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By M. L. Fuller

MOST commercial alloys undergo changes in phase composition after casting. This is a natural result of the fact that the alloys are not in a state of phase equilibrium as cast and phase changes will therefore take place, with more or less rapidity, in an attempt to attain equilibrium. The practical aspect of aging in zinc-alloy die castings concerns the changes in physical properties and in dimensions that may accompany aging phase changes. Harmful alterations have been reduced to a minimum and zinc-alloy die castings are being produced today that are so stable with respect to dimensions and physical properties that they are entirely suitable for most practical purposes1. In the first paper2 of this series, and in this paper, aging phase changes of zinc alloy die castings have been investigated and the possible influence of these changes on dimensional changes of the castings has been evalu-ated and compared with the dimensional changes actually experienced. The change of dimensions has been selected for practical comparison in these papers because the effect of phase changes on the dimensions of a casting is directly calculable; from X-ray crystal-analysis data of the phase structure. The die-casting alloys considered contain, in addition to zinc, 4 per cent of aluminum, about 0:03 per cent magnesium, and from 0 to 3 per cent of copper. It was shown in the former paper that the eutectoidal decomposition of the beta aluminum-zinc phase, while intrinsically capable of causing a considerable shrinkage, can have very little effect on the observed shrinkage of die castings because it takes place within a few days of aging, whereas the observed shrinkage continues for five weeks. It was therefore concluded that the other existing phase change,

Jan 1, 1935

By Earl W. Palmer, Cyril Stanley Smith

A study of the precipitation-hardening of copper steels1 led the authors to investigate malleable iron containing copper, for the low-carbon ferritic matrix in malleable iron should lend itself admirably to precipitation-hardening. It was soon found that in addition to rendering malleable iron susceptible to improvement by precipitation-hardening treatments, copper has another potentially useful effect as an accelerator of graphitization. Brief mention of these effects was given in a general paper by Lorig and one of the present authors2; the present paper gives further details on the graphitization and precipitation-hardening effects only. After the completion of this work a paper by L. Lykkin3 appeared, confirming the authors' conclusions regarding graphitization. Material Used After some preliminary heats had been made in the laboratory to determine the effect of copper, several castings from commercial air-furnace heats were obtained, and data from these alone are given here. Part of the metal was poured directly and part was treated in the ladle with the desired amount of copper before pouring. Green-sand molds were used, each holding two tensile test pieces of the form adopted by the Malleable Iron Research Institute, or two bars for graphitization studies, 5/8 in, in diameter and 9 in. long, fed through two enlarged sections equidistant from the middle and ends of the bars. Risers of suitable size insured sound castings. Tensile tests were made on the castings after commercial mallealleizing and after special heat treatments to be described. The analyses of the white irons are given in Table 1.

Jan 1, 1935

By Cyril Stanley Smith, Earl W. Palmer

A study of the precipitation-hardening of copper steels1 led the authors to investigate malleable iron containing copper, for the low-carbon ferritic matrix in malleable iron should lend itself admirably to precipitation-hardening. It was soon found that in addition to rendering malleable iron susceptible to improvement by precipitation-hardening treatments, copper has another potentially useful effect as an accelerator of graphitization. Brief mention of these effects was given in a general paper by Lorig and one of the present authors2; the present paper gives further details on the graphitization and precipitation-hardening effects only. After the completion of this work a paper by L. Lykkin3 appeared, confirming the authors' conclusions regarding graphitization. Material Used After some preliminary heats had been made in the laboratory to determine the effect of copper, several castings from commercial air-furnace heats were obtained, and data from these alone are given here. Part of the metal was poured directly and part was treated in the ladle with the desired amount of copper before pouring. Green-sand molds were used, each holding two tensile test pieces of the form adopted by the Malleable Iron Research Institute, or two bars for graphitization studies, 5/8 in, in diameter and 9 in. long, fed through two enlarged sections equidistant from the middle and ends of the bars. Risers of suitable size insured sound castings. Tensile tests were made on the castings after commercial mallealleizing and after special heat treatments to be described. The analyses of the white irons are given in Table 1.

Jan 1, 1935

By Kenneth C. Vincent, A. M. Gaudin

In a study1 of the action of amyl xan-thate on chalcocite in water suspension, it was found that if the xanthate is added in relatively large quantity the xanthate group can be accounted for in three forms: (1) as xanthate ion remaining in water, (2) as benzene-soluble cuprous xanthate on the chalcocite, (3) as a benzene-insoluble coating on the chalcocite. Reduction in the amount of xanthate added leads to disappearance of form I then of form 2. With minute quantities of added xanthate, substantially all the reagent is of the "unleachable" kind. Yet this unleach-able xanthate can be dissolved by pyridine to form a soluble cuprous xanthate complex, and it is sufficient in effectiveness to make chalcocite flotable even if insufficient in quantity to form a complete mono-molecular film on the mineral. In that study it was also found that chalcocite abstracts cuprous xanthate from benzene so1ution, in what may (or may not) be a case of molecular adsorption. It seemed desirable, therefore, to study further the "unleachable" xanthate on the chalcocite, and particularly to ascertain whether it is formed as a result of the benzene leach or is actually formed during the conditioning of chalcocite in aqueous xanthate solution. A 'splendid tool to make such studies has recently been perfected; that is, the use of radioactive spies or tracer atoms. With this tool, it was thought possible to answer the problem stated above, but, unfortunately, this did not prove to be true. Answer to the flotation question was clouded by the existence of rapid and selective diffusion of copper atoms in the solid mineral—a phenomenon that was totally unexpected yet remains interesting and perhaps important. Method of Radioactive Spies The method of radioactive spies is discussed in many places. Two convenient references are the article by Evans2 and the book by pollard and Davidson.3 The method was first developed by van Hevesy and paneth in 1013, when only natural radioactive isotopes were available. These isotopes are few in number, and so the method remained limited in scope. Recently the synthesis of over 350 active isotopes of all the known stable chemical elements4 has opened widely expanded possibilities for the method, A fundamental tenet of the method is that a radioactive atom and a nonradio-active atom are exactly alike until disintegration of the radioactive atom. Then, by its sudden death, the spy reveals its location. The relative abundance of spies at various locations makes it possible to ascertain the relative abundance of the corresponding nonradioactive atoms at the same times and locations. A second fundamental tenet of the method of radioactive tracers is that the radioactivity lies in the nucleus of the atom: transfer of radioactivity from one

Jan 1, 1947

By Kenneth C. Vincent, A. M. Gaudin

In a study1 of the action of amyl xan-thate on chalcocite in water suspension, it was found that if the xanthate is added in relatively large quantity the xanthate group can be accounted for in three forms: (1) as xanthate ion remaining in water, (2) as benzene-soluble cuprous xanthate on the chalcocite, (3) as a benzene-insoluble coating on the chalcocite. Reduction in the amount of xanthate added leads to disappearance of form I then of form 2. With minute quantities of added xanthate, substantially all the reagent is of the "unleachable" kind. Yet this unleach-able xanthate can be dissolved by pyridine to form a soluble cuprous xanthate complex, and it is sufficient in effectiveness to make chalcocite flotable even if insufficient in quantity to form a complete mono-molecular film on the mineral. In that study it was also found that chalcocite abstracts cuprous xanthate from benzene so1ution, in what may (or may not) be a case of molecular adsorption. It seemed desirable, therefore, to study further the "unleachable" xanthate on the chalcocite, and particularly to ascertain whether it is formed as a result of the benzene leach or is actually formed during the conditioning of chalcocite in aqueous xanthate solution. A 'splendid tool to make such studies has recently been perfected; that is, the use of radioactive spies or tracer atoms. With this tool, it was thought possible to answer the problem stated above, but, unfortunately, this did not prove to be true. Answer to the flotation question was clouded by the existence of rapid and selective diffusion of copper atoms in the solid mineral—a phenomenon that was totally unexpected yet remains interesting and perhaps important. Method of Radioactive Spies The method of radioactive spies is discussed in many places. Two convenient references are the article by Evans2 and the book by pollard and Davidson.3 The method was first developed by van Hevesy and paneth in 1013, when only natural radioactive isotopes were available. These isotopes are few in number, and so the method remained limited in scope. Recently the synthesis of over 350 active isotopes of all the known stable chemical elements4 has opened widely expanded possibilities for the method, A fundamental tenet of the method is that a radioactive atom and a nonradio-active atom are exactly alike until disintegration of the radioactive atom. Then, by its sudden death, the spy reveals its location. The relative abundance of spies at various locations makes it possible to ascertain the relative abundance of the corresponding nonradioactive atoms at the same times and locations. A second fundamental tenet of the method of radioactive tracers is that the radioactivity lies in the nucleus of the atom: transfer of radioactivity from one

Jan 1, 1947

By I. L. Dillamore

I. L. Dillamore (University of Birmingham)—The different textures developed in various fcc metals have long awaited satisfactory explanation and it has now become clear that these differences are related to parallel differences in the deformation characteristics of the metals. Liu is correct, therefore, in seeking to account for the observed textures in terms of the flow mechanisms but I believe, for the reasons outlined below, that the particular interpretation of flow mechanisms proposed by Liu is open to substantial objections. By considering the forty-eight possible designations of the twelve octahedral slip systems found in fcc metals as distinct and separate deformation modes, Liu has fallen into the error of assuming that only positive glide dislocations associated with each system are present. In fact both positive and negative dislocations will be present and the only difference between for instance the systems B4 and B4' (in Liu's notation) is that under a stress of given sign the direction of motion of a dislocation is reversed on changing from B4 to B4'. For both orientations positive and negative dislocations will be present. In considering possible dislocation interactions it is, therefore, inadmissible to differentiate between R4 and R4' as Liu does. Liu considers those dislocation interactions which give the biggest reduction in energy to be the most favorable and neglects, on the grounds that they will form strong barriers to slip, interactions between dislocations with perpendicular Burgers vectors. Setting aside interactions between positive and negative dislocations of the same slip system, which must occur regardless of the combination of slip systems chosen, the biggest reduction in energy occurs for the Lomer-Cottrell interaction and it is Lomer-Cottrell barriers which are thought to provide the stronger dislocation obstacles. On the other hand the intersection of dislocations with perpendicular Burgers vectors is thought to be a low-energy process which contributes only a fairly small temperature-dependent part of the total work hardening. On this basis it seems doubtful whether the reduction in energy through possible dislocation interactions provides a reasonable criterion for choosing the operative slip systems. From the point of view of texture development it is unsatisfactory to ignore the slip rotations leading to an end position and to neglect to consider the stability of the chosen end point. It is also unsatisfactory to treat the two stress axes as interchangeable since, if the stress system is idealized as biaxial, one stress is compressive and the other is tensile. For the same reason the rotations of the two stress axes are not made compatible simply by assuming that the same slip directions are responsible for the rotations of the two stress axes. It is, in short, essential to treat the two stress axes as acting together on the same slip systems. Turning to the question of the difference between the copper-type and the brass-type texture, there now remains little doubt that the difference is attributable to differences in stacking-fault energy (y), as noted by Liu, but it is doubtful whether the temperature dependence of the texture in copper and in silver is due to increasing stacking-fault energy with increasing temperature. The results of Swann and Nutting42 cited by Liu were obtained in Cu-A1 alloys and the apparent increase in stacking-fault energy on raising the temperature may be influenced by short-range ordering. In pure metals such effects are absent and the only data available on the variation of y with temperature are those of Buhler et a1.43 for silver. They report a minimum at 200°C which does not fit the hypothesis put forward by Liu. It is much more likely that thermal activation of cross slip is important in determining which texture develops, as proposed by Dillamore and tors. These workers have proposed an explanation for the differences in observed texture among the fcc metals and the pole figures predicted consist of an orientation spread which is in better agreement with observation than the limited number of discrete orientations suggested by Liu. The theory of Dillamore and Roberts is also able to account for the differences between aluminum and copper which Liu still leaves unexplained. Y. C. Liu (author's veply)—The writer appreciates the interest of Dr. Dillamore, but must discuss some of his comments in order to avoid cross purposes. The phrase, "forty-eight slip systems," which appeared twice in the text—in the caption of Fig. 1 and the first paragraph in the Discussion—might unfortunately have led Dr. Dillamore to disagree

Jan 1, 1965

By R. W. Gurry

WHEN a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, vet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. EXPERIMENTAL PROCEDURE Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;1 it suffices to state here that the carburization lasted about 140 hr. at 760°C. (1760°F.) and 44 hr. at 1110°C. (2030°F.), these periods being long enough-on the basis of the calculations presented later-to ensure that the specimen was about 9.99 per cent saturated at each temperature. The speci¬men was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully [carburized] specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By W. T. Roberts, N. G. Turner

A study of the fatigue properties of several grades of commercially pure titanium has established that the strain-aging process is of minor importance in the development of a fatigue limit and a relatively high fatigue strength ratio. Metallographic observations and damping measurements at room temperature indicate that striations are able to spread from grain to grain only at stress levels above the fatigue limit. This suggests that the fatigue limit represents the stress above which large-scale dislocation unlocking takes place. Fatigue tests on annealed material at - 60" and - 196" c showed that under conditions when a thermally activated diffusion process would be suppressed the fatigue limit is not eliminated. Prestraining at room temperature did not have a detrimental effect on fatigue strength at room temperature but a decrease was recorded at — 60°C. This is further evidence that initial dislocation locking is a important strengthening mechanism. TITANIUM and titanium alloys have S-N curves with a definite fatigue limit, and a high ratio of fatigue limit to UTS can be attained. Other materials which show similar fatigue characteristics are mild steel and some Al-Mg alloys. The fatigue limit of these materials has been associated with their strain-aging capacity. It is well-known that commercial-purity titanium contains interstitial impurities which can give rise to a sharp yield point, and a small strain-aging effect following static strain has been demonstrated.7 This type of aging reaction is differentiated from the dynamic aging process when aging occurs during plastic deformation, and which is generally observed at elevated temperatures. In a titanium at room temperature, dislocation locking is associated with the interaction of interstitial oxygen, nitrogen, and carbon atoms with dislocations. Ehr-lich has shown that the distortion produced by introduction of these atoms into the hcp lattice has no shear stress component and hence there is no interaction between the stress field and the screw component of a dislocation. Thus the dislocations as a whole are only weakly locked. It is clear that strain-aging effects in hcp a titanium will be much less pronounced than those observed in bcc iron and steel. In recent years, the attribution of the fatigue limit solely to strain aging has been questioned. It has been pointed out that a definite fatigue limit is observed at temperatures as low as -196°C in some titanium alloys,' and strain aging is not expected to be effective at this temperature. The role of initial locking of dislocations in determining fatigue behavior has been examined in low-carbon steel by Oates and Wilson. They showed that under conditions in which the aging potential is low the factors which control the buildup of local stresses and hence affect dislocation unlocking, e.g., grain size, are important. There are indications that other metals can have a definite fatigue limit with no established strain-aging capacity, an example being magnesium12 which has the same crystal structure as a titanium. The spread of plasticity from grain to grain in hexagonal metals may be more difficult than in cubic metals because of the limited number of slip systems in the former, and this may account in part for their fatigue behavior. The present work was undertaken to elucidate the relative importance of crystal structure, strain aging, and initial dislocation locking in determining the properties of commercially pure titanium when subjected to cyclic stressing. 1) EXPERIMENTAL METHODS Three grades of commercial-purity titanium were used and a material of lower interstitial content was prepared by melting high-purity Japanese sponge titanium (referred to as H.P. Ti). The compositions and typical mechanical properties of the materials are shown in Table I. Fatigue tests were made in push-pull (zero mean stress) using an Amsler Vibraphore machine at a frequency of about 160 cps. Two types of fatigue specimen were used—one with a waisted gage length for determination of S-N curves and the other with a parallel gage length for metallographic studies and damping measurements. After careful machining and mechanical polishing, all specimens were electropolished prior to fatigue testing. The electrolyte consisted of 10 parts methyl alcohol, 6 parts 2-butoxyethanol, and 1 part perchloric acid (SG 1.54) and it was maintained at a temperature of -10" to -20°C during polishing. Tests at room temperature were normally carried out with the specimen immersed in a silicone oil bath which could be heated for elevated-temperature tests.

Jan 1, 1969

By W. N. Miner, R. O. Elliott

Electrical-resistivity )measurments were made be-trueetz room temperatrive and 1.5 oK on five different stocks of cerium metal, and the results were correlated with the types, amounts, and distribution of the impurities present. Magnesium, which appeared to be distributed as a solute throughout the cerium matrix, was found to have a large effect on the residual resistivity, 1 at. pct Mg being sufficient to increase the residual resistivity by about 10 microhm-cm. The formation of ß by repeated thermal cycling between room temperature and liquid-helium temperature is attributed to the deformation and faulting that occurs during the ? D a transformation. In preparation for starting a proposed study of cerium-rich alloys, we examined samples from severa1 stocks of cerium metal in order to choose the purest stock for future use in making the alloys. Low-temperature electrical-resistivity data were used to gain initial information about the purities of the stocks. Additional information was subsequently obtained from chemical analyses, density measurements, optical metallography, and electron-micro-probe analyses. Cerium that has been annealed at high temperature and cooled to room temperature has the fee crystal structure (? phase) with a = 5.16Å. When cooled further, in the region between about 250" and 150°K, some of the fee phase transforms to the double hcp form (ß phase) with a = 3.68 and c = 11.92Å. The remainder of the room-temperature fee form (and perhaps some of the hexagonal phase) transforms electronically in the vicinity of 100° K to the more dense or "collapsed" fee form (a phase), a - 4.85A, by transferring about 0.5 electron per atom from the 4f level to the valence band. Very little work related specifically to the effects of impurities on the physical properties of cerium has been reported in the literature. Gaume-Mahn1, 2 has studied the effects of calcium, magnesium. iron, silicon, and tantalum on the electrical resistivity and magnetic susceptibility of cerium between 60o and 300°K. Gschneidner, Elliott, and McDonald3 have discussed the effects of total impurity content on the hysteresis of the a —? (reversible) transformation and on the formation of the 4 and "a-? intermediate" phases. Smith and Morrice* have reported the effect of total impurity content on the resistivity of cerium at 4 and 293°K. In none of these reports, however, is it apparent that the distributions of the impurities were determined, L.r., whether the impurities were present in inclusions or in solid solution in the matrix is not mentioned; nor does it appear that the phase purity of the cerium was always considered. In the present study, five different stocks of cerium were involved. One was represented by a single sample of electrowon cerium, which was all that had remained from a stock of high-purity material obtained from the U.S. Bureau of Mines, Reno, Nev., in 1959. The other four stocks were recently purchased from commercial sources and were specified to be 99.9 wt pct pure. EXPERIMENTAL Cerium stocks designated as #1, #2, #4, and #5 were obtained from commercial suppliers for the specific purpose of finding a reliable source of high-purity cerium. Although the purity level of the cerium was specified to be 99.9 pet, the specifications did not include limits as to the amounts of various impurities that would be acceptable. Consequently the chemical analyses of the different stocks varied widely. Stock #3, which had been obtained from the U.S. Bureau of Mines and which was the purest on the basis of chemical analyses, consisted of a single specimen of electrowon cerium. It was included in the examination for purposes of comparison. Table I contains the chemical and spectrographic-

Jan 1, 1968

By Charles Bell

THE Telluride mining district of southwestern Colorado is defined by the 37° 45' and 38° parallels of latitude and 107° 45' and 108° meridians of longitude. Telluride was never a boom camp, but has had a steady growth. In recent years, notwithstanding the business depression of 1920, the business has been the same as in normal years. The first prospector is said to have appeared in 1875, in which year locations on the Smuggler vein were made. Shipments were made in 1877 and 1878, and in 1879 milling the ores was attempted. While the district produced high-grade ores, it did not become important until 1890, when the Rio Grande Southern R. R. was completed from Ridgway to Telluride. The railroad has since been extended to Durango. In the fall of 1896, 400 stamps were in operation, and the annual production was $3,000,000.00, two-thirds of which was gold. The total production from 1875 to 1923 was: Gold $58,274,527; silver 41,830,920 oz., valued at $31,016,893; copper 15,258,866 lb., valued at $2,533,291; lead 166,056,484 lb., valued at $8,324,910; zinc 18,141,182 lb. valued at $1,323,787; or a total production of $101,473,408. All: claims are held in fee. Most of them are 1500 by 300 ft. but claims located within the last few years are 1500 by 600 ft. General supplies are obtained at Telluride, Denver, and Salt Lake. The largest mines are within 6 miles of the town of Telluride. Denver is 422 miles and Salt Lake is 439 miles, by rail, from Telluride. One-half of the distance to Denver and one-sixth of the distance from Telluride to Salt Lake is by narrow-gage railroad. The labor is efficient. The best miners are Italians and Austrians, then Slavs, Greeks, and Mexicans follow in the order mentioned. There are no labor unions. There are no serious mine pumping problems, the drainage being through adits. The Tomboy and Smuggler companies pump water from their reservoirs, the former for, milling and domestic purposes and the latter for milling, power, and domestic purposes.

Jan 2, 1924

By J. B. Morrow, D. H. Davis

THERE are two general approaches to the problem of increasing profits from an operation. One is to lower expense; the other is to raise income. Mechanical preparation of coal may be used for either purpose but a prudent consideration of many details must precede any decision lest the results be negative instead of positive. It is quite possible that any net gain will result from a combination of the two. Since mechanically prepared coal invariably is a better product qualitatively than a hand-picked coal from the same mine, it is a reason- able expectation that the customer will be willing to increase the producer's income by paying a higher price. Or there may be the possibility that a combination of mechanical mining plus mechanical cleaning will give a lower over-all production cost for the coal in the railroad car. More likely, there will be found a combination of these two factors. From the customer's point of view, the competitive delivered cost per B.t.u. considered in relation to such incidental factors as dust nuisance, handling properties, ash disposal, and ash fusibility determines what he will pay. In a bulk tonnage product such as coal, freight is a very considerable part of the delivered fuel cost, and obviously freight paid on incombustible ash has no economic attractions. INCENTIVE FOR CLEANING Coal is prepared in four major ways: 1 (I) by screening or sizing, (a) by mixing or blending, (3) by cleaning, including hand picking and mechanical cleaning, (4) by dustless treatment. By a combination of any or all of these methods, coal can be prepared to standard specifications. It is easily possible to have good cleaning and still get a poor final product because of faulty screening or mixing,

Jan 1, 1943

GWILLIAM H. CLAMER (Philadelphia, Pa.).-About 16,000 tons of tin is used annually in the production of white metals. The real reason for using the so-called genuine babbitt, which is a high-tin base babbitt, perhaps in the majority of cases, is that tin has always been. a high-priced metal and people naturally believe that what they pay a high price for must be good. Mr. Jones has shown that the common metal, lead, is a superior base for most purposes for Which babbitt metal is used. The addition of lead is often looked upon as adulterant to genuine babbitt, and specifications for this reason rigidly restrict the lead content. A sub-committee of the Society for Testing Materials, at the meeting in June, presented tentative specifications on babbitt metal, in which were included twelve formulas, containing from zero to: 20, per cent. of tin, and several containing from 65 and 92 per cent. Babbitts. containing

Jan 1, 1919

By J. L. Walter

Tungsten ingots with and without small amounts of aluminum, silicon, and potassium were prepared by conventional powder-metallurgy techniques and hot-rolled to 0.001-in.-thick sheet. The ingots were rolled three different ways: I) initially cross-rolled, then straight-rolled; 2) straight-rolled, and 3) straig-ht-rolled, then cross-rolled. Total reductions were 99.8 pct. Samples of the sheet were annealed, in vacuo, at temperatures from 1200" to 2200°C. Substructures and textures were determined by transmission electron microscopy and X-ray diffraction. The doping agents were found to form particles of mullite (Al,Si,O,,) which, on rolling., appear to form strings of particles aligned parallel to the rolling direction. These strings of purticles are associated with an increase in the recrystal-lizution temperature from 1400°C for undoped sheet ThE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of drawn and recrystallized wire.'" The grains generally do not occupy the entire cross section of the wire and have lengths many times the wire diameter. The grain boundaries are, in general, nearly parallel to the wire axis and have long ''fingers" projecting one into the other as may be seen in Fig. 1, a longitudinal section of recrystallized doped wire. When unsuitable additions or no additions are made or the wire is not sufficiently reduced during draw- to 2000°C for doped sheet. The particles also limit lateral grain growth while allowing growth parallel to the rolling direction. This results in the formation by primary re crystallization of large highly elongated grains of specific preferred orientation. The undoped sheet recrystallized to small equiaxed gains. The preferred orientations of the large grains were determined from axis density plots to be (113) (691). (0i3) (362), (116) (304) types for the initially cross-rolled then straight rolled material. These orientations are similar to the orientations of the large elongated grains in doped and heavily drawn tungsten wire. The nucleation of the large grains appears to occur by recovery of certain of the polygonized regions of specific orientation, followed by strain-induced boundary migration.

Jan 1, 1968

By L.W. Eastwood, Arthur E. Bousu, C. T. Eddy

The recrystallization and grain-growth phenomena of cold-worked metals have considerable industrial importance because of their role in the fabrication of metals. For this reason, and because of the general academic interest in the subject, these processes have received considerable attention since the time of J. E. Stead's paper1 on The Crystalline Structure of Iron and Steel. There are considerable differences of opinion regarding the theory of recrystallization and grain growth and also differences in the observation of the modus operandi of the processes themselves. The value of many of the existing quantitative data on grain growth is decreased by the failure to distinguish between the grain sizes just after complete recrystallization and those resulting from coalescence. For this reason also, the value of the diagrams of stable grain sizes, like those produced by Bass and Glocker2 and Czochralski3, is lessened in so far as an interpretation of the facts of recrystallization is concerned. It is hoped that the data presentcd in this paper will help to clarify and to simplify the facts relating to recrystallization, and at the same time will show that some of the present-day conceptions are untenable. A paper on the theory of recrystallization, with additional data, will be completed in the near future by the writers. Since the literature on the subject has been adequately and frequently reviewed, the only referenccs to it in this paper will be those necessary in the discussion of the data presented.

Jan 1, 1935

By Arthur E. Bousu, C. T. Eddy, L. W. Eastwood

The recrystallization and grain-growth phenomena of cold-worked metals have considerable industrial importance because of their role in the fabrication of metals. For this reason, and because of the general academic interest in the subject, these processes have received considerable attention since the time of J. E. Stead's paper1 on The Crystalline Structure of Iron and Steel. There are considerable differences of opinion regarding the theory of recrystallization and grain growth and also differences in the observation of the modus operandi of the processes themselves. The value of many of the existing quantitative data on grain growth is decreased by the failure to distinguish between the grain sizes just after complete recrystallization and those resulting from coalescence. For this reason also, the value of the diagrams of stable grain sizes, like those produced by Bass and Glocker2 and Czochralski3, is lessened in so far as an interpretation of the facts of recrystallization is concerned. It is hoped that the data presentcd in this paper will help to clarify and to simplify the facts relating to recrystallization, and at the same time will show that some of the present-day conceptions are untenable. A paper on the theory of recrystallization, with additional data, will be completed in the near future by the writers. Since the literature on the subject has been adequately and frequently reviewed, the only referenccs to it in this paper will be those necessary in the discussion of the data presented.

Jan 1, 1935

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

Iodide zirconium was combined with calculated amounts of nitrided zirconium sponge and arc melted to prepare alloys in the 0 to 6 wt pct N region. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat-treated specimens permitted construction of the binary phase diagram from 0 to 6 pct N. Features of the diagram include the peritectic formation of both a and ß solid solutions. The maximum solubility of nitrogen is 0.8 pct in 8 zirconium and 4.8 pct in a zirconium. An X-ray study of nitrided materials was made in the range 6 to 13 wt pct N region because serious nitrogen losses were experienced when attempts were made to arc melt these high nitrogen alloys. PHASE relationships in the Zr-N system have been determined. Due to the inability to retain nitrogen in nitrogen-rich alloys subjected to arc melting, definitive work was possible only in the range 0 to 6 wt pct (0 to 30 atomic pct) N. Sufficient complementary X-ray work was done to permit construction of the binary phase diagram up to 13.3 wt pct (50 atomic pct) N (ZrN). Small ingots were prepared by arc melting master alloys with enough zirconium to produce an alloy of the desired composition. Following pretreatment, alloys were annealed at temperature levels between 600" and 2020°C. Determination of the phase boundaries was then accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to corroborate solidus curves, and X-ray diffraction was employed to study the nitrogen-rich region of the a + ZrN phase field. Materials Westinghouse Grade 1 iodide zirconium crystal bar served as the base material for this investigation. The as-received bars were lightly sandblasted, pickled in a 20 pct HN0-5 pct HF aqueous solution, rinsed in water and acetone, and dried. They were rolled to about 1/32 in. strip and acid-pickled, followed by water and then acetone rinses. The material was sheared to approximately 1/4 in. squares, cleaned with acetone, and stored for use. Pure zirconium nitride is not commercially available, according to correspondence with possible suppliers. A literature survey indicated that nitrogen may be introduced into zirconium metal by passing nitrogen or ammonia gas over zirconium at an elevated temperature. After considerable experimentation, a train was devised whereby high quality nitrogen was passed through a series of bubblers to remove the last traces of oxygen, through an H,SO, bubbler and a cold trap to remove moisture, and finally over zirconium within a resistance furnace. Hand-picked Bureau of Mines magnesium-reduced zirconium sponge proved more amenable to nitriding than the crystal bar. The nitrogen used was extra pure gas purchased from Linde Air Products Co. The first two bubblers through which the gas was passed contained a solution suggested by L. F. Fieser" as being ideal for removing the last traces of oxygen from nitrogen. The solution contains 20 g KOH, 2 g sodium-anthraquinone ,9-sulphonate, and 15 g NaHSO, dissolved in 100 ml water. It is blood-red and turns brown when contaminated with oxygen. A saturated lead acetate solution, next in the series of bubblers, removed any H2S which might have formed in the 0, removal stage. An H,SO, bubbler and cold trap removed moisture before the nitrogen was passed over the zirconium. The zirconium was contained in a stainless steel screen within a Vycor or quartz tube in a resistance furnace. Unreacted nitrogen passed out of the system through a mercury bubbler. A nitriding run was performed in the following manner: Zirconium was placed in the screen within the furnace tube. The unit was assembled, suitably clamped off, and evacuated to remove the air and moisture within the tube and that trapped by the zirconium sponge. The unit was flushed with nitrogen and evacuated twice. After nitrogen was allowed to pass over the zirconium for about 30 min, the furnace was turned on; several hours were required to reach temperature. The reaction was allowed to continue at temperature for about 4 hr and the screen was then withdrawn from the hot zone of the furnace by means of a Nichrome or Kanthal rod. The screen and its contents were allowed to cool at the end of the tube and were then removed. At 800°C no more than about 5 pct N could be introduced into the sponge zirconium. This material was designated M-1 (master alloy No. 1) and reserved for the preparation of alloys in the dilute nitrogen region. A second set of experiments was conducted at 1000°C; no more than 7.2 pct N could be introduced into the zirconium at this temperature. Enough material (M-2) of this nitrogen content was prepared to produce a second set of alloys to complement the first and to provide alloys in the 0 to 6 wt pct N range. It was hoped that a diffusion anneal plus a re-nitriding might yield a material of higher nitrogen content. The material containing about 7 pct N was therefore given a homogenization treatment at 1000°C for 6 hr under an argon atmosphere. It was

Jan 1, 1957

By W. A. Bruce

Studies of reservoir behavior of 12 Smackover limestone oil and condensate pools are presented. Buckner, Midway, McKamie, Magnolia, Mt. Holly, Schuler (Reynolds) and Village are treated in considerable detail and subjected to analysis with an electrical device for analyzing reservoir behavior. Results and comparisons of these analyses are presented. In addition to these reservoir-behavior studies, an attempt is made to assemble trans-missibility and storage data on the Smackover limestone formation from cores and logs taken in dry holes and producers. This together with the behavior of individual reservoirs leads to a better understanding of the formation as a porous aquifer. The ultimate purpose of this type of study is to improve predictions concerning the future behavior of these pools in such a system. Predictions are presented for several pools. Introduction In 1937 the Phillips Petroleum Co. drilled its J. D. Reynolds No. I to the Smackover limestone formation at Snow Hill, Arkansas. This well found oil in the porous, permeable, upper part of the Smackover, thereafter referred to as the Reynolds lime. Since then, six oil pools and six condensate pools have been discovered in the Reynolds lime, and more than 75 dry holes have explored parts of this formation. By the first of 1943, 44 million barrels of oil and 83 billion cubic feet of gas had been withdrawn from the various reservoirs. The original reserves estimated by the Arkansas Oil and Gas Commission were 342 million barrels of oil and rzoo billion cubic feet of gas. So far all of the production has been from anticlinal structures, most of which are asymmetric and have their axes roughly perpendicular to the dip of the formation top. This is indicated in Fig. I, which shows the pools, dry holes drilled, and contours on top of the Smackover.' These pools are of particular interest for reservoir-behavior studies because the production and drilling has been controlled, and in most cases the records of reservoir data are complete. In addition to the excellent production and pressure information available, more than one half of the wells drilled were cored and all of them were electrically logged. All of the pools show evidence of water drive. While this paper is in a sense a collection of reservoir-behavior studies for several different pools, there has been an attempt to go one step further and to show the importance of the iormation as a porous continuum or a single aquifer in which the withdrawals of fluids from any pool has an important effect on the behavior of all of the pools. An effort will be made to show that the water drives of these pools are dependent upon a much larger area of the Smackover limestone than that occupied by the petroleum accumulations.

Jan 1, 1944

By W. A. Bruce

Studies of reservoir behavior of 12 Smackover limestone oil and condensate pools are presented. Buckner, Midway, McKamie, Magnolia, Mt. Holly, Schuler (Reynolds) and Village are treated in considerable detail and subjected to analysis with an electrical device for analyzing reservoir behavior. Results and comparisons of these analyses are presented. In addition to these reservoir-behavior studies, an attempt is made to assemble trans-missibility and storage data on the Smackover limestone formation from cores and logs taken in dry holes and producers. This together with the behavior of individual reservoirs leads to a better understanding of the formation as a porous aquifer. The ultimate purpose of this type of study is to improve predictions concerning the future behavior of these pools in such a system. Predictions are presented for several pools. Introduction In 1937 the Phillips Petroleum Co. drilled its J. D. Reynolds No. I to the Smackover limestone formation at Snow Hill, Arkansas. This well found oil in the porous, permeable, upper part of the Smackover, thereafter referred to as the Reynolds lime. Since then, six oil pools and six condensate pools have been discovered in the Reynolds lime, and more than 75 dry holes have explored parts of this formation. By the first of 1943, 44 million barrels of oil and 83 billion cubic feet of gas had been withdrawn from the various reservoirs. The original reserves estimated by the Arkansas Oil and Gas Commission were 342 million barrels of oil and rzoo billion cubic feet of gas. So far all of the production has been from anticlinal structures, most of which are asymmetric and have their axes roughly perpendicular to the dip of the formation top. This is indicated in Fig. I, which shows the pools, dry holes drilled, and contours on top of the Smackover.' These pools are of particular interest for reservoir-behavior studies because the production and drilling has been controlled, and in most cases the records of reservoir data are complete. In addition to the excellent production and pressure information available, more than one half of the wells drilled were cored and all of them were electrically logged. All of the pools show evidence of water drive. While this paper is in a sense a collection of reservoir-behavior studies for several different pools, there has been an attempt to go one step further and to show the importance of the iormation as a porous continuum or a single aquifer in which the withdrawals of fluids from any pool has an important effect on the behavior of all of the pools. An effort will be made to show that the water drives of these pools are dependent upon a much larger area of the Smackover limestone than that occupied by the petroleum accumulations.

Jan 1, 1944

By F. J. Plecity, J. T. Michalak, W. C. Leslie

Isothermal recrystallization and grain growth in zone- and vacuum-melted irons and Fe-Mn alloys, up to 0.60 pct Mn, were studied in the range 480° to 650° C, after 60 pct cold reduction. In initial stages, rate of grain growth and rate of recrystallization of iron decrease with time. The recrystallization is typical of a growth-controlled process, and rate of growth is determined by the extent of recovery. Mn decreases rates of growth and of recrystallizatzon. The recrystallization process changes at about 0.30 pct Mn and nucleation may become time-depetzdet~t. In recent years, considerable effort has been expended in determining the effects of solute elements on recrystallization and boundary migration in fcc metals. The results have indicated that the effects produced by single solute additions are dependent upon both the element added and its concentration.'-' In contrast, there have been very few attempts to determine the characteristics of recrystallization and boundary migration in high-purity bcc metals, especially after heavy deformation, and the effects thereon of single solute elements.9-11 This study was undertaken to determine the recrystallization characteristics of various "high-purity" irons and the effects of manganese additions at two levels of base purity. It was hoped that the information obtained would improve our understanding of the recrystallization of pure metals and aid in formulating a theory for the effect of solute elements. The interest was not entirely academic, for the annealing of low-carbon steels, which is of very great commercial importance, is but poorly understood. MATERIALS The compositions of the irons and iron-manganese alloys used are listed in Table I. The zone-melted iron and Fe-Mn alloys were made by Battelle Memorial Institute. Iron S-1 was arc-melted in a water-cooled steel mold in an argon atmosphere. The ingot was forged into a bar, then given two horizontal zone-refining passes in an alumina boat. Iron V-4 was treated in a similar manner, but was not zone-refined. The iron for the zone-melted Fe-Mn alloys was induction melted in vacuum in MgO crucibles and cast into alumina molds. The ingots were forged into bars, machined to shape, and a groove milled down one side of each. The best available electrolytic Mn was placed in the grooves, and the bars were zone melted. The vacuum-melted Fe-Mn alloys were induction melted in this Laboratory in MgO crucibles and poured into cast-iron molds. Iron V-5 was purchased from National Research Corp. in the form of a small vacuum-cast ingot. The low-carbon steel was made by induction melting in air at the U.S. Steel Corp. Applied Research Laboratory. The history of the materials prior to the final cold reduction differed; these details are given in the Appendix. The penultimate grain size of the principal materials was kept in the range ASTM 2 to 4, except for the low-carbon steel. PROCEDURES The cold work prior to the final recrystallization anneal was kept constant at 60 pct. It is known that rolling procedure can influence the kinetics of recrystallization of ironI2; therefore, all specimens were rolled in one direction only, between clean,

Jan 1, 1962