. F. Yancey, M. R. Greer

John Griffen (Consulting Engineer, Pittsburgh)— This paper presents much data offering tentative answers to many technical questions that have been raised by the employment of dense-medium processes and, particularly. by use of the drum-type vessel. It is to be hoped that the Bureau of Mines will publish complete detailed data for the 50 or more tests so that it may be studied and analyzed by everyone interested. Such study will take considerable time and effort. The writer is therefore obliged to confine his discussion to a few points he has noted as being open to question. The data in Table VI which shows the recovery efficiency for the 1 to ½-in. fraction as 100 pct raised a question concerning the accuracy of these calculated figures; washability data on the washed coal and refuse show that such a figure is impossible. When the ash content of the misplaced material in the washed coal is higher than that of the misplaced material in the refuse, recovery efficiency must be less than 100 pct. A etudy of the data In Tables 111, IV, V, and VI suggest that this error probably arose from slight errors in calculating the data in Table V and more probably from the small scale used in plotting the washability curves from the Table V data. Using the size consist data and the weight and ash percentages of individual gravity fractions of each size as given in Tables 111 and IV and the reported recovery of 80 pct of washed coal, a revised Table V was calculated, carrying weight and ash percentages to hundredths of a percent instead of rounding off at tenths. This washability data for each size of Belling-ham reconstituted feed was then plotted on large scale washability curves. From this data the new Table XIV was prepared, which agrees very closely with data shown in Table VI except for two important values, theoretical yields and recovery efficiencies. As will be noted the recovery efficiencies in Table XIV are significantly lower than those given in Table VI. A study was then made of the data showing distribution of the specific gravity fractions to washed coal and refuse. This study indicated that when this distribution was based on the fractions as tested at 0.1-sp gr intervals the number of points obtained were insufficient to establish the distribution curves with reasonable precision, which in turn would affect the accuracy of the values for the specific gravity of separation and the error areas. The data in Tables III and IV of the paper and curves prepared therefrom make it possible for the specific gravity fractions to be subdivided further. This was done using 0.05-sp gr fractions and the distribution data so obtained is given in Table XIV, with resulting values for the specific gravity of separation and the error areas. The writer believes that the derived values shown on Table XIV are more accurate than the correspond-

Jan 1, 1955

By D. R. Walker, M. C. Shaw

The laws of Kick and Rittinger are explained as functions of particle size with metal cutting theory. Comminution is shown to be basically the same process as metal grinding. The machine shop type of grinding operation is used to study mineral crushing. Evidence indicates that plastic flow occurs in comminution. THE laws of comminution of Kick and Rittinger have been debated for many years. Certain data obtained from ball mill and drop tests are found to be in approximate agreement with Rittinger's law while other data would seem to support Kick's law. In all these tests the energy required to produce a wide variety of particle sizes has been studied. Surface area has also been measured with considerable difficulty, at first because it was thought that the energy associated with crushing was that required to create new surface, later because of precedent and because a more fundamental variable was unknown. Tests made with the machine shop type of grinding process show that normally brittle materials that are usually crushed can behave like the more ductile metals. Brittleness is then a relative prop- erty largely dependent on specimen size and stress state. The machine grinding operation offers a convenient means for studying the comminution of materials in which the important size variable retains its identity. The energy required to grind a certain volume of material is shown to be strongly dependent on size. Kick's law is found to hold very well for particles below 1 micron in size, while Rittinger's law holds approximately in the comminution of larger particles. While a physical origin of Kick's law is established in terms of the theoretical strength of materials having a perfect lattice structure, there is found to be no physical basis for Rittinger's law. Because of its industrial importance, comminution has commanded considerable technical attention and has been the subject of continuous study for nearly a century. A number of empirical rules have been proposed to make it possible for grinding energies to be predicted. Of these so-called laws of comminution those bearing the names of Kick and Rittinger have been most widely applied and debated.

Jan 1, 1955

By H. Reiss

The zone-melting process in which redistribution of solute in a solid bar is effected by the passage of a molten zone is considered mathematically. Simple approximate techniques are developed for computing the manner in which redistribution occurs as molten zones continue to pass. The introduction of the "zone-melting flux" provides valuable insight into the nature of the phenomenon, as well as a central mathematical theme in terms of which the process can be discussed. Curves are presented for typical and general cases. AN extremely efficient purification technique was described recently by Pfann.1 Known as zone refining, it consisted of the slow passage of a series of molten zones, produced by external heaters, through a long solid ingot of the substance to be purified. Equations were given for the maximum separation attainable, and a numerical computation method was described for obtaining the concentration in the ingot after a given number of zone passes. The present paper offers an interpretation of the physical nature of zone melting in terms of a transport process in which formal diffusive and convec-tive flows occur. This interpretation, in addition to providing insight into the physical nature of the process, also provides a basis for its mathematical treatment. From this basis, useful equations are developed for the solute concentration in the ingot as a function of the number of zone passes. These are applicable particularly where large numbers of passes are necessary and where numerical computational methods might be laborious. All considerations will deal with the limiting form of the process, described by Pfann,' in which: 1—Diffusion in the solid is considered negligible. 2—Mixing in the liquid is supposed, complete. 3—The distribution coefficient, k, measuring the ratio (at equilibrium) of solute concentration in the solid to that in the liquid is supposed, independent of composition. In general, this paper will be concerned with a bar of uniform (actually unit) cross section, ex- tending in the x-direction from x = 0 to x = L, where L may be infinite. Zone melting is a transport process, and as such must admit of interpretation in terms of a flux of transported quantity. However, the progress of operation is not measured in units of time but in terms of the number of completed zone passes. Consequently, the zone-melting flux will be a rate, per unit pass, rather than per unit time. The description of this flux and the examination of its properties is given below. Zone-Melting Flux Fig. 1 represents an intermediate stage of the nth pass. Concentration C is plotted against distance, x. The molten zone with its back at the point x and front at x + I moves in the direction indicated by the arrow. As it moves, it leaves behind the nth

Jan 1, 1955

By H. M. Fisher, R. E. Snow, S. C. Sun

RAPID colorimetric estimation of the amount of transparent minerals has been applied successfully to instream mill products at the cryolite flotation plant of the Pennsylvania Salt Mfg. Co., Na-trona, Pa. Apparatus used was a Bausch & Lomb monochromatic colorimeter. The optical assembly of the colorimeter, shown in Fig. 1, passes light from a 6-v, 32-cp, prefocus incandescent lamp through two condensing lenses, a heat-absorbing filter, an aperture-control diaphragm, an interference filter, and a sample container. The light finally strikes a barrier-layer photocell and the output current of the photocell is measured by a galvanometer. The engraved index line of the collective lens, located between the lamp and the galvanometer, is imaged upon the transmission scale of the colorimeter by the galvanometer mirror. Reflected light from the galvanometer mirror, the position of which is determined by the output current of the photocell, enables reading of percent transmission throughout the mineral sample being tested. The colorimeter, Fig. 1, was standardized as follows: 1—The colorimeter was' connected to a Sola constant voltage transformer, A, of 6-v output operated from a 110-v ac supply. 2—Turning the toggle switch, C, illuminated the transmission scale, B, and the control knob, D, was adjusted with a blank in the optical system until the hairline on the scale read zero. 3—A No. 430 interference filter, E, was inserted into the filter channel, F. 4—A test tube, G, containing 7 cc of distilled water was pressed into the sample space, H, and the fine adjustment knob,

Jan 1, 1955

By J. D. Forrester, Erich Sarapuu, T. C. Cheasley

Electrocarbonization of coal will produce cheap fuel for electric power plants. The complete electrification of industry and domestic power consumption of gas generated as fuel in situ is a worthwhile goal for the coal industry. Production of synthetic oils, gasoline, and coal chemicals from coal gas will create additional new markets for the coal industry. RANKING high in the nation's wealth of natural resources, readily available liquid and gaseous hydrocarbons are nevertheless falling steadily in supply, while industrial requirements for hydrocarbon compounds are greater today than during the peak period of World War 11. Theoretically, several processes will increase the future supply of liquid and gaseous fuels, but the practical application of these methods depends on two controlling factors: 1—that enough carbon-bearing material be available to warrant industrial exploitation, and 2—that the given process be physically, chemically, and economically applicable. With regard to the first factor, the Western Hemisphere is fortunately well supplied, see Table I. Table I not only shows the extensive occurrence of many fuel sources, but also the wide discrepancy among quantities of fuel substances in various materials. Great quantities of potentially available fuel have not been recovered. Many coal seams and other hydrocarbon-bearing deposits are so situated that production is uneconomical by present-day mining or oilwell pumping methods, and even in many exploitable deposits where the most efficient production methods are used a large proportion of material is never recovered. Industrial production of hydrocarbon liquids and gases must be better balanced, and processes must be developed which will convert coals, oil sand, and oil shales into fabricated commodities. Among the techniques employed by scientists and engineers to secure fuel masses not economically available at present are several processes of underground gasification. These are all concerned with converting raw materials into gaseous products by thermal treatment of source substances while they are still in the ground and therefore require that a subsurface heat (fire) zone be induced to affect pervasively the buried raw fuel deposit. This is possible only where sufficiently high temperature exists and where the fuel material is satisfactorily opened or channelized. Also, to compete successfully with common mining or oilfield practices, a given method must be controllable and must not involve greater operational expense than regular methods. Preferably, it should be less expensive. Since the close of World War 11, England has continued field studies of underground gasification methods. Experiments have also been conducted in Sweden, Estonia, France, Belgium, Italy, and Germany. The U. S. Government has sponsored field studies at Gorgas, Ala., and because gasification in situ is vitally important to establishment of the nation's fuel resources, the mining engineering department at the Missouri School of Mines has been actively interested in developing the process of underground electrocarbonization. Research was conceived by Erich Sarapuu, and preliminary experiments in treating bituminous coal were begun at the school in September 1947. The work consisted of laboratory experimentation until June 1948, at which time, through a cooperative agreement with the Sinclair Coal Co. of Missouri, pilot plant studies were instituted at the Tiger mine of the Hume-Sinclair Coal Co. near Hume, Mo., to test the encouraging laboratory findings. This comprehensive field program was pursued continuously until the beginning of 1952."'" The broad term underground electrocarbonization describes a unique gasification process that releases by electricity the desired economic constituents from a raw carbon-bearing material, converting the substance of such deposits into deliverable form and greatly reducing the cost-of-mining factor. Underground electrocarbonization is not subject to the major limitations of many other underground gasifi-

Jan 1, 1955

By R. W. Jenkins

RACKLESS equipment is being used by the T Coplay Cement Manufacturing Co. to develop a folded limestone deposit economically and safely with inexperienced men. Cost and quality of development stone results in a saving when it is used instead of outside sources of limestone. This favorable cost has been attained by following a methods development and training program described in this paper. It is expected that further savings in favor of the mined stone will be made when stopes now being prepared are in production. The present equipment will be used for loading from stope draw points. The limestone is blended with quarried cement rock to serve as raw material for Portland cement, first produced in this country by Coplay Cement Manufacturing Co. from a process developed by its president, David 0. Saylor, in 1873. For many years the cement rock alone or with a small amount of added limestone was used for raw materials. Later as specifications were raised and the richer portions of quarries were depleted, limestone from outside sources was required in increasing amounts. In 1925 D. J. Uhle, the general manager, began to prospect company property for limestone. It was known that the argillaceous cement rock was underlain by crystalline high calcium limestone. After an extensive drilling program it was found that there were large reserves of limestone underlying a recumbent syncline exposed in the south wall of the company's No. 3 cement rock quarry. A quarry was started on the vertical limb of this fold in 1927, and by 1930 the full requirement of the plant was met. After 1945 production diminished because of the occurrence of dolomite beds in the south wall. The quarry floor was then 135 ft below the cement rock level and 285 ft below surface. In 1949 Gerald I?.

Jan 1, 1955

By John L. Baum

Tests show that 50 times the earth's normal field can exist near stacked drill rods. Protection against the effect of these strong fields can be obtained by means of a removable sleeve of common iron pipe. GEOLOGISTS and engineers working around a diamond drill rig have often had the opportunity to observe the magnetic attraction of drill rods pulled out of the hole for core removal. This is sometimes an amusing pastime, but this same magnetic force inadvertently applied to a compass needle can cause it to lose its polarity entirely or to become reverse polarized when placed in the immediate vicinity of stacked rods. The first recommendation, of course, would be to avoid the rods, but in surveying an operating drillhole this is not always possible; therefore steps must be taken to neutralize the magnetic effect of the drill rods. Early in the summer of 1949 the geological department of the New Jersey Zinc Co. undertook at Franklin, N. J., an extensive program of surveying the course of deep diamond drillholes. The majority of the holes were surveyed while in the process of being drilled, and considerable difficulty was encountered. A pattern for the deviation of drillholes had been established for the district from surveys in holes from which the drill rig had been removed. It was observed that a certain operating deep drillhole being surveyed did not fit this pattern. In the resulting confusion of repeated surveys and cementing a plug for wedging operations, the lower 1800 ft of the hole was lost. Because of this incident studies were initiated to determine the source of the difficulties and to develop safeguards against recurrence of faulty surveys. Using a hand magnet easily shows that the polarity of a compass needle can be reversed if rotation of the needle is hindered through tilting of the compass or clamping of the mechanism. Such experiments are not recommended, especially in the case of the clockwork type of instruments. A magnetized hairspring in a clockwork instrument will cause the compass card to assume a periodic motion which will not stop until the clockwork runs down. Routine check readings of instrument north before and after each survey are not always sufficient to catch instances of reversed polarity of the compass needle. Although the majority of instances probably take place while the instrument is being removed from the hole with needle in fixed position, it is demonstrable that a 'luggish needle, weakened during a previous test, can be reverse polarized

Jan 1, 1955

By O. N. Carlson, H. A. Wilhelm, J. M. Dickinson

On the basis of microscopic studies, melting-point observations, and X-ray analyses, a phase diagram is proposed for the Cb-V system. A complete series of solid solutions is formed with a minimum in the solidus at 1810°C near 35 wt pct Cb. No compounds or intermediate phases were found in the system above 650°C. THERE is an ever increasing need for better structural metals and alloys for use in nuclear reactors. In addition to the normal properties of engineering structural materials, such as high temperature strength, resistance to corrosion, and fabric-abil~ty, the nuclear properties of the material must be considered. In a nuclear reactor it is important to conserve neutrons, so a material which removes these neutrons from the reaction excessively is considered to have unfavorable nuclear properties. In nuclear-reactor design the engineer must have nuclear as well as other data available on alloys in order to make a wise selection of materials. Due to the fact that many of the common structural materials have undesirable nuclear properties, it is vital that new alloys of metals having more favorable nuclear properties be investigated. Columbium and vanadium are both high melting metals, both exhibit resistance to chemical attack, and no great difficulty is encountered in fabricating them into desired shapes. With proper treatment both metals can be cold rolled extensively without failure. In addition they have desirable nuclear properties for certain types of reactors. Therefore, the alloys of columbium and vanadium should be of interest in the atomic energy program. Since an alloy-development program is enhanced by a knowledge of the phase equilibria of the components, this investigation was undertaken to establish the phase diagram for the Cb-V system. According to the Hume-Rothery rules for alloying,' the chemical similarity, crystal structure, and atomic-size factor are favorable for a complete series of solid solutions for this system. Both elements are in the same family of group V of the periodic table and thus are quite similar chemically. The crystal structures of columbium and vanadium are compatible for extensive solid solubility, since both have body-centered-cubic structures. The atomic diameters of columbium and vanadium are 2.85 and 2.62Å, respectively. This difference of slightly more than 8 pct is well within the 15 pct maximum difference allowed for extensive solid solubility. Experimental Procedures Source of Materials: Columbium powder and sheet trimmings were obtained from the Fansteel Metallurgical Corp. According to the manufacturer the metal contains less than 1 pct impurity. An analysis of the metal showed approximately 1800 ppm C in the powder while the sheet trimmings contained less than 500 ppm C. Spectrographic analysis showed minor amounts of Ca, Cr, Fe, Mn, Si, Ti, V, and Zr in both forms of the columbium. No commercial source of vanadium having the ductility and purity desired was available to the authors at the beginning of this investigation. As a result, all of the vanadium used in this study was prepared by the bomb reduction of vanadium pen-toxide with calcium employing the method reported by Long.' Yields of massive vanadium normally were about 80 pct. Chemical analysis of the vanadium prepared in this manner showed the presence of 200 to 500 ppm N and 800 to 1000 ppm C. Minor amounts of Ca, Fe, Mn, Si, Zr, Cr, and Cb were detected by spectrographic analysis. This vanadium metal was ductile and was cold rolled into 5 mil sheet. Annealing was not necessary during this rolling and the metal retained its cold-rolling characteristic after are-melting. Preparation of Alloys: The Cb-V alloys were prepared by melting pieces of vanadium sheet togethel-with columbium in the form of sheet or pellets of powder. The melting was carried out under argon in conventional arc-melting equipment employing a tungsten electrode and a water-cooled copper crucible. Each alloy was remelted three or four times, inverting the alloy after each melting in order to assure complete mixing. Alloys normally were obtained as round flat disks, weighed approximately 70 grams, and had roughly the shape of a disk 1 1/2 in. in diameter and 1/4 in. thick. Half of each alloy

Jan 1, 1955