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By R. J. Brison, W. C. Bleimeister

The International Salt Company has long been interested in finding an efficient process for the removal of impurities from rock salt, and particularly from the rock salt produced at the Detroit mine. Methods which have been used previously at the Detroit mine included both hand sorting and differential crushing in a Bradford breaker with rejection of the oversize. Neither of these methods was adequately effective. The development of a new process for removal of impurities from rock salt has been described in the preceding article." Basically, the process consists of exposure of crude rock salt to radiant heating which selectively heats the impure particles. Subsequently the heated particles are removed by adhesion to a heat sensitive-coating on a conveyor belt. This method was found to be effective in improving both the quality and appearance of rock salt by the rejection of the dark, impure particles. The first commercial unit employing the new thermoadhesive method of dry separation of minerals was installed at the Detroit mine of International Salt Company in Detroit, Mich. (Fig. l). This unit was first put into operation in March 1957. The purpose of the Detroit installation was 1) to serve as a pilot plant for evaluating the process on a commercial scale and 2) to produce marketable quantities of rock salt of improved quality and ap- pearance. The design of this plant was based on the results and information obtained from a 1-tph pilot plant at Battelle Memorial Institute. DESCRIPTION OF PLANT Location: The separation plant was installed underground near the crushing and screening plant, for this was the most suitable location from the standpoint of material handling. Furthermore, ample space was availabe at this location. Because the process requires a relatively constant temperature, the uniform year-around temperature of the mine (57°F) gave an added advantage to an underground operation. Feeding: The rock salt is conveyed to a surge bin, from which it is fed to the heating unit by a conveyor. The feed-rate control consists simply of an adjustable gate at the bottom of the surge bin. The plant may be fed either No. 1 grade of rock salt (0.279 to 0.375 in.) or No. 2 grade (0.375 to 0.500 in.) with a maximum input capacity of 500 tons per 15-hour day. Heating Unit: The heating unit (Fig. 2) consists of a panel of infrared lamps suspended inside a low-speed revolving screen. The radiant-heat panel, which is curved for most effective utilization of the heat, holds 240 infrared lamps of standard industrial type, each rated at 500 watts. The position of the panel is adjustable so that it can be placed centrally over and to within 6 in. of the salt bed on the screen. The entire heat panel is suspended by rollers in ¦ R. J. Brison and O. F. Tangel: Development of a Thermo-adhesive Method for Dry Separation of Minerals.

Jan 1, 1961

By N. J. Grant, Masao Adachi

A number of Cu-SiO, and Cu-A1203 alloys of low oxide content, produced by internal oxidation of copper-silicon and copper-aluminum dilute solid solutions, were exposed at temperatures up to 1050°C for fairly long times to bring about partial or total re crystallization. The creep-rupture properties of these re crystallized alloys were compared to those in the as-extruded condition at 450° C. Some of the alloys were cold worked after re crystallization to note changes in creep-rupture properties, also at 450OC. SINCE the introduction of the SAP alloy in 1949,~ many studies have been carried out on similar oxide and intermetallic dispersion hardened alloys to determine properties and to establish the mechanisms involved in the strengthening process which led to stable, high-temperature behavior.'-' To date, it has been indicated that, however achieved, the structure should be composed of a continuous ductile metal matrix in which is dispersed a fine, submicron size, hard, insoluble second phase (or at least, essentially insoluble at temperatures very near the melting point), with a submicron or near submicron interparticle spacing. Stored energy, obtained by a high strain rate deformation process appears desirable, as an additional strengthening means beyond pure dispersion.=

Jan 1, 1961

By A. W. Ruff

In the last ten years large gains have been made in the field of blasting. These gains have been both in the theoretical and in the practical application of explosives. One of the most publicized changes in the practical application of commercial explosives is the now-prevalent use of ammonium nitrate and fuel oil. The new water-compatible mixture of ammonium nitrate and TNT should also have a large field of application. Most of the theoretical gains have been concerned with the actual rock breakage obtained with explosives. In the last ten years, large gains have been made in the field of blasting. These gains have been both in the theoretical and in the practical application of explosives. One of the most publicized changes in the practical application of commercial explosives is the now prevalent use of ammonium nitrate and fuel oil. The new water-compatible mixture of ammonium nitrate and TNT should also have a large field of application. Most of the theoretical gains have been concerned with the actual rock breakage obtained with explosives. EXPANDING-GAS-BUBBLE THEORY There has been an outstanding change in the conception of how an explosive produces rock failure. The early theory which explained rock breakage was correct for some of the first force-producing agents such as quicklime. When a drillhole was filled with quicklime and water added, the material expanded and steam was generated. The expanding material and the steam exerted a slowly increasing pressure on the sides of the drillhole. The force broke the rock by splitting. Because a great quantity of gas was produced by the deflagration of gunpowder, the same process of the gas pressure splitting the rock was assumed to take place. Even after 80 years of use, the rock-breaking action of all high explosives was thought to be caused entirely by the expanding gas bubble which tore and split the rock. Fig. 1 shows a vertical section through an exploding spherical charge of high explosive. It illustrates the early theory which attributed the entire breakage to the expanding gas bubble. The basic idea of this theory is that the breakage started at the explosive charge and progressed toward the free face. REFLECTED-WAVE THEORY me expanding-gas- bubble theory has gradually been replaced by the reflected-wave theory. The reflected-wave theory explains rock failure by explosives in the following manner: The enormously high gas pressure in the drillhole produces fracturing of the rock on the sides of the drillhole. The fracturing around a 1 1/2-in. diam drillhole is usually confined to an area with about a 6-in. diam. In the fractured area, the pressure of the gas is reduced until the force on the walls is no longer capable of fracturing the rock. Although the gas pressure does not continue to fracture the rock, the pressure imposes a high impact stress on the wall rock. In addition, a pressure or seismic pulse is produced in the rock. The pulse is probably entirely a compression pulse when originally produced in the rock. But, with distance, part of the energy of the compression pulse is transformed into a tension pulse which follows the compression pulse. The explosive charges and burdens used in conventional mine blasting are such that the tension pulse of the original wave is probably too small to be considered in a practical evaluation of the theory. The compression pulse is transmitted through the rock with no associated fracturing.

Jan 1, 1961

By C. E. Westley, R. R. Beebe

Recent works by Plaksh et al.,1,2 Glembotsky,3 and others have renewed interest in the effects of oxidation on the surface activity of the sulfides. Since considerable supporting data are available on galena-potassium ethyl xanthate, this system is being studied at South Dakota School of Mines and Technology by contact angle measurement, using the technique of McGlashan and McLeod.4 The contact-angle method is well adapted to investigation of the influence of small amounts of oxygen on the establishment of a stable contact angle on galena in potassium ethyl xanthate solution. Samples of massive galena containing less than 0.001 pct Cu, 0.001 pct Ag, and 0.01 pct Zn are mounted in castable plastic and ground and polished manually in a glove box containing the desired proportions of oxygen and purified nitrogen. Oxygen and nitrogen contents of the test atmosphere are determined with an Orsatt analyzer. In this way a reproducible surface is created in contact with whatever oxygen concentration is desired. Water and all reagents are prepared and stored in the test atmosphere. An absorbent is used to control carbon dioxide that might be present. Final polishing is done with levigated alumina on a glass plate. The prepared sample is placed in the test solution and transferred to the contact angle apparatus in a sealed box, and the test is conducted while both sample and solution are maintained under a slight positive pressure of the test atmosphere. Table I gives the results of contact angle measurements made at various 02-Nz concentrations.5 Each value of contact angle is the average of at least six individual measurements made with different bubbles at different locations on the sample surface. A period of 20 to 25 min has been found by preliminary tests to be sufficient to permit develop- ment of maximum angle, and all measurements are made after at least this much time has elapsed. Exposure of prepared samples to pure water under the test atmosphere before exposure to the xanthate results in a small but measureable and consistent reduction in contact angle. This is particularly true in the oxygen-deficient atmospheres; for example, at 2.2 pct O2 such water contact reduces the average angle about 8" from that obtained by immediate testing in xanthate. The general trend of increasing contact angle with increasing oxygen concentration corresponds to the results of Plaksin et a12 The absence of diminish-ment of contact angle at very high oxygen concentration has been attributed to the high concentration of xanthate per unit of galena surface: At oxygen concentrations below 1 pct (the limit of accuracy of the Orsatt analyzer), no contact angle is obtained. Furthermore, no contact angle is obtained at any oxygen concentration in the absence of xanthate. This result seems to be in disagreement with those cited by Plaksin.1 Further work on the interaction of galena and potassium ethyl xanthate or a similar collector as influenced by oxygen is contemplated. The true nature of the interrelation is as yet unknown. For example, it is not known whether the governing oxygen reaction is with the mineral, with the reagent, or with both.

Jan 1, 1961

By A. R. Troiano, E. A. Steigerwald, F. W. Schaller

The initiation of localized cracking in hydrogenated high strength steel was dependent on the developmeni of a critical hydrogen conceniration and relatively insensitive to the magnitude of the applied stress. The stress was believed to influence the deluyed failure process by providing the means for grouping the hydrogen. On the basis of an assumed distribution law the observed changes in the lower critical stress as a function of notch acuity, yield strength, and temperature were predictable over a significant range of these variables. THE phenomenological characteristics of delayed failure in high-strength steel have been comprehensively investigated and the behavior has been attributed to the strong embrittling action of hydrogen.1-3 Delayed failure or, as it is also termed, static fatigue, is the most sensitive means of detecting hydrogen embrittlement since it allows the maximum time for hydrogen diffusion during a test.3 The nature of delayed failure cail be aptly described by four parameters which are schematically depicted in Fig. 1. The upper critical stress corresponds to the rupture stress in a conventional notch tensile test. The lower critical stress or static fatigue limit is the stress below which no delayed failure will occur. The incubation period is the time required for the formation of the first crack and the fourth parameter is the failure time. An increase in hydrogen content, notch acuity, or strength level of the material increases the susceptibility for delayed failure by decreasing the lower critical stress, the incubation period, and the time to failure.lY3 A decrease in test temperature prolongs the incubation period in accordance with the lower diffusion rate of hydrogen, and also de-

Jan 1, 1961

By Abdul-Fattah K. Kaddou, P. C. Rosenthal

THE authors have studied the problem of temper brittleness in steel1 employing an internal friction method. The specimens are in the form of wire, 14 B and S gage (0.064 in diam), 6 in. long. It was very desirable to have an apparatus to test the wire specimens for temper brittleness without making standard notched-bar Izod or Charpy impact tests. Such a device would have two favorable advantages: the first is that no standard impact specimen would be necessary, thus saving time and labor; the second is that there would be a direct correlation with internal friction results, thus eliminating the size factor if standard impact specimens had to be used. A search was made without result to find a commercial apparatus for this purpose. The literature was surveyed to investigate if such a test had been utilized. No such work has been reported in the literature; however, zapffe2 has described an apparatus used for testing for hydrogen embrittlement in

Jan 1, 1961

By P. L. Allsman

A method of analyzing blasting action indicates that major cost savings are possible by revising practice and bringing the classical blasting formulas up to date; difficult problems such as taconite and throw-breakup can be attacked by engineering Denonation pressure — the peak pressure developed by the explosive reaction; "shatter blasting." Average detonation pressure — the average pressure over the time the reaction continues; "heave blasting." Radial presswe — the stress in a radially expanding sphere about the detonation. Corresponds to the diminishing peak pressure. Lateral stress - the stress in a circumferential direction, induced by outward movement of the rock away from the detonation. Limiting stress or Slim— the rock property at which failure will occur in the case at hand; may be tensile or compressive strength, or combinations. Recent developments in explosives technology, following the advent of nuclear explosions, have led to a rather complete understanding of their action. A survey was made for the purpose of uncovering any knowledge which might be applicable in the mining and quarrying industries, the principal users of explosives. Although no revolutionary techniques have become apparent, much basic data pertaining to blasting — fortunately not classified — have been developed by recent research, from which a good general understanding of the process can be derived. It is hoped this explanation of the scientific principles governing explosive action, together with a proposed analysis of blasting practice, will further the development of mining engineering. NATURE OF THE REACTION: The phenomenon of explosion, termed detonation, is in reality a rather complex chemical reaction, and as such is completely explainable by physical and chemical laws. Detonation is characterized by high temperature and pressure, extreme rapidity — often being complete within one microsecond — and most importantly by formation of a shock pulse which accompanies the reaction zone. As with any chemical reaction, there is a critical value of temperature and pressure below which detonation can not occur; this is termed the "critical point". Whereas an explosive substance will decompose slowly at ordinary temperature, with the formation of gases which readily dissipate; at elevated temperature the reaction is considerably speeded. If pressure is suddenly applied at some point in an explosive medium, adiabatic compression results, and the temperature is locally raised. When the temperature becomes high enough the decomposition will be so rapid that the gaseous products do not have time to dissipate, but contribute to a further build-up of pressure. This, in turn, furthers adiabatic temperature rise over a widening area, and with any heat generated by an exothermic reaction, causes a rapid increase in temperature. Both temperature and pressure are spontaneously built up in this manner until the critical point is reached, resulting in detonation. The values of pressure and temperature necessary to create detonation are established by the unusual nature of the process. If temperature alone is raised above the critical point, without sufficient increase in pressure, deflagration or "low-order detonation" occurs. In the true, or "high-order detonation", the shock pulse resulting from the violent decomposition becomes an integral part of the reaction, and itself aids in increasing the detonation

Jan 1, 1961

[Admissions: Aurel E. Smith, Chairman Edmond F. Egan Lawrence S. Fennell John S. Fuller Howard J. Ritts, Jr. Gene E. Roark Kenneth W. Robbins Ben M. Gottlieb Advertising: Bernard F. Klein, Chairman Henry N. Lyle R. E. Howard H. M. Krause, Jr. Mrs. Evelyn R. Robertson]

Jan 1, 1961

By M. Kaufman, A. E. Palty

THE mechanical properties of an alloy under given test conditions are in the main determined by the grain size and the phases present, their distribution and temperature-time dependence. Alloys intended for use at elevated temperatures, especially multiphase alloys depending upon precipitation reactions for strengthening, are particularly susceptible to changes in the phases present. Unfortunately, for modern superalloys, very little published information exists which relates the mechanical properties to the basic structural variables. The present work is an effort to do this for an alloy widely used in aircraft gas turbines and related applications, Udimet 500.* The mechanical properties inves- two heats is within the normal specifications for the alloy. However, the elements which most strongly influence the phase reactions, C, Ti, Al, and Mo, are comparable in the two heats. There was no intentional addition of boron, but normal pickup is about 0.002 pct. The vacuum-melted material was received in the form of centerless ground wrought bar stock % in. diam. PHASE STUDIES A) Methods—Two methods were used to determine the phases present: X-ray diffraction measurements on electrolytically digested residues, and microscopic examination. No single commonly used electrolyte will reveal all the phases that may be present; therefore, two complementary acids were selected: HCl and H3PO4. The necessity for this will be shown below in the results. The acid concentrations used were 10 pct HC1 in alcohol and 10 pct H3 PO4 in water. The current density was maintained below 0.1 amp per sq in. Residues were rinsed and separated by centrifuga-tion. X-ray diffraction patterns were obtained in a 114 mm Debye-Scherrer type camera using cobalt radiation. A temperature of 2250°F was selected to obtain as complete solutioning of phases as possible without encountering incipient melting. Specimens were

Jan 1, 1961

By R. E. Reed-Hill

The lattice reorientations in (1011) and (1013) twins of pure magnesium have been investigated using polarized light. Both forms (Ire subject 20 almost complete second-order twinning on the (1012) plane of the first-order twin. The observed deviations of composition planes by 6 and 3 deg, respectively, from coherent twinning planes are caused by second-order twinning. The experimental data indicate that (1011) and (1013) are reciprocal twins with a twinning shear 0.136. In a previous paper1 it was shown that the primary fracture mechanism in single crystals of magnesium strained in tension parallel to the basal plane is parting or fracture inside twins. In the temperature interval 25oto286oC, the observed twinning form, dominant in fracture, was a very small twin which formed in bands. Because these twins were very small and appeared in extensively deformed regions they did not lend themselves to X-ray analysis. Lacking Cou-ling and Pearsall&apos;s2 recently reported polarized light technique for magnesium, the twinning plane indices (K1) were originally determined by two surface composition plane measurements. This plane fell in a major zone (axis < 1120>) at an angle of 55.75 deg to the parent crystal basal plane. Because its habit deviated by 6 deg from{l0ll), 61.9 deg, the experimental data per se were not consistent with simple (1011) twinning and, for expedience, the twin was designated with habit plane indices (30341, 54.5 deg, representing the lowest set of indices corresponding to measured angles. Couling, Pashak, and sturkey3 have also found bands of reoriented lattice with a similar habit in polycrystalline specimens of magnesium and certain dilute magnesium alloys. These bands are significant because their formation in large numbers during plastic flow permit specific magnesium alloys to undergo very extensive deformation by cold rolling. Using polarized light2 they showed that the basal plane in the reoriented material was nearly parallel to the band habit and, as a result, proposed a mechanism for band formation involving a double twinning process in which (1011) twins form and then retwin according to (1012). Because of the obvious similarity between the twin bands observed in single crystals and in polycrystalline specimens, it was decided to investigate if the two phenomena were not identical and, if possible, to verify the retwinning hypothesis. The present paper is a report of this investigation and shows that the twins with the (3034) habit correspond closely to retwinned (l011) twins. Evi- dence is also given for an analogous retwinning process in (1013) twins. EXPERIMENTAL PROCEDURE Rectangular single-crystal specimen deformed in tension (stress axis in the basal plane parallel to [1010], as previously described,4 were polished electrolytically by Jacquet&apos;s method5 and etched in acetic picral.2 All twins studied in this investigation belong to a major zone, whose axis, [1210], was perpendicular to both stress axis and two sides of each specimen [(1210) surfaces]. These latter contain the plane of shear of the twins and measurements of the basal plane trace of twins on these surfaces determines the lattice orientations of the twins. The position of the basal plane in each case was determined with a polarizing microscope using a modification of the technique of Couling and Pearsall.2 For each twin the four positions of maximum extinction were measured, the data averaged, and then the pair of extinctions corresponding to the basal plane was determined by rotating the microscope stage and observing the position at which the color changed from orange to blue with a gypsum red, first-order plate inserted between the crossed Nicol prisms. EXPERIMENTAL RESULTS (1013) Twins—In general, especially in speci-mens deformed at 150°C, (1073) twins appear in greater numbers and larger sizes than (1011) twins, and the lattice reorientation inside these twins is therefore easier to study and measure. Fig. 1 shows an area of an unetched and unpolished (1210) crystal surface containing a number of (1073) twins sloping upward to the right at about 29 deg with the basal plane of the original crystal (horizontal direction). Slip line segments may be seen in both the parent crystal (running horizontally) and in the twins (sloping downward to the right at approximately -22 deg with the horizontal). As may be seen in Fig. 2, the slip lines in the twin are not at the proper angle (64 deg from basal plane of the

Jan 1, 1961

By M. A. Cook

Sutherland used an ion-pair adsorption model to derive the author&apos;s hy-drolytic pee-acid) adsorption equation for the contact bubble curves of Wark and Cox. To do so it was necessary to postulate that the sum of coverages of surface anion sites by the collector and depressant anions is practically unity. It is here shown that the free energy of Sutherland&apos;s postulated collector ion (x-)-depressant ion (OH-) exchange reaction (for no other than the OH- to compete with X-), namely EX + (OH-) Z SOH- + X-, is in some cases positive and X- should not even adsorb. Also, in many cases the (OH-) adsorption must be quite negligible even though the collector covers only about a sixth of the mineral surface at the threshold of air bubble contact. This, however, contradicts the postulate that permits one to derive the correct bubble contact eqwztion for the ion-pair model. Furthermore, the requirement for charge neutrality leads in the ion-pair model to the (impossible) constancy of the ratio @+)/(OH-) along a contact bubble curve in which pH may change by more than seven units. HYDROLYTIC ADSORPTION EQUATION Hydrolytic (free-acid or free-base) and ion-pair (H&apos;, X-, or R&apos;, OH-) adsorption models of the collector in metal sulfide and similar flotation systems are superficially alike and somewhat difficult to differentiate. This is because they yield, under seemingly valid assumptions, equivalent forms of the equations describing the distribution of the collector between the aqueous solution and the mineral surface. This has been discussed by the author and associates1-4 and more recently by Sutherland,&apos; both for simple collector-mineral and for more complicated collector-depressant-mineral systems. In the hydrolytic adsorption model the equations describing the contact bubble curves of Wark and coxeJ7 are as follows :2 Here X is the collector anion, D- the depressant anion, 9, and On are the fractions of the free-acid sites S on the surface of the mineral covered by collector and depressant free acids, respectively, and @ is the fraction of uncovered sites. Kx is the free-acid collector dissociation equilibrium con- stant, K1 that for the free-acid collector adsorption, KD that for the free-acid depressant dissociation, and K2 the equilibrium constant for the free-acid depressant adsorption. Eqs. 1 to 5 yield upon simultaneous solution the result is the critical free-acid concentration for bubble contact in the absence of depressant-free acid. Eq. 8 expresses the conditions along a simple collector-mineral contact bubble curve for the case HD = 0, or V = 0. Last and Cook showed that Eq. 6 applies generally and with good accuracy in the collector-depressant-metal sulfide mineral systems. Inci-dentally, it has been shown by infrared absorption studies that in some cases the free-acid adsorption process splits out water.&apos; In this case, Eq. 2 might be written SHOH + HX Z SHX + H20, with a similar equation replacing Eq. 4 for depressant-free acid-water exchange. This possibility does not change, however, the basic equations or considerations of the hydrolytic adsorption model. Indeed, this type of free acid-water exchange reaction was predicted for fluorite and iron ore flotation by oleic acid in the dry grinding and boiling processes.410

Jan 1, 1961

By Charles Luner

ALTHOUGH the kinetics of the atmospheric oxidation of tin have been studied,1-3 the kinetics in pure oxygen have not been reported. This note presents some results of the kinetics of the oxidation of tin foil in pure oxygen. The tin foil used in this investigation was 99.78 pct pure, the two major impurities being Pb (0.17 pct) and Sb (0.024 pct). The foil was degreased and air-dried prior to oxidation. The air-formed film was estimated by coulometric reduction4 of the surface oxides to be about 25A. The samples, which were in strip form and had a total geometric surface area of about 300 sq cm, were first evacuated at room temperature in an oxidation bulb to 1 X 10 -5 mm Hg and subsequently degassed for 1 hr at the temperature of the experiment. Spectroscopically pure oxygen was then introduced into the bulb. The rates of oxidation were measured by following the rate of pressure change due to oxygen consumption in a closed system, the volume of which was sufficiently large so that the pressure change during an experiment was 10 to 15 per cent of the total pressure. An oil-mercury manometer,5 with a sensitivity of 3 X x mm Hg (which corresponds approximately to 5 X 10 -7 gm of oxygen) was used to measure the pressure change. The oxidation bulb was heated by an oil-bath and controlled to within -10.3 C. The reproducibility of the rates was good, as determined by the coincidence of rates at 190oC for duplicate experiments. Fig. 1 shows the oxidation curves in the temperature range 168 to 211.5oC at 8 mm Hg pressure. The effect of pressure on the rate of oxidation at 190°C is also shown. The rate of oxidation was not markedly affected by changes in pressure in the range 4 to 9 mm Hg, except perhaps at the lowest pressure, 4 mm Hg, where after about 70 min there appeared to be a decline in the rate, as compared with the rate at the higher pressures. At the lower tem- perature, 168oC, and for short reaction times, it is difficult to distinguish between a linear relationship and a slight curvature in the oxidation rate. However, for longer times, there was a somewhat larger indication of curvature. The samples after oxidation were gold-colored in appearance. The oxide that was formed at 170°C was identified as a-SnO by reflection electron diffraction. This is in agreement with results obtained by other workers.6, 7 The rate data best fitted the logarithmic-oxidation rate law, w = K1n ln(1 + -t/to) [1] where w is the weight of oxygen consumed, t is the time, and K In, and to are constants. First estimates to were obtained according to the method of Taylor Thon8 and were then employed to obtain the best simuItaneous estimates of to and K In, that would fit the logarithmic expression. These estimates were found numerically, so that the residual variance could be minimized. The calculations were performed on an

Jan 1, 1961

By J. I. Budnick, W. B. Ittner III, D. P. Seraphim

A reliable technique has been developed for producing single crystals of tantalum in the form of small diameter wires. By suitably heat treating these and polycrystal samples, first in an oxygen atmosphere and finally in vacuum, it has been found possible to reduce residual resistivities to 10-3 microhm-cm. The purity of these samples is thus comparable to the purities obtained in zone-refined silver, copper, and aluminum. THE growth and purification of pure single crystals of the transition metals is, in general, difficult. The high melting and annealing temperatures of these metals make it necessary to employ rather special techniques in any crystallization process. In addition, the transition metals show a great affinity for and are easily contaminated by nitrogen, oxygen, and carbon. Recently, however. a number of investigators have been successful in growing,

Jan 1, 1961

By W. J. Babyak, F. N. Rhines

It has long been supposed that, regardless of the mechanism by which grain boundaries increase the hardness of a ductile metal, the effect should be linearly proportional to the grain boundary area. At the present time two methods for determining grain boundary area in an isotropic aggregate are available. The first, derived by Angus and Summers,&apos; presumes that the grain boundary area is equal to 3vn, where n is the number of grains per sq mm in a random section through the metal. This estimate is based upon the assumption that the grains are equivalent to cubes whose faces correspond with the grains as observed in the micro-section. Measurements on copper, bronze, and a brass showed that a nearly linear relation exists between 3vn and hardness. This is illustrated, for the case of brass, in Fig. 1. The second method, developed independently by Smith and Guttman2 and by Duff in, Meussner, and Rhines,3 is absolute and employs a simple linear intercept count for measuring grain boundary area. It involves no assumptions with respect to the shape and distribution of the grain boundaries. The total surface in unit volume is 2 NL , where NL is the number of intercepts between grain boundary and unit length of a test line passed randomly through the sample. In practice, NL,, the average number of grain boundaries intercepted by unit length of traverse across a prepared microsection, is ob-

Jan 1, 1961

By M. J. Sinnot, J. C. Shyne

Low-frequency mechanical damping measurements were made to investigate internal friction in Fe-A1 alloys. The atomic ordering of the Fe-A1 system strongly influenced the stress-induced ordering internal friction. Magnetoelastic damping was also encounteyed and was shown to be reduced by the application of a static stress. THIS paper describes some damping experiments made on alloys of Fe and Al. Stress-induced ordering internal friction was measured with samples containing from 9.8 to 31.3 at. pct Al. Aluminum is soluble in a-Fe to about 50 at. pct and forms at least two long-range ordered structures, Fe3Al and Feu.&apos; Stress-induced ordering internal friction is known to occur in many substitutional solid solutions, but few measurements of this damping effect have been made with alloy systems that have pronounced ordering tendencies. LeClair and Lomer developed expressions relating the relaxation strength of the damping process to the degree of atomic ordering and predicted that stress-induced ordering internal friction would be zero with complete ordering.&apos; This concept was confirmed experimentally by Lulay and Wert using the system cd-Mg It is also consistent with the weak stress-induced ordering peaks observed in P -brass by Artman and in 16 wt pct Al Fe-Al by bert.&apos; It was expected, therefore that the ordering characteristics of the system Fe-Al would strongly influence the stress-induced ordering internal friction exhibited by the experimental alloys. SAMPLE PREPARATION The alloys used in this investigation were induction melted under vacuum using high-purity melting stock. The iron was electrolytically refined Plastiron 101 which contained 99.85 wt pct Fe. The aluminum was a special 99.95 pct pure grade supplied by Alcoa. The only other raw material was spectrographically pure graphite which was used in small quantities as a deoxidant. The amount of carbon used was slightly in excess of the amount required to completely deoxidize the melt; this resulted in residual carbon contents of 0.01 to 0.02 pct in the finished alloys. The vacuum cast 2 1/2-in. diam ingots were hot rolled to 5/8-in. diam round bars. Portions of these bars were hot swaged and hot drawn to 0.050-in. diam wire. Straight pieces of the hot drawn wire were slowly heated to a temperature of 1300°C in a He atmosphere. After holding for 4 hr, the samples were allowed to cool in the furnace. This annealing treatment resulted in grain growth in the samples, the final grain size being about the same as the wire diameter. The grain boundaries were oriented perpendicularly to the wire axis, giving a bamboo grain structure. The existence of a preferred orientation could not be detected in these coarse grained samples. If the samples had a fiber structure, this probably would have been the same in all samples because of similar processing, thus the influence of crystal orientation on the relaxation strength would have been similar in all samples. The aluminum contents of the alloys are listed in Table I. EQUIPMENT The principle of the torsion pendulum was used for the internal friction measuring device. The

Jan 1, 1961

By P. Chiotti, G. R. Kilp

IN the study of zinc-zirconium1 and zinc-uranium2 systems, vapor-pressure measurements were made in order to establish the equilibrium phase diagrams for a pressure of 1 atm. In each of these systems, only zinc has an appreciable vapor pressure over the temperature range investigated. The zinc pressure was measured over a sufficiently wide temperature and composition range to permit calculation of the standard free energy, enthalpy, and entropy of formation for the compounds ZrZn, ZrZn2, ZrZn3, ZrZn6, ZrZn14 , and U2Zn17. In these calculations the compounds were treated as line compounds. Although the exact composition range was not determined, metallographic and thermal data indicate that the solubility range for these compounds is small. It is to be noted that the compound initially reported to correspond to the formula UZn9, 2 has been shown by the crystal structure work of Makarov and vinogradov3 to correspond to the formula U2Zn17,. The crystal structure is similar to that for the compounds Th2M17, investigated by Florio,4 et al; here M represents iron, cobalt, or nickel. Therefore, thermodynamic calculations are based on the formpla U2Zn17 EXPERIMENTAL The dew-point method employed to measure the vapor pressure of zinc over uranium-zinc alloys has been described previously.2 The same procedure and apparatus were used in measuring the zinc pressure over zinc-zirconium alloys. In the case of alloys in the two-phase region consisting of a zirconium and the compound ZrZn, the Knudsen effusion method was employed to obtain a few values in the temperature range 600" to 560°C. In most cases, tantalum crucibles were used to contain the zirconium alloys. THERMODYNAMIC PROPERTIES OFU2Zn17 A least-squares treatment of the vapor-pressure data obtained for 35 and 65 wt pct U alloys in the temperature range 650° to 940°C gave lOg10PAtm = 7,713/T + 6.33 Here, as in following equations, T represents degrees kelvin and P represents the zinc vapor pressure in atmospheres. The probable errors for the two constants were calculated to be 60.68 and 0.0563, respectively. This relation represents the equilibrium dissociation pressure for the reaction U2Zn17 (s) - 2U(s) + 17Zn(v) The solubility of zinc in solid uranium is negligible and the only additional information required to calculate the free energy of formation of U2Zn17 is the free energy of vaporization of pure zinc. K. K. Kelley5 gives the relations, AF°= 30,902 + 6.03Tlog T + 0.275 X 10-3T2 - 45.03T

Jan 1, 1961

[ARTICLE I. NAME AND OBJECT Section 1. This Society shall be known as the Society of Petroleum Engineers of the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. Section 2. The object of the Society of Petroleum Engineers shall be to furnish a medium of cooperation among those interested in the petroleum-natural gas industry an to promote the advancement of this branch of mineral technology through meetings to stimulate the preparation, reading, discussion and circulation of papers connected therewith. ARTICLE II. MEMBERS Section 1. Any person who is a member of AIME may become a member of this Society by the specified process. Section 2. Local organizations may be formed by the Society of Petroleum Engineers as subsidiary units, the membership of which shall be subject to and in accordance with the by-laws of the Institute.]

Jan 1, 1961

By H. W. Schadler

Single crystals of tungsten, which were grown by electron bombardment floating zone refining, were strained 2 pet in tension and bending at 298°, 77°, and 20°K to determine the modes and crystallography of the plastic deformation of these temperatures. At 77° and 20°K plastic deformation occurs by slip on systems of the type (011) [111] and by twinning on (112)-type planes. For crystals strained at 298°K, deformation occurs by slip in [111] directions on either (Oil)- or (112)-type planes. CURRENT models for the initiation of brittle fracture in crystalline materials are based on a knowledge of the details of their plastic deformation.1 Body-centered cubic tungsten exhibits brittle failure at temperatures below about 500 °K yet the modes and crystallography of its plastic deformation have not been studied below 1000°K. In 1924, Goucher2 reported that tungsten single crystals with a total impurity content of less than 0.01 wt pet deformed by slip on the (112) [111] system in the temperature range 1000° to 3000°K. He also observed (001) [010] slip in one crystal which was constrained by the presence of a large fissure. According to Barrett3 tungsten also deforms by twinning on the (112) plane in the [111] direction, but he gives no details on the tendency for twin formation or the temperature range in which twinning occurs. Therefore, as a necessary part of a study of the factors influencing the brittle fracture of tungsten, the modes and crystallography of the plastic deformation were determined at 298°, 77°, and 20°K. Tungsten single crystals, grown using the electron-bombardment zone-refining technique first described by Calverly,4 were deformed to between 1 and 2 pet plastic strain in tension and bending. The surface offset resulting from slip or twinning was observed with an optical microscope to determine the crystallography of the deformation. The existence of twins was proven by the standard polishing and etching technique; and the crystallography of dislocation motion was followed using the dislocation etchant described by Wolff.5 Some observations on the fracture characteristics of tungsten single crystals are included. EXPERIMENTAL TECHNIQUES Growth, Purity, and Perfection of the Crystals-Several years ago Calverly, Davis, and Lever4 dem-onstrated the feasibility of growing tungsten single crystals by the electron-bombardment floating zone-refining technique, and Carlson6 showed that crystals produced in this way had a high degree of purity and were ductile at room temperature. Tungsten single crystals produced by this technique in equipment similar to that described by Carlson were used in this study. The starting material, a powder metallurgy product, was obtained in the form of a swaged 1/8-in. rod from the General Electric Wire Plant in Cleveland, Ohio. The crystals were grown from this material in a vacuum of 10"4 mm of Hg by passing a molten zone 1/8 in. long down the rod twice at a speed of 3 mm per min. At this zone speed

Jan 1, 1961

By J. M. Roberts, N. Brown

The stress-strain behavior of zinc single crystals was measured over a strain range of 10-6 to 10-2. The phenomenon of macroyielding was observed in detail and plastic strains were detected at almost zero-stress. Closed hysteresis loops were observed during loading and unloading in the strain region of about 10-5. From the hysteresis a frictional stress on the dislocation of about 6 psi was obtained. A preliminary analysis indicates that impurities are primarily responsible for the friction. Nonelastic Strains as much as 10 -4 were recovered depending on the amount of prior deformation. Part of the recovered strain occurs instantaneously upon unloading and the remainder occurs at zero stress. The time dependence of the recovered strain was measured. THIS investigation is concerned with the details of plastic deformation preceding the ordinary yield point as measured with the usual strain sensitivity of about 10-4. The approach leads to internal friction observations in the hitherto neglected frequency range below 10-1 cycles per sec. It is believed that if the phenomenon of macroscopic yielding is to be understood, then the stress-strain curve in the neighborhood of the macroyield point should be greatly magnified. It may then be possible to determine whether macroscopic yielding is a unique event or whether it is a process which begins gradually at a lower stress. In the case of low-carbon steel a unique event obviously occurs at the macroscopic yield point as indicated by a drop in the load, but copper appears to exhibit a gradual transition from the elastic to the plastic state. In zinc the yield point is rather abrupt although the data indicates that some plastic deformation precedes large scale yielding.&apos; One of the purposes of this investigation is to determine whether there is an abrupt transition from the preyield microstrain region to the region of macroscopic deformation. Such a rapid transition would support the concept that there is a critical stress for yielding. The concept that yielding is a unique event associated with such phenomenon as activating a Frank-Read source, freeing the dislocation from solute atoms, dislocations cutting through dislocations, or dislocations moving freely by one another, has been expounded widely on theoretical grounds. It is hoped that highly sensitive measurements of strain in the neighborhood of the macroscopic yield point will shed some light on the event known as the "Yield Point". EXPERIMENTAL METHOD 1) Specimens—High-purity zinc was cast into spherical graphite moulds in air and grown into spherical single crystals by the Bridgman method under a positive pressure of Argon gas. Spectro-graphic analysis of cleaved sections from four crystals showed a purity of 99.994 pet Zn. The specimens were acid machined with an 1/8 in. gage section in a form similar to those used by Parker and co-workers.2 Bausch type grips were fastened to the specimen by Epon VI adhesive. The specimens were oriented so that only [1120] (0001) slip occurred. Fig. 1 shows two of the specimens in the grips. Prior to each test, the gage section of the specimen was given a concentrated HNO3 chemical polish followed by alcohol rinsing and air blast drying. 2) Test Method- The shear tests were performed on an Instron testing machine and the experimental set-up was made very "hard". Strain could be measured to a sensitivity of 10 -6 by means of a capacitance gage extensometer. The design and calibration of this type of extensometer to measure microstrain, as applied to pure shear and tensile tests of metals, will be the subject of a separate paper—therefore, only a brief account will be presented here. The method essentially consists of attaching a

Jan 1, 1961

By John Chipman, Daniel Dutilloy

The equilibrium of gaseolis H2O-H2 mixtures with liquid iron-phosphorus alloys in the range 0 to 3 pct P is used to establish the increuse of the activity coefficient of oxygen, in the presence of phosphorus. Two different sampling techniques are used. THE importance of oxygen as a refining agent in steelmaking operations makes it desirable to improve our understanding of its behavior. Phosphorus which is always present in the ores has adverse effects on steel properties and its removal is necessary. The present study was undertaken to evaluate the interaction of oxygen and phosphorus in molten iron. Bookey, Richardson, and welch1 have studied the phosphorus-oxygen equilibria in liquid iron in the presence of lime. They used a mixture of hydrogen and water vapor to control the oxygen potential and worked with crucibles made of tetracalcium phosphate and lime. At low phosphorus concentration, i.e., at high oxygen, they observed a marked deviation in their results. They tentatively ascribed this to a large negative effect of oxygen on the activity of phosphorus. This was then included by chipman2 in his review of interactions in liquid iron. Pearson and Turkdogan 3 have later reported an interaction parameter They equilibrated a mixture of hydrogen and water vapor with an iron-phosphorus alloy contained in an alumina crucible and sampled the melt by suction in a silica tube. The solubility of oxygen in iron-phosphorus alloys has been studied by Levenets and Samarin.4 They reported an interaction parameter

Jan 1, 1961