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By F. S. Buffington, Morris Cohen

THERE is little quantitative information available concerning the effect of applied stress, in both the elastic and plastic ranges, on diffusion kinetics. Accordingly, a program has been undertaken to determine the rate of self-diffusion in high purity iron, with the specimens subjected to stress during the course of diffusion. Results are reported here for body-centered cubic iron at a diffusion temperature of 890°C. The iron used was 99.97 pct Fe, the principal impurities being 0.002 pct C, 0.008 pct 0, and 0.02 pct Si. The surface-decrease method of self-diffusion analysis was employed, and Fe55 Mn x-radiation, 2.9 years half-life) was the tracer element. Details of specimen preparation and equipment are given elsewhere.' Disks of the high purity iron, % in. diam x 1/4 in. thick, were annealed at 890°C for 18 hr in dry hydrogen to produce large grains of a ferrite. The faces of the disks were then surface ground, and possible grinding stresses were relieved by annealing at 890 °C for 45 min in vacuum. A layer of radioactive iron 0.00186 cm thick was electroplated on one face of each disk. The self-diffusion coefficient was calculated from the ratio of the radiation intensities emanating from each of these faces, as measured before and after diffusion.' The heating was carried out in a vacuum furnace (10-5 mm Hg) controlled to ±1.5°C. The specimens were loaded in compression between two quartz disks during the diffusion runs by means of a lever system operating through a vacuum seal. Thus one quartz disk was pressed directly against the radioactive face of the specimen, minimizing the vapor loss of radioactive iron. Steady-state creep occurred in all instances where permanent deformation could be detected, but the specimens did not exhibit appreciable transverse barreling until natural strains of 0.2 to 0.3 were attained. Essentially, the diffusion took place under uniaxial stress. The plastic strain in each case was obtained at the diffusion zone by measuring the diameter d there before and after the run: e = 2 In — do Let Du equal the self-diffusion coefficient which would have prevailed at the given temperature if no stress had been applied. This was calculated from the temperature-dependence equation which had been previously determined: —59,800 D, = 6.2 exp ( I sq cm per sec* [I]

Jan 1, 1953

By Nathaniel Arbiter, Arthur F. Taggart

THE chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 c.c. of a solution containing 495 mg. of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative proof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type [R+ + Y- + MX =± RX + M+ + Y¬] where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the massaction and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or Y-. Experimental work comprised determination of (1) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (2) the contact angles1 of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run with barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1944

By Alexander Knoll, Dwight L. Baker

THIS paper is a report on work undertaken to investigate the results and conclusions of Ravitz and Porter1,2 that galena freed of surface oxidation products and lead carbonate ("clean" galena) is waterrepellent, and that the action of xanthates in flotation is the action of a cleansing agent, enabling oxidized galena particles to expose a pure lead sulphide, water-repellent surface. The apparatus, in construction and use, was essentially that of Ravitz and Porter. The only significant modification introduced by the present authors was the substitution of a three-necked flask for the flotation cell as the "reaction vessel." Our procedure was to place 50 grams of freshly ground, minus 200-mesh galena in the reaction vessel, sweep out all molecular oxygen from the system with oxygen-free nitrogen, and proceed to wash the galena surface free of its oxidation products with repeated small portions of (I) ammonium acetate (500 c.c. of water, 200 grams of ammonium acetate) or (2) ammonium chloride, hydrochloric acid (2 liters containing 200 grams of ammonium chloride and 25 c.c. Of 1.18 sp. gr hydrochloric acid). The galena was next washed with many 100-c.c. portions of oxygen-free, distilled water. The galena was finally considered free of soluble salts when wash water that had been in contact with the mineral for at least 48 hr.* gave negative tests for: (x) lead ion with sulphide; (2) chloride with silver ion; (3) acetate with cuprous chloride, sodium chloride; and (4) ammonium ion with Nessler's reagent. Next 500 c.c. of potassium ethyl xanthate solution, free of dissolved oxygen, was run onto the "clean" galena particles. For this system there were determined: I. The wetting properties of the clean galena particles by shaking the reaction flask and noting the degree of mineral collection at the liquid-air interface. This was, of course, simply a qualitative test, but it proved adequate for our purpose. 2. The removal of xanthate ion from the potassium xanthate solution on being shaken with the "cleansed" mineral. Xanthate concentrations were determined by iodine titration according to the methods of Taylor and Knoll.3 3. The pH of the xanthate solution after having been shaken with the "cleansed" galena. The pH was determined colorimetrically.4 The results of five experiments of the type mentioned above are given in Table x.

Jan 1, 1941

By Alden B. Greninger

Many recent contributions in the field of theoretical metallography have been concerned with crystallographic definitions or descriptions of various phenomena. The lattice orientation of the crystal being studied must be known before such definitions can be made. Practically all the metallic crystals used do not have crystal faces—other than the unknown "plane of polish"; hence resort must be had to other means of determining orientations. Some use has been made of etch-figures, slip bands, optical properties, etc., for this purpose; but for accurate results, and because of the fewer restrictions to their use, the various X-ray methods have been the most satisfactory.' The methods that have been used may be divided into two general classes: (1) oscillation methods, and (2) transmission Laue methods.² The disadvantages of these methods are numerous, chief among them being the time required to determine a complete orientation. No method proposed so far is wholly satisfactory for determining the orientation of a small macrograin within a polycrystalline aggregate.

Jan 1, 1935

By Alden B. Greninger

Many recent contributions in the field of theoretical metallography have been concerned with crystallographic definitions or descriptions of various phenomena. The lattice orientation of the crystal being studied must be known before such definitions can be made. Practically all the metallic crystals used do not have crystal faces—other than the unknown "plane of polish"; hence resort must be had to other means of determining orientations. Some use has been made of etch-figures, slip bands, optical properties, etc., for this purpose; but for accurate results, and because of the fewer restrictions to their use, the various X-ray methods have been the most satisfactory.' The methods that have been used may be divided into two general classes: (1) oscillation methods, and (2) transmission Laue methods.² The disadvantages of these methods are numerous, chief among them being the time required to determine a complete orientation. No method proposed so far is wholly satisfactory for determining the orientation of a small macrograin within a polycrystalline aggregate.

Jan 1, 1935

By W. J. Parton

THE efficient recovery and preparation of small sizes of anthracite called No. 4 Buckwheat (3/3 2 by 1/3 2 in.) and No. 5 Buckwheat (1/3 2 in. by 0), present a difficult problem to the anthracite operators. In many instances preparation of these sizes, particularly No. 5 anthracite, is extremely inefficient. In many of the older preparation plants, inadequate facilities, and often none at all, were provided as an integral part of the plant for cleaning this fine anthracite. Consequently, much of the material smaller than s, 32 in. was discarded. As the demand for these sizes increased, facilities for preparing the fine sizes were often crowded into existing structures with consequent sacrifices of capacities and efficiency. In addition to this condition, the methods of preparing the finest sizes are being developed in an attempt to improve their efficiencies. Because the demand for small sizes of anthracite still is increasing, many operators would benefit by investigating and improving the cleaning equipment employed on these sizes.

Jan 1, 1949

By P. W. Bridgman

DURING the war, the Navy undertook the construction, under my direction, of an experimental gun embodying features designed to lessen the cost and time of production. These experiments were initiated after representations as to their, desirability had been offered by myself, by the Naval Consulting Board, and by the National Research Council. The first drawings were made in June, 1917, and the experiment was completed in November, 1918. For the sake of clearness it will pay to recapitulate briefly the fundamental idea of gun construction. It is well known that if a hollow cylinder is subjected to internal fluid pressure, the maximum stress occurs in the inside layers, the outer parts carrying much less than their due share of the stress. This inequality of stress is more pronounced the thicker the walls of the cylinder. If such a cylinder is pushed to the elastic limit, failure in elasticity will take place long before the outer layers have reached the limit of their capacity. Economical use of the material would demand, however, that all parts of the cylinder reach the limits of their capacity simultaneously. This may be brought about, at least in cylinders of not too great thickness, by producing in. the inner layers an initial compression, and in the outer layers an initial tension. The effect of internal pressure is at, first to relieve the compression of the inside layers, while increasing the tension of the outside layers. If the initial stresses are properly distributed, all parts of the cylinder will reach their elastic limits simultaneously, thus giving a cylinder of maximum strength for its weight. In gun construction as hitherto practiced, this initial distribution of stress is produced either by winding the inner tube with wire, a common English practice, or by shrinking hoops over the inner tube, which has been the standard American practice. Either process is long and expensive, particularly with the larger guns, 12- or 14-in., which require

Jan 2, 1920

By N. J. Themelis, A. W. Last

Autogenous grinding, broadly defined as the self-comminution of ore in a cylindrical tumbling mill without using auxiliary grinding media, was first applied in the early 1930s in the so-called Hadsel mills (Hardinge, 1955) as seen in [Fig. 1], mainly used in gold mines on the US West Coast. A number of these mills were built in sizes of 6.1 to 7.3 m (20 to 24 ft) in diameter and 1.5 to 1.8 m (5 to 6 ft) in length but were later abandoned because of operating and maintenance problems. Further development of autogenous grinding led to the Hardinge wet grinding mill, the Aerofall dry grinding mill, and others. A tabulation of all known autogenous and semiautogenous installations around the world was sent recently to the authors by G. J. Kushner of Koppers Metal Processing Division. In the size range of 7.3 to 9.8 m (24 to 32 ft) in diameter, it lists a total of thirty mills used in the processing of copper ores. An additional 120 units are listed in the same size range for the processing of iron ores and other minerals. The largest mills in existence are 11.1-m-diam X 4.6-m-long (36-ft-diam X 15-ft-long) mills in Minnesota, powered by 8950 kW (12,000 hp) motors and used in taconite beneficiation. It is indicative of the phenomenal growth of this technology that none of the above 150 mills was in operation prior to 1964. Grinding rates in autogenous mills are very sensitive to variations in ore breakage characteristics and even with fairly constant ore type can exhibit large fluctuations in throughput. Autogenous grinding also depends on availability of a fraction of the ore to be ground in the form of "competent" rock which can withstand to a certain degree the tumbling and impact action within the mill. If the ore is uniformly "soft", it will soon be crushed into small size particles and further grinding, which depends on the existence of large size rocks in the mill, becomes impossible. This apparently is the case with most copper ores, as discussed by Bachman, Last and Nabbs (1970) who described pilot testing of a large number of ore samples from Kennecott 's Chino Mines. Under circumstances where autogenous grinding is impractical, it is possible to realize most of its benefits by utilizing large grinding balls in place of the "competent" rock and practice what has become known in the mining industry as semiautogenous grinding. In semiautogenous grinding (SAG), a grate discharge tumbling mill is fed the product of a primary crusher or run-of-mine rock. Forged steel or alloy grinding balls, in proportions ranging from 3.10% of the total volume in the mill, are used to complement the self-grinding ability of the ore. Semiautogenous circuits can be either designed for single-stage closed-circuit grinding which produces a final product for recovery processes, or for two-stage operation in which the SAG mill product is fed to a second stage of grinding in a conventional ball mill.

Jan 1, 1981

By E. P. Abrahamson

The effect of transition element binary solid solution additions upon the re crystallization temperature of nickel has been investigated. All additions raised the re crystallization temperature. Both the rate of change of re crystallization temperature with at. pet solute and the limit of initial linearity are found to correlate with the free atom ground state outer electron configuration of the solute element. A comparison of all of the correlations for the transition elements studied has yielded a set of empirical relations, which allows the prediction of the effect of dilute binary transition elements on the recrystallization temperature of other transition elements. The work of Abrahamson, et al.1-7 on dilute binary solution alloys indicated a correlation between the free atom ground state electron configuration of the solute and both the brittle-ductile transition and re-crystallization temperature. Further, it has been shown3,4 that the limit of initial linearity may also be correlated with the solute electron configuration. Since previous studies have dealt with bee and hexagonal base elements, this study is made to note what effect, if any, the fee base structure might have. Nickel also serves to give a solvent configuration which will allow the comparison of all of the transition element solvents. Olsen8 has studied the effect of some trace elements upon the recrystallization of nickel. He included only Ti, Zr, W, Mn, and Co of the transition elements. The differences in change of recrystallization temperature were attributed to the solute atom size and to the solubility of the solute in nickel. PROCEDURE All alloys were made using 99.9 + pet Ni with 0.003 C, 0.015 Fe, 0.007 0, and 0.0007 H. The solute elements were 99.9 + pet pure. According to the published binary phase diagrams9 and metallo-graphic examinations at X750, all solute elements were in solid solution. The alloys were arc melted and remelted four times in the form of cubic 200-g buttons under an argon atmosphere. They were then hot forged at 800oC to 0.750 in. diam, machined to 0.60 in., vacuum annealed for 1 hr at 700°c, swaged to 0.40 in. and annealed at 700oC for 1 hr in vacuum. The grain size was checked and found to be 77 * 20 grains per sq mm. The specimens were then swaged to 0.187 in., yielding 76 ± 1 pet cold work. All alloys were then chemically analyzed for the solute addition. The interstitial contents remained at the values of the starting material when checked on random alloy specimens. The swaged rod was cut into 8.25 in. lengths and heat treated in a gradient furnace for 1 hr. The gradient was maintained at 250" to 850°C over an eight inch length, recorded by twelve thermocouples. Control was ± 3oC, accomplished at the hot end. The recrystallization was determined metallo-graphically over the entire specimen. The criterion chosen was that point on the specimen showing the first recrystallized grain at a constant magnification, X200. Specimens were repeated, and the agreement was found to be generally ± 3oC.

Jan 1, 1962

By D. H. Polonis, M. B. Kasen

AN unusual thermal etching phenomenon has been observed on the surface of a Cu-Si alloy. The observations were made during studies of vacancy condensation pit formation which were reported in previous papers.1,2 Figs. 1 and 2 are photomicrographs of the surface of a Cu-4.8 pct Si alloy after heating in vacuo (3 x X mm Hg) to 525°C and subsequently holding at that temperature for 16 hr in an impure (air-contaminated) argon atmosphere. Under these conditions preferential removal of silicon from the matrix by oxidation results in a surface which is entirely a phase overlying an a plus y structure. The light areas of Fig. 1 are regions in which very little thermal etching has occurred, while the majority of the surface has experienced severe etching. Similar regions in Fig. 2 are seen as plateaus above contours produced by net transfer of material from the specimen surface. Twin boundaries are also visible in Fig. 2. The difference in matrix mi-crostructure between Figs. l and 2 reflects the par- ticular orientation of low-index planes with respect to the surface of observation. Thermal etching contours of this type have been studied in detail by Hondros and Moore Both of the photomicrographs show that one or more dark spots are located approximately at the center of every protected area; where two spots are in close proximity, the protected areas have merged. The microstructures indicate that the anomalous resistance to thermal etching is related to the presence of these spots. Williams and Hayfield have shown that local regions of unusually high oxidation resistance can be caused by a surface monolayer of atoms with a work function higher than that of the base material. The result is an inhibition of the rate of electron removal from the base material and a decrease in the oxidation rate. The source of the protected layer may be either surface diffusion from contaminants on the specimen surface or pipe diffusion of solute atoms followed by migration across the surface. In the latter case the driving force is a difference in chemical potential resulting in a Gibbs adsorption phenomenon. In the present case, chemical polishing of the specimen surface precluded contaminants of a strictly surface nature. Consequently, diffusion of impurity atoms from within the lattice appears to be the most tenable explanation of the observed phenomena. The authors propose that the structures of Figs. 1 and 2 reflect the diffusion of impurity atoms along extended dislocations within the individual a phase grains prior to surface oxidation. The central spots within the protected regions are seen as sites of dislocation emergence which have become locally decorated with oxide in the manner discussed in Ref. 1. Williams and Hayfield observed protected regions adjacent to the grain boundaries of iron-contaminated copper which they attributed to the segregation of iron to the grain boundaries coupled with high dif-fusivity along the complex dislocation array at such boundaries. No evidence of such grain boundary protection was observed in the Cu-Si alloy; this

Jan 1, 1964

By J. W. Fredrickson

VERY little information is available in the literature concerning the solubility of magnesium in titanium. Aust and Pidgeon&apos; report the solubility of titanium in magnesium to be 0.0025 pct at 650°C and 0.015 pct at 850°C. X-ray diffraction studies failed to detect any evidence of solid solubility. Based on the fact that the addition of titanium to magnesium increases the c/a ratio of magnesium, Busk&apos; suggested that the Mg-Ti system, like the Mg-Zr, is a peritectic. Eisenreich- eported the solubility of titanium in magnesium to be 0.003 pct at 655°C and 0.064 pct at 760°C. Removal of hydrogen from the melt increased the solubility of titanium to 0.115 pct at 800°C. Eisenreich proposes a peritectic-type diagram for the high magnesium side of the system. Recent work&apos; with Ti-Mg diffusion couples indicate that the solid solubility of titanium in magnesium is extremely small and that there is limited solid solubility of magnesium in titanium. Experimental work on the Ti-Mg system is complicated by the fact that the boiling point of magnesium is considerably below the melting point of titanium. Consequently, the usual alloying methods are impractical. Alloying was accomplished in this investigation by sheath-rolling compressed compacts." The alloys were made from titanium sponge and high purity magnesium. Chemical analysis of the sponge showed 0.04 pct Mg, <0.005 pct Al, <0.001 pct Cu, 0.05 pct Fe, 0.022 pct Mn, <0.0025 pct Ni, 0.007 pct Si, <0.005 pct V, and <0.01 pct Zn. All heat treating was conducted in a protective atmosphere by encapsulating the specimens in fused silica ampules under a partial pressure of helium. Equilibrium was achieved by holding the specimens at temperature for periods of 24 to 120 hr. The alloys were hot rolled, cold rolled, and annealed prior to solution heat treatment. Fig. 1 shows the constitutional diagram obtained for the Ti-Mg system up to 1.5 pct Mg. Oxygen was known to be present in the alloys; therefore, it is necessary to consider the alloys as ternary rather than binary and the diagram should be viewed as a plot of a section through the Ti-Mg-0 system. Other investigatorso have shown that the addition of oxy- gen to titanium stabilizes the a phase. The data presented in Fig. 1 indicate that the addition of magnesium to titanium tends to stabilize the p phase. Armour Research Foundation7 has shown that the addition of magnesium to zirconium lowers the a transus and is classified as a p stabilizer in that system. Magnesium is soluble in solid titanium to the extent of at least 1.5 pct in both the a and /3 phases. No intermetallic compounds or magnesium-rich phases were observed either by light microscopy or X-ray diffraction. However, this does not negate the possibility that such phases exist at higher alloy concentrations.

Jan 1, 1956

By J. S. Bryner

INTRODUCTION IN the study of metallographic specimens in the electron microscope, there is need for a method of locating the same field in both the light microscope and the electron microscope. This need arises chiefly from the fact that in the electron microscope the magnification and degree of resolution are so much higher, and the field so much smaller than in the light microscope that it is often difficult, if not impossible, to identify positively what is being observed. The difficulty is increased by the fact that, because a transparent film replica of the metal surface must be used in the electron microscope, micro-constituents can be identified not by their color but only by their texture and contours. For these reasons it is desirable to obtain a series of photographs showing the same field in both microscopes in order that the appearance of common microstructures and micro-constituents in the electron microscope may be identified and catalogued for future reference. The need for a method of locating the same field in both microscopes arises also when it becomes desirable to enlarge in the electron microscope for more detailed study a particular interesting structure observed in the light microscope. Using the standard polystyrene-silica1,2 replica technique, in which the silica film replica is fished from the ethyl bromide on a 1/3 in. diam 200-mesh specimen screen, the possibilities of locating a particular area on the film in the electron microscope are rather remote. The desired structure may be obscured by the wires of the specimen screen or unrecognizable at the high magnification. A solution to the problem would be provided if a specially designed specimen screen, containing an opening which could be absolutely identified and quickly located in the electron microscope, could be fastened to the silica film replica in such a position that the desired field on the specimen would be located at the identifiable opening in the specimen screen. The design for such a specimen screen, a method for producing it, and a technique for fastening it to the silica film replica are described below. DESCRIPTION OF METHOD The Specimen Screen A simple design for a specimen screen containing an opening easy to identify and locate in the electron microscope is one with two lines of openings at right angles in the form of a cross. Such a screen is shown in Fig I. The opening at the center of the cross is identified easily and can be located quickly in the light microscope and in the objective image of the electron microscope. The specially designed specimen screens for this work were produced in quantity by electroforming. On both sides of a polished strip of copper 1 X 3 X 1/8 in., twenty patterns of the cross of openings were punched with a diamond point micro-hardness tester, using a load of magnitude

Jan 1, 1948

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement, breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By B. G. Ricketts, A. Kelly, P. A. Beck

The isothermal kinetics (at 200" to 400°C) of subgrain growth and of softening were studied in a 99.997 pct pure Al crystal rolled to 80 pct RA, under conditions where recrystallization did not take place. It was found that the kinetics of subgrain growth and of softening were similar, and that the correlation between subgrain growth and softening was in first approximation independent of the annealing temperature. It has been shown by Heidenreich&apos; by means of electron transmission microscopy and by Hirsch and Kellar2 by means of an X-ray microbeam technique that the crystals of heavily cold-worked polycrystalline aluminum consist of subgrains of approximately 2µ diam, which are slightly disoriented with respect to each other. This substructure is found on cold working at room temperature, without annealing. A preliminary study has been previously published3 of the softening upon annealing at 350°C of a heavily cold-rolled aluminum single crystal. Softening and X-ray line sharpening for such a rolled aluminum crystal were later studied in more detail as a function of annealing time and temperature.4 Perryman5, 6 has studied the recovery of polycrystalline aluminum after cold rolling. By means of phase contrast microscopy he found that the subgrain size increases with the annealing temperature but does not alter very much with annealing time at a given temperature. In the present work further study was made of softening as a function of annealing time and temperature and subgrain sizes were determined by two different techniques in an attempt to find any correlation that may exist between softening and subgrain growth. Subgrain size measurements were made both by the X-ray microbeam technique and by transmission electron microscopy. EXPERIMENTAL PROCEDURE For the X-ray studies specimens were cut from

Jan 1, 1960

By R. C. Ruder, C. E. Birchenall

The method of decrease in surface activity was used to determine the rates of diffusion of Co" into cobalt and into nickel. Since the absorption curves for cobalt radiation were quite complex under the conditions of these experiments, the effects of geometry and surface preparation on the diffusion results were investigated. The cobalt self-diffusion coefficients obey the equation DCoco = e-61100/RT cm2 per sec. For dilute cobalt diffusing in nickel, DConi, == 1.46 e-/R&apos; cm2 er sec. AS part of the general program to measure the self-diffusion and dilute-solution diffusion rates of the iron-group metals, the diffusion coefficients of cobalt into cobalt and nickel have been measured using the radioactive isotope Co"&apos;. Self-diffusion studies in iron have been previously reported by Birchenall and Mehl.&apos; The technique of measurement used was the decrease in surface activity method described by Steigman, Shockley, and Nix.&apos; It has been determined that scattering of the measured beta radiation by the specimen matrix is significantly influenced by the condition of the surface and the counting geometry. Accurate diffusion coefficients can be calculated from the activity data provided that the specimens have plane diffusion surfaces and that the absorption properties of the emitted radiation are determined under geometrical conditions duplicating with external absorbers the absorption and scattering in a thin film at the specimen surface as nearly as possible. The cobalt used in this research was originally in the form of hydrogen reduced rondels 99.9+ pct pure. The nickel had been prepared by the carbonyl process and was found by spectrographic analysis to contain 0.03 pct Fe, 0.04 pct Co and smaller traces of other metallic elements for a balance purity of 99.9+ pet Ni. Both materials were vacuum melted and cast in rectangular ingots. Specimens 7/8x7/8x1/4 in. were machined from these ingots. The specimens were then ground to 4-0 emery paper and annealed in hydrogen for at least a day at 1200°C. Some of the specimens were used in preliminary experimentation after which their diffusion faces were machined to remove the radioactive material from the previous diffusion experiments. After grinding, the specimens were polished using an electrolytic lapping technique described by Mazia." This lapping was continued until at least 0.005 in. was removed from the diffusion surface. The final surfaces were metallographically smooth except for a few fine scratches caused by the glass cloth. A large percentage of the area was undisturbed as determined by microscopic examination. The grain diameters of the diffusion specimens varied from 0.1 to 5 mm. There were no effects due to grain boundary diffusion in the experiments

Jan 1, 1952

By C. C. Harris

The characteristics of some common size distribution equations are critically discussed. A generalized form of several well-known size distribution equations is obtained from a differential equation describing statistical distributions. The equation contains three parameters and can describe the major features of size distributions in the fine and the coarse size regions. A graphical method for its implementation is provided. The application of this and other equations to sets of data are compared both for the quality of fit and from a comminution kinetics viewpoint. If a narrow size range of a brittle material is broken sufficiently to obliterate the feed sizes, but not so severely that excessive secondary breakage occurs, a plot of cumulative fraction by weight undersize (Y) vs. sieve size (X) on a log log grid (sometimes called the Gates-Gaudin-Schuhmann plot)1-3 gives a straight line of slope ~ 1 over much of its range. On closer inspection, deviations in the extreme coarse range covering perhaps 10 to 30% of the total sample may be apparent (frequently, a change in slope from ~ 1 to a value different from unity) together with over-all slight irregular departures from a smooth line. One model of breakage postulates that the same fracture pattern persists throughout all size ranges.4 The fracture pattern is characterized by the slope of the line on a log log grid. Accordingly, a distribution of sizes broken in the manner specified earlier is expected to produce a size distribution having the same slope as that of a broken narrow size range. Additionally, the slight irregularities mentioned above should even out in the summation process, giving a smooth straight line of slope ~1 on a log log plot. This idealized state of affairs does not, however, describe the distribution of a multi-event process such as that for a tumbling mill product. On the average, these curves (plotted again log log) tend to have a slope in the fine region different from and usually less than unity,5 while the coarse size region curves with increasing slope for cases of mild reduction, and with decreasing slope when moderate or severe size reduction has occurred. In addition, there are usually slight irregular deviations from a smooth curve. Most curves display two distinct regions — fine and coarse — and a few curves show one or more intermediate regions. Feed size studies6,7 show an effect which theory is required to explain. For the same material, mill loading and other operating conditions, and the same time of grinding, plotting the dimensionless ratios Y vs. X/(feed size) does not reduce the size distribution data to the same curve. Y vs. X does not correlate the coarse region, but it can provide a crude correlation of the fine region which improves as size diminishes and as grinding time increases. The size distribution in the coarse region is somewhat more dependent on the feed size than is the distribution in the fine region wherein the degree of dependence diminishes as time proceeds; the distribution of sizes in the fine region are determined largely by the nature of the material and the comminution conditions. A comprehensive model of comminution must recognize that several different patterns or modes of breakage can occur in a mill; 5,8,9 that there can be some selection in that some size ranges are broken more than others; and that, while some particles may be the product of a single fracture event, or may even remain unbroken, others result from multiple rebreak-age. Thus, breakage in a tumbling mill is more complex than the Schuhmann4 model admits in that several different types of comminution micro-events* occur rather than just one type, and these events, though different in size scale, are of the same overall pattern as that which is visualized by the model. The concept of an average comminution micro-event has, therefore, a mathematical rather than a physical connotation, at least for tumbling milling. Equations with which to describe particle size distributions have been sought for over half a century.10-13 No equation presently in general use was first derived from an analysis of the statistical mechanics of breakage; whatever theoretical basis the existing

Jan 1, 1969

By D. A. Elgillani, S. Atak, D. A. Rice, M. C. Fuerstenau, R. B. Bhappu

Quartz and feldspar cannot be floated with sulfonate at any pH; spodumene floats over a narrow acid pH range, while beryl responds moderately over a broad pH range. After wet-grinding in a steel mill, beryl, quartz, and spodumene float well with sulfonate below about pH 7, whereas the improvement in the response of feldspar is not so marked. A mechanism by which iron can be adsorbed on these minerals is presented. Also, the responses of leached, natural, and wet-ground beryl to amine, sulfonate, and oleate flotation are shown and related to the measured zero-points-of-charge of these materials. Earlier work with leached beryl showed that good flotation could be obtained with alkyl aryl sulfonate over a rather wide pH range using a Fagergren flotation cell.&apos; When a similar response was observed with leached quartz, it was decided that unintentional activation was being obtained from the metallic components of the Fagergren cell. To obviate this difficulty, a microflotation cell was designed, and an experimental technique was devised. These have been described elsewhere. Experiments conducted with the small cell showed that leached quartz could not be floated at any pH with any sulfonate addition,3 which is in agreement with the observations of Kraeber and Boppel.4 Similarly, it was also found that leached beryl responded to sulfonate flotation only over a narrow pH range rather than the broad range reported earlier.1 This early work,1 however, revealed the important effect that wet-grinding in a steel mill has on the flotation response of certain silicates. That is, it was found that quartz and especially beryl floated well over an unusually wide pH range after wet-grinding in a steel mill. Microcline, however, floated poorly below pH 4, even though wet-ground under the same conditions. The work of Eigeles6 on adsorption of oleic acid on leached quartz and iron-contaminated quartz at constant pH is in agreement with these flotation data. Other research has shown that ferric iron, added as a salt to the system, functions as an activator in the narrow pH range in which Fe +++ iron hydrolyzes to its hydroxy complexes.3,5 These phenomena indicate that iron functions differently in flotation systems depending on its method of introduction. The object of this paper is to determine the mechanism by which iron is adsorbed on certain minerals, the mechanism of collector adsorption after iron abstraction, and the role that Fe++ and Fe+++ assume in the selective separation of these minerals. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate, mol wt 450,7 pure potassium oleate, and pure dodecylamine were used as collectors. All other chemicals were reagent grade in quality, i.e., n-amyl alcohol as frother; HC1, H2SO4, and KOH for pH adjustment; and ferric chloride as activator. Conductivity water, made by passing distilled water through an ion exchange column, was used in the experimental work. All minerals used in the investigation were hand-picked specimens. Sample Preparation: Each of the minerals was crushed through 8 mesh, and the product was divided into two groups, one to be ground dry and the other wet. Dry grinding was accomplished with an alumina mortar and pestle. The product was dry-screened to 48 x 150 mesh, cleaned magnetically, deslimed in conductivity water, and dried. Preparation of the samples by wet-grinding involved grinding a 200-g charge of the mineral (-8 mesh) at 60% solids with natural water in a mild steel rod mill for four minutes. This charge was then wet-screened immediately with natural water to 48 x 150 mesh, dried, and cleaned magnetically. Some experiments were also conducted with leached beryl and quartz. These products were prepared by leaching the sized sample (48 x 150 mesh) with concentrated HC1 with a percolation technique until no iron could be detected in the leach liquor. Following this step, the sample was rinsed with conductivity

Jan 1, 1967

By S. Feuerstein, L. Rice

The effect of low pressures on the flow and fracture behavior of molybdenum is described. For poly crystalline samples, room-temperature tensile tests indicate greater ductility under 10 Torr than under intermediate pressures up to and including atmospheric pressure (760 Torr). In addition, tests conducted at 760 Torr under atmospheres of air, dry nitrogen, and purified argon exhibited no apparent difference in mechanical properties. Critical tests involving baking in situ as well as those involving single-crystal deformation further imply that the ductility effect is a pressure-dependent phenomenon related only to the fracture process. This dependency is discussed in terms of adsorption and diffusion contributions. THE effect of very low pressures on material properties has heretofore been presumed to be important only for substances possessing relatively high vapor pressures at ambient temperatures. Research has therefore been concentrated primarily on organic solids and liquids, and in some instances on metals such as zinc and cadmium. Most vacuum-effect studies&apos; on the mechanical behavior of metals have been performed under conditions of either cyclic loading or creep rupture at elevated temperatures, i.e., over extended time periods. These studies were not restricted to high vapor pressure materials but also encompassed such metals as gold, copper, and nickel. Very little concern, however, was placed upon the importance of a vacuum environment on the mechanical behavior of metals subjected to a simple unidirectional deformation at ambient temperatures. A tension test is generally of short duration as compared to a creep test, and at room temperature vacuum effects if any would be expected to be surface-limited. In early 1963, Kramer and podlaseck2 reported a change in the bulk flow behavior of aluminum single crystals during room-temperature tension tests. The deformations were performed under pressure conditions of 760 to 3.4 X 10-8 Torr and indicated for the first time a vacuum surface effect contributing to the bulk tensile behavior of metal specimens. As a consequence, an experimental program was initiated in this Laboratory to study the effects of ultrahigh-vacuum conditions on the mechanical behavior of metals. The results of a preliminary study on poly-crystalline molybdenum3 revealed, unlike Kramer&apos;s observations of changes in the stress-strain behavior, only an increased ductility under ultrahigh vacuum. Flow behaviors were nearly identical for all tests re- gardless of pressure. This paper presents comprehensive results obtained in this area of research. 1) EXPERIMENTAL PROCEDURE Three material categories were used in this study: sintered and are-cast polycrystalline molybdenum of nominal purity 99.93+ pct and single-pass electron-beam zone-refined molybdenum single crystals having a nominal purity level of 99.99+ pct. The interstitial levels (weight percent) as determined by the Materials Testing Laboratories, Division of Magnaflux Corp., were as follows: sintered molybdenum (C— 0.005, H—0.0004, O—0.015, N—0.008); and arc-cast molybdenum (C-0.0038, H-0.0003, O-0.015, N-0.023). Single-crystal molybdenum obtained from Materials Research Corp. had a typical interstitial analysis of C-0.0015, H-0.00007, O—0.00045, and N-0.0001. Tensile specimens having a 5 mm diam by 50.8 mm length were prepared from these materials. An average grain diameter of 0.059 mm was obtained for the sintered specimens following a 4-hr, 1600°C heat treatment. Grain sizes from 0.019 to 0.149 mm were obtained in the arc-cast specimens following heat treatments from 1100° to 1600°C for 1 hr. This series of specimens was used exclusively for the grain-size effect studies. All samples were electrolytically polished in 97 pct sulfuric acid solution prior to testing. Experiments were performed at room temperature in an ion-pumped ultrahigh-vacuum system positioned in an Instron tensile machine, Fig. 1. A constant strain rate of 4.2 x 10-4 sec-1 as derived from crosshead displacement was assumed for the deformations. Starting vacuums ranged from 2 to 0.5 X 10-10 Torr. These pressure measurements were made using corrected values4 of an NRC Redhead gage. Comparative readings were also made against a G.E. triggered dis-

Jan 1, 1967

By J. T. Norton, A. L. Mowry

The monocarbides of the A subgroup elements in the fourth and fifth group of the periodic table in addition to being hard and refractory are of special interest in that they are isomorphous in crystalline structure. They are cubic with a sodium chloride type structure in which the metal atoms are essentially close packed in a face-centered cubic arrangement with the carbon atoms placed in the interstices between. Interstitial structures of this close packed type were first investigated systematically by Egg1 and he gave the rule for their formation, stating that the radius ratio of the nonmetal to the metal atom should not exceed the value of 0.59. The carbides of interest are those of titanium and zirconium of the fourth group and vanadium, columbium and tantalum of the fifth group. Table 1 shows the radius ratio using the Goldschmidt radii for 12 coordination for the metal atoms and the diamond radius for the carbon atom. It will be noted that while there is considerable variation in the size of the metal atom, in all cases the ratio is smaller than the limit of 0.59 placed by Hägg. It has been known for some time that these cubic carbides are soluble in one another, at least to some extent or, in other words, the metal atoms can be replaced, one by another without destroying the stability of the structure. Since the stability of these close packed interstitial substances appears to depend more upon geometry than upon the exact chemical nature of the atoms involved, it is of interest to examine the possibilities of replacement in these carbides in some detail. Hume-Rothery2 has pointed out the importance of the difference in size of solute and solvent atom as a factor in limiting the solubility in simple binary solid solutions. Largely on an empirical basis, he states that if the difference in size between solvent and solute atom is more than 14-15 pct of the solvent atom, the range of solubility is very restricted. The atom size was based on the distance of closest approach in the elements involved. While there is some question as to how one should calculate the size of the metal atom in the carbide structures, reference to Table 1 will show that zirconium is the largest and vanadium the smallest of the group and that the difference is about 15 pct. The Ti-Zr difference is about 9 pct and the others are smaller. Thus one would predict that if the size factor controls the solubility, all of the pairs except VC-ZrC would have wide or complete solubility whereas this latter pair is on the border line and might have restricted solubility. The purpose of the present investi- gation was to examine the solubility of the several pairs of carbides by heating them together until equilibrium was established and then examining the product by X rays. Previous Work Agte3 and his associates prepared various transition metal carbides and determined the melting points of binary mixtures. He concluded from the shapes of the melting point curves that there was extensive solubility in the case of the cubic carbides. Umanskii and his colleagues made an investigation of a number of pairs of the cubic carbides, using X rays and plotted lattice parameter vs. composition curves for the systems TaC-Tic, CbC-Tic, TaC-ZrC and CbC-ZrC. All pairs showed a continuous series of solid solutions. The first two pairs gave a linear relation while the latter two showed a negative deviation from Vegard&apos;s law. Kiefer and Nowotny, in a paper which became available after the present work was well advanced, investigated the binary pairs of the five cubic carbides by means of X rays. Relatively few points were obtained and results indicated that in some cases, at least, equilibrium was not reached at the temperatures used. The results indicated that solubility in the VC-ZrC system was not complete. All of the results of previous investigations indicated the desirability of a more detailed study. Materials The raw materials used were mono-carbides of titanium, zirconium, vanadium, columbium and tantalum and were the purest which could readily be obtained commercially. Spectrographic qualitative analysis showed that the CbC and TaC contained less than 1 pct

Jan 1, 1950

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell&apos; It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully&apos;s theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955