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By G. P. Bowman, D. F. Howard, R. K. Saxer, J. R. Myers

This study was undertaken to redetermine the phase diagram of the lead molybdate-bismuth molyb-date salt system. A portion of this diagram was originally determined by Zambonini in 1920, and more recently by Beale. Thermal analysis and X-ray methods were used to define this system. The diagram was found to be a simple eutectic type with an eutectic at 11 mol pet lead molybdate and 634OC. A maximum solid solubility of 6 mol pet was found at the lead molybdate end of the diagram. Solid solubility at the bismuth molybdate end of' the diagram appeared to be quite limited and possibly nonexistent. These results generally agree with those of Beale, but differ significantly from those of Zambonini. MOLTEN salt systems have been vigorously investigated since World War 11. Much of this work has been performed as pure research; however, consideration has recently been given to their possible use as coolants in nuclear reactors. Because of this application and other potential applications, it was decided to reinvestigate the lead molybdate-bismuth molybdate phase diagram. This diagram was originally determined by Professor F. Zambonini of the University of Turin in 1920.' In 1961, a portion of this diagram was redetermined by Beale.2 With the quality equipment and high-purity materials available today, it was expected that discrepancies between the results of this present investigation and Zambonini's work would be obtained. This investigation was conducted in two parts. First, the general shape of the phase diagram was determined by cooling-curve analysis. Next, the primary solid-solution phase at the lead molybdate end of the diagram was investigated by means of X-ray diffraction techniques. EXPERIMENTAL PROCEDURE High-purity lead molybdate, assaying 99.993 pet, and high-purity bismuth molybdate, assaying 99.989 pet, were employed during this investigation.* The results of a spectrographic analysis of the two salts are presented in Table I. Twenty-two experimental compositions were prepared for cooling-curve analysis. Compositions selected are presented in Table 11. Several randomly selected samples were analyzed chemically to check that the compositions of the prepared specimens were within the limit of

Jan 1, 1964

By G. F. LOUCHLIN

A FEATURE of the International Geological Congress to be held at Pretoria, South Africa, in the summer of 1929,. will be a symposium on the gold resources of the world. In this connection the U. S. Geological Survey and Bureau of Mines have been asked to prepare a report, showing production in the United States, describing the geology of its principal gold- producing districts, and estimating reserves (a) assuming a continuation of presen6economic conditions, and (b) assuming lower costs. This report will not be completed before April 1, but data thus far assembled are here presented with the hope of profiting by discussion and by information from those well informed on any of the important gold-producing districts. Gold production in the United States rose to a maximum exceeding $100,000,000 in 1915 and then rapidly declined to about $52,000,000 in 1920. Since then it has fluctuated, but on the whole slightly declined. Reviews of the eight leading states afford the following tentative conclusions :

Jan 1, 1929

By AIME AIME

DATA in this report enable comparisons to be made within the bituminous coal industry and comparison as well with copper and steel in respect to capacity and overdevelopment. The conclusions reached from the data will tend to correct numerous current misconceptions. The data have been prepared by various members of the Coal and Coke Committee of the A.I.M.E., from the most authentic sources avail¬able, and cover the period 1913-1924 wherever possible. CAPACITY AND OVERDEVELOPMENT Table 1 shows statistics for the industry, mainly from the U. S. Geological Survey sources, but partly from the U. S. Coal Commission reports. The mine capacity with equipment and labor as of given date is calculated for each state by obtaining the total man days worked as reported by the operators, and dividing this figure into the total production, getting the production per man day; this figure times the number of men employed times 308 (a theoretical full working year) equals estimated full-time capacity. Two major objections are made to this method-one that the total number of men employed is used instead of the number actually working, and the other that the number of days used only deducts Sundays and five holidays. Covering the first, the same number of men is used in estimating capacity as is used in actual production, and this condition exists at all times. Regarding the second, the opinion is general among coal men that 280 days is as great a figure as should be used, as it is practically impossible to keep any mine working full time at the same daily rate as when it is working part time. The capacity, as estimated on this basis, is much more nearly the true capacity, although even with present railroad efficiency this amount of coal could not be moved.

Jan 1, 1926

By AIME AIME

LOCAL COMMITTEES. EXECUTIVE.-W. A. Lathrop, Chairman; R. V. Norris, Secretary; S. D. Warriner, Treasurer; Irving A.. Stearns, W. J. Richards, H. S. Drinker, C. D. Simpson. GENERAL RECEPTION.-Irving A. Stearns, Chairman. Archibald, James, Jr., Pottsville. Lawall, E. H., Wilkes-Barre. Ashley, H. H., Wilkes-Barre. Lentz, W. 0., Mauch Chunk. Ayres, WV. S., Hazleton. Lewis, Albert, Bear Creek. Beard, J. T., Scranton. Loomis, W. H., Jeddo. Bridgman, J. C., Wilkes-Barre. Markle, Alvan, Hazleton. Bunting, Douglas, Wilkes-Barre. Markle, John, Jeddo. Chase, F. M., Wilkes-Barre. Neale, J. B., Minersville. Coroner, Eli T., Scranton. Norris, R. V., Wilkes-Barre. Cote, E. B., Jr., Drifton. Oliver, Paul A., Oliver's Mills. Davies, W. H., Hazleton. Owens, W. D., Pittston. Davis, H. G., Dorranceton. Pardee, 1. P., Hazleton. Dodge, W. F., Wilkes-Barre. Quin, R. A., Wilkes-Barre.

Jul 1, 1911

By Leonid V. Azároff, H. N. Murty

In the course of investigating the soft X-ray absorption spectra of Ni-A1 alloys, Das and ~zfiroff' observed an anomalous brittleness in solid solutions containing 3 to 5 at. pct Al. The brittle alloys also had anomalously larger lattice constants' and the fine structure at the nickel K edge of an alloy containing 3.96 at. pct A1 unexpectedly resembled that of NiA1 more closely than that of a solid solution containing 5.51 at. pct Al. This led them to suggest the possibility that short-range ordering was produced during the homogenization anneal to which each specimen was subjected, similar to that observed in dilute solutions of vanadium and of chromium in nickel: as the principal cause of embrittlement. It was decided to repeat the above measurements on several alloys in this composition range in order to test the above hypothesis and to establish the effect of heat treatment on the alloys' properties. Three solid solutions in this range were prepared containing, respectively, 3.16, 4.00, and 4.54 at. pct Al, in addition to alloys containing 6 and 9 pct. All samples were annealed in vacuum at 1800°F for 100 hr and then furnace-cooled to room temperature, as in the original study. The lattice constants of these alloys are shown by open circles in Fig. 1 and can be seen to fit quite closely the curve established by the previously measured values, indicated by solid circles. (The experimental errors are of the order of the size of the circles, +o.oo~R.) The three alloys containing 3 to 5 at. pct A1 were found to be quite brittle, as previously reported. In order to test the possibility of ordering, these three solid solutions were again heated to 1800°F and, following a few hours at that temperature, were quenched directly to room temperature. All three alloys lost their brittleness. In order to verify the proposed ordering hypothesis, it was decided to subject each sample to several cycles of quenching and annealing (disordering and ordering). After some experimentation, it was established that reproducible results could be obtained by anneal-

Jan 1, 1968

By Jay N. Fairbanks, Richard G. Robinson

This paper discusses a computer program and related formulas for fire fighting responses by coal mine personnel. The computer will interpret the mine air analysis, print reports, and provide relevant graphs allowing quick and accurate responses to coal mine fires.

Jan 1, 1983

By HENRY M. PARKS

THE total production of all metals in Oregon to date is estimated at $160,000,000; ~115,000,000 from eastern Oregon and $45,000,000 from the western part of the state. In 1916 the metal production of the state was approximately $4,000,000, while the present annual production has dwindled to a little less than $1,000,000. Western Oregon The state of Oregon contains several metal-bearing areas, widely scattered in different regions. More than half of its coast is fringed with a belt of auriferous sands which sometimes are rich in fine gold. A second mining field, the chief producing one of western Oregon, is situated in the southwestern part of the, state and includes Jackson, Josephine, Douglas, Coos and Curry counties. It may be considered as the northern extension of the gold and copper belt of California. A third region in western Oregon is that on the western slope of the great Cascade range in the Bohemia, Blue River, Quartzville, North Santiam and Ogle Creek districts-from the Siskiyous on the south almost to the base of Mt. Hood near the Columbia River on the north.

Jan 1, 1925

By H. M. Howe

THIS paper presents an experimental verification of some of the predictions made by one of us' concerning 'the influence of certain conditions of casting upon the size and position of the pipe', and the position of the segregate, in steel ingots. The predictions which we have been able to verify are the following A. That the pipe is shortened and the segregate raised 1. By slow casting; 2. By casting with the large end up instead of down; 3. By retarding the cooling of the top, e.g., by means of a sinking-head. B. That the pipe is shortened by slow cooling. C. That the pipe and segregate lie in the last freezing-part. Our procedure was to cast ingots of wax (commercially pure stearic acid) containing a little bright green copper oleate (usually 1.5 per cent.) under varying conditions; to saw each ingot open along a longitudinal plane passing through its axis ; and to examine the longitudinal section thus laid bare. In order to make the segregate or enriched part more distinct in color from the impoverished part, a very little red cerasine was added. An experiment which will be described later showed that the cerasine itself does not segregate markedly, if at all. Hence we may assume that the strong contrasts between the green and red shown in so many of our ingots are due, not to segregation of cerasine, but to that of the green oleate, in the wax which in itself is uniformly reddened with cerasine.

Jul 1, 1907

By Edward Steidle

TWO years ago the Committee on Latin American Education Relations, Mineral Industries Education Division, started a study of mineral industries education in the Latin Americas. Information was obtainable only with great difficulty. Some information was available piecemeal but no complete resume had ever been assembled. Initial assistance was gained from the United States Office of Education and the Pan American Union. This, and first-hand knowledge of the writer, provided a list of colleges and universities which were believed to offer work lead. ing to a degree in one or more branches of the mineral industries. Detailed information could be obtained only by direct contact with each university through air mail service. Questionnaire letters were sent to officials of 34 colleges and universities. Twenty-one gracious replies were received. Fourteen of the colleges and universities concerned offer curricula in mining, five in metallurgy, three in petroleum, seven in geology, one in geographical engineering, one in topographical engineering, and one in geophysics. Two institutions offer advanced training in petroleum engineering. No institution offers any courses under the caption of ceramics or fuel technology.

Jan 1, 1945

By Christopher Haycocks, Lawrence P. Johnson, George M. Neall, James M. Townsend

No method of roof control yet devised has proven to be universally acceptable for the wide range of strata conditions experienced in U. S. coal mines. However, a relatively new innovation, the roof truss, has proven itself capable of preventing roof failures which both conventional and resin bolting could not. Presently, the economics of roof trusses are not favorable when compared to bolting due primarily to drilling and installation procedures, but this is expected to change with improved truss and equipment designs. To realize the full potential of this new method of roof control, design criteria are needed which can optimize the effect of the truss for varying strata conditions. A review of the literature reveals that some work has been conducted on the roof truss. Cambrell and Haynes1 (1970) showed that the roof truss is superior to angled roofbolts installed through a header. Sheorey, Verma, and Singh2 (1973) used statics to prove that the optimum angle of inclination should be greater than 45°. However, to date, no systematic attempt has been made to establish design criteria. In this paper, the problem was approached in three ways. First, model studies were performed to determine general trends of truss support as a function of a number of variables. This provided a better understanding of the support mechanism involved. Secondly, beam theory was employed to calculate the actual support capacity of a truss, realizing the many simplifications, assumptions, and shortcomings of this approach to such a complicated problem. Last, field testing will be utilized to test the hypotheses previously developed and provide hard data to further synthesize roof truss design criteria. Field testing has recently commenced and should be complete before mid 1977.

Jan 1, 1979

By Samuel S. M. Chan

The magnetic susceptibilities of some ores and the major rock formations of the Precambrian Belt Supergroup in the Coeur d'Alene mining district were determined both in the laboratory by the use of the Gouy method and in the field with a Bison susceptibility unit. Trace element analysis of the same group of rock samples was also made using the atomic adsorption technique. Results of this preliminary study indicate that some correlation exists between the magnetic susceptibilities and the various rock formations. This may be useful for regional mapping and mineral exploration.

Jan 1, 1974

By W. C. T. Yeh, T. G. Oakwood, A. A. Hendrickson, R. H. Hammar

The objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for by the influence of the solute addition on the dislocation structure oj- the crystals. The additions of both tin and indium produced only small changes in the dislocation densities and arrangements in silver crystals. However, as found previously, small solute additions have large effects on the tensile properties; the inj-luence of the tin and indium additions on the temperature dependence of the flow stress and the easy-glide range is especially strong; It is concluded that the indirect strengthening effect of the solute due to variations in the dislocation density as proposed by Seeger is of minor importance and that solute atom-dislocation interactions are responsible for the observed strengthenirzg effects. The experimental results were combined with those of Rogausch to test the concenlvatiorz dependence of solute strengthening. Both the first and one-half power dependences of the critical resoleed shear stress on concentratiorz fail in very dilute solutions. THE objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for, at least in part, by the influence of the solute addition on the dislocation structure of the crystals. It is recognized that the addition of solute atoms may influence the strength properties of a metal through both "direct" and "indirect" effects. The former refer to the strengthening mechanisms that result from the interaction of solute atoms with dislocations; in the latter case, the strengthening effects arise as a result of solute's influence on quantities such as dislocation density, dislocation arrangement, stacking-fault energy, diffusivities, the elastic constants, and so forth. It is clear that the correct interpretation of solid-solution strengthening phenomena cannot be given until the importance of indirect strengthening effects is properly evaluated. In the particular case of close-packed metal crystals, Seeger showed that solute strengthening effects in dilute solutions of copper and silver might be accounted for by an increase in dislocation density due to the addition of the solute. Seeger's argument was that the strengthening effects extrapolated from more concentrated solutions indicate that small concentrations of impurities raise the critical resolved shear stress much more than is predicted by a concentration-independent dislocation density. The above idea was a very reasonable one. The dislocation theories of work hardening of Taylor,2 Cot-trell, 3 Mott, 4 and seeger5 had already associated the increased flow stresses with increased dislocation densities in deformed metals; investigations of the dislocation structure of metal crystals had provided a logical basis for expecting an increased dislocation density in crystals containing impurities (see for example, Ref. 6). The numbers involved seem reasonable, too. It can be expected that the flow stress of the crystal would increase as the one-half power of the dislocation density.' Solute additions of 1 at. pct to metal crystals result in strength increases by factors in the range of three to ten. If one assumes that the strengths of the pure metal crystals are determined by their dislocation densities, then dislocation-density increases of one to two orders of magnitude as a result of solute addition would be required to account for the observed strengthening—not an unreasonable expectation. In addition to the effect of the solute addition on dislocation density, one might also anticipate important strengthening contributions to result from the solute's influence on the dislocation arrangement. Parker and washburns have reviewed a number of experimental evidences which show important strengthening effects due to the presence of subboundaries. Further, lattice strains due to impurity segregation would be expected to influence the distribution as well as the dislocation density of the as-grown crystal. As pointed out in the reviews of Chalmers,6 Elbaum,9 and winegard,lo micro segregation of impurities occurs at all interfaces of crystals in cellular growth; the impurity gradient results in lattice strains which can be reduced with the presence of dislocation arrays in the region of the impurity gradient. Hence, one would expect the presence of a solute to favor the formation of dislocation subgrain structures and that the subgrains would have an important influence on the strength of the crystal. The experimental observations that concern the possibility of an important strengthening contribution through the influence of the solute on the dislocation density or arrangement are not in agreement. Haasen has reviewed the observations of Meakin and Wils-dorf,12 Howie,13 and Bocek 36 and concluded that the solute's influence on dislocation density is not sufficient to account for strengthening effects in concentrated solutions but might, as seegerl suggested, make an important contribution in very dilute solutions. On the other hand, Hendrickson and Fine 14 concluded that changes in the dislocation density and dislocation width accounted for the solid-solution strengthening effects observed in silver-based aluminum solid solutions. Goss et a 1.I5 observed dislocation arrays in Ge-6 at. pct Si, Ge-0.2 at. pct Sn, and Ge-0.2 at. pct B crystals that were not observed in germanium crystals of

Jan 1, 1968

By H. Cecil Spicer

The results described in this article are based on field work conducted during the periods APril-May, 1939, and MaY-JulY, 1940. The United States Potash CO. is mining potash on Government land under a permit from the Department of the Interior and the geophysical investigation mas completed under a cooperative arrangemerit made between that company and the Conservation Branch of the Geological Survey. The writer, a member of the Section of Chemistry and Physics of the Geologic Branch, was assigned to this investigation. Four definite objectives were in mind for the geophysical work in the studies over the salt deposits. The first was to determine the measure of success that could be attained in this type of work with the resistivity methods that were to be employed. These methods had been introduced into the work of the Conservation Branch by Benjamin E. Jones for the investigation of dam sites, and have been used under his direction by the author for such work. If the method proved to be applicable, an l was to be made to contour the top of the salt beds and also the other formation boundaries known to be present in this area. Salt-water aquifers were to be studied in an effort to determine their boundaries, and an attempt was to be made to delineate the potash-bearing beds. Others have made, and reported, resistivity studies over saliferous deposits in different areas. Friedell and Messrs. Schlumberger2 reported geophysical work performed in the disrovery of the salt domes of Alsace; Carrette and Kelly3 described the geology of the same area. Leonardon and Kelly4 published a resistivity curve obtained over the Hettenschlag dome, and a further discussion of this same area was given by the Messrs. Schlum-berger5 in a communication. Messrs. Alty6 described studies 0" salt deposits in which the sing[e-probe method was used. Sinerez7 mentions that electrical methods were tried over salt deposits in Spain. Geoffrey and Charrin8 show a resistivity curve obtained over marl, gypsiferous marl and salt which is similar to that obtained over the New Mexico salt deposits. Kelly9 reported resistivity work performetl with the ground comparator of Zuschlag over the salt deposits near Syracuse, N. Y., where the Salina formation is at a depth of 700 to 800 ft. Some structural studies on the potash basin of Alsace are described by Poldini.10 Another single-probe resistivity study, made over salt deposits in New Mexico, is briefly described by Heiland,ll through the courtesy of Harry Aurand, of the Midwest Refining CO.

Jan 1, 1942

By H. Cecil Spicer

The results described in this article are based on field work conducted during the periods APril-May, 1939, and MaY-JulY, 1940. The United States Potash CO. is mining potash on Government land under a permit from the Department of the Interior and the geophysical investigation mas completed under a cooperative arrangemerit made between that company and the Conservation Branch of the Geological Survey. The writer, a member of the Section of Chemistry and Physics of the Geologic Branch, was assigned to this investigation. Four definite objectives were in mind for the geophysical work in the studies over the salt deposits. The first was to determine the measure of success that could be attained in this type of work with the resistivity methods that were to be employed. These methods had been introduced into the work of the Conservation Branch by Benjamin E. Jones for the investigation of dam sites, and have been used under his direction by the author for such work. If the method proved to be applicable, an l was to be made to contour the top of the salt beds and also the other formation boundaries known to be present in this area. Salt-water aquifers were to be studied in an effort to determine their boundaries, and an attempt was to be made to delineate the potash-bearing beds. Others have made, and reported, resistivity studies over saliferous deposits in different areas. Friedell and Messrs. Schlumberger2 reported geophysical work performed in the disrovery of the salt domes of Alsace; Carrette and Kelly3 described the geology of the same area. Leonardon and Kelly4 published a resistivity curve obtained over the Hettenschlag dome, and a further discussion of this same area was given by the Messrs. Schlum-berger5 in a communication. Messrs. Alty6 described studies 0" salt deposits in which the sing[e-probe method was used. Sinerez7 mentions that electrical methods were tried over salt deposits in Spain. Geoffrey and Charrin8 show a resistivity curve obtained over marl, gypsiferous marl and salt which is similar to that obtained over the New Mexico salt deposits. Kelly9 reported resistivity work performetl with the ground comparator of Zuschlag over the salt deposits near Syracuse, N. Y., where the Salina formation is at a depth of 700 to 800 ft. Some structural studies on the potash basin of Alsace are described by Poldini.10 Another single-probe resistivity study, made over salt deposits in New Mexico, is briefly described by Heiland,ll through the courtesy of Harry Aurand, of the Midwest Refining CO.

Jan 1, 1942

By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson' reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however', for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

By G. E. Pellissier, P. H. Salmon Cox, B. G. Reisdorf

Banding that occurred in plates rolled from the early production heats of 18Ni(250) maraging steel is described and related to the segvegation of certain alloying elements (nickel, molybdenum, titanium), the extent of which was quantitatively evaluated by means of electron-microprobe analysis. The effect of banding on mechanical properties is discussed, with particular reference to observed directional differences in plane-strain fracture toughness of plates. It is shown that banding originates as interdendritic segvegation during ingot solidification and persists in some degree through normal soaking and hot reduction to plate. The results of the study showed that heating sections of small laboratory-cast ingots at 2200°F for 4 hr was sufficient to markedly reduce microsegregation and to considerably improve mechanical properties. Hot rolling of 7-in.-thick ingot sections to 1/2-in.-thick plate effected a similar reduction of microsegregation, but resulted in even greater increases in ductility and toughness than that obtained by homogenization treatment alone. DURING the past few years, considerable attention has been directed towards the low-carbon, high-alloy maraging steels and in particular towards the 18Ni-8Co-5Mo-0.4Ti alloy. The steels of this group, having an excellent combination of high strength and toughness, have a number of advantages over their more conventional medium-carbon low-alloy, quenched-and-tempered counterparts. In the annealed condition, the maraging steels are in the form of a ductile marten-site; aging at a relatively low temperature, typically 900°F for 3 hr, increases greatly the strength through the precipitation of intermetallic compounds. One problem in the early production heats of maraging steel was that the finished plate frequently displayed a banded structure. Previous work on other steels1-' had established that banding in wrought products is either a direct or an indirect consequence of chemical segregation, which occurs during solidification and persists to some extent through normal thermal and mechanical treatments. For example, Smith and others: in a study of low-alloy steel, were able to correlate the severity of banding in the wrought product with the degree of interdendritic segregation of nickel and chromium in the as-cast ingot. The effect of banding on the mechanical properties of steels is usually considered to be detrimental, although there is only limited evidence to suggest that a marked improvement in properties can be obtained with less heterogeneous structures. Comparison of the longitudinal and transverse tensile properties of banded and of homogenized 4340 steel showed that only the transverse ductility was improved by homogenization, but even then the improvement was not commercially significant.' Conversely, homogenization of through-the-thickness tension specimens of quenched-and-tempered steel plate, containing 1.47 pct Mn, increased the strength by as much as 10 pct and the tensile ductility by at least a factor of twos5 This improvement was related to the elimination of manganese-rich bands, which also are one of the factors responsible for cold cracking in the heat-affected zone of metal-arc welds.7 In the present study the nature and severity of banding in early commercial 18Ni(250) maraging steel plate and in laboratory-melted 18Ni(250) maraging steel plate was determined. The effects of banding on plane-strain fracture toughness and the effects of thermal homogenization treatments on the strength, tensile ductility, and toughness of 18Ni(250) maraging-steel as-cast ingots and rolled plate were evaluated. In addition, the effects of hot deformation by rolling on the mechanical properties of ingots were determined. 1) STUDIES OF BANDING IN EARLY PRODUCTION PLATE The chemical composition of the steel (A) used in this part of the investigation is shown in Table I. Banding was not clearly evident in either as-rolled or annealed* plate, but annealed and agedc** plate had a banded structure. The typical banded condition, Fig. 1, consists of layers of unetched austenite (white) and dark-etching martensite in a light-etching martensitic matrix. X-ray diffraction measurements showed that this steel contained more than 6 pct austenite. An electron-probe X-ray microanalyzer (using a focused beam of electrons) was used to determine the composition of the bands and of the material between the bands with respect to the main alloying elements— nickel, molybdenum, titanium, and cobalt. The recorded X-ray intensities were converted to concentration values with the use of a standard of similar composition. To facilitate probe positioning, all analyses were conducted on specimens that had been given a light etch. The influence of this etching on the analytical results was negligible; analyses made on the identical area before and after etching yielded essentially the same concentration values. The results of the electron-microprobe analyses at selected points revealed that the layers of austenite and adjacent dark-etching martensite contained greater amounts of nickel, molybdenum, and titanium than did the surrounding matrix, Table 11. The austenite layers

Jan 1, 1968

By R. G. Ward, D. R. Gaskell

Using the maximum bubble pressure technique, the densities of iron silicates at 1410°C have been measured blowing helium, nitrogen, and argon. By ensuring equilibrium between the melt and the blowing gas with respect to oxygen potential and by minimizing tempcrature cycling of the furnace, iron precipitation in the melt has been prevented. Thus the previously reported effect of blowing-gas composition on the densities of the melts has been eliminated. Consideration of the oxygen densities of the melts gives an indication of the structural changes accompanying composition change. The density-composition relationship of iron oxide-silica melts in contact with solid iron has been the subject of several investigations1-7 and considerable disparities exist among the various results obtained. Of these investigations, all except one5 have employed the maximum bubble pressure method. In the most recently reported of these investigations1 the density-composition relationship obtained blowing nitrogen differed from that obtained blowing argon. The measured densities obtained under nitrogen were greater than those obtained under argon, the difference being a maximum at the pure liquid iron oxide composition and decreasing with increasing silica content. This observation rationalized the disparities existing among the results of the earlier investigations, showing that two lines, one for nitrogen and the other for argon, could be drawn to fit all the earlier results. No explanation for this phenomenon could be offered. Chemical analysis of rapidly quenched samples of melt for dissolved nitrogen, and direct weighing measurements, excluded solution of nitrogen in the melt from being the cause of the increase in density. The range of blowing gases was extended by Ward and Hendersons who measured the density of liquid iron oxide bubbling helium, nitrogen, neon, argon, and krypton. The measured density was found to decrease smoothly with increasing atomic number of the bubbling gas. The work reported here is a continuation of the program initiated by Ward and Sachdev7 to study the densities in multicomponent melts in which the iron oxide-silica system is the solvent. As such it is necessary to explain or eliminate the anomalous densities of iron silicates under different atmospheres, and the present rede termination was carried out towards this end. EXPERIMENTAL The maximum bubble pressure method of density determination was again employed and the experimen- tal apparatus used was essentially the same as that used by Ward and Sachdev.7 A molybdenum-wound resistance furnace heated an ingot iron crucible of internal diameter 1 in. containing a 2-in. depth of melt. The bubbling gas was blown through a 1/4 -in.-diam mild steel tube onto the end of which was welded a 2-in. extension of 1/4 -in.-diam ingot iron rod, drilled out to 5/32 in., and chamfered to an angle of 45 deg. The blowing tube was introduced to the furnace through a sliding seal and its position was controlled by a vertically mounted micrometer screw which allowed the depth of immersion to be determined with an accuracy of ± 0.01 cm. A Pt/Pt-10 pct Rh thermocouple was located below the crucible and temperature control was effected initially by means of an on-off controller and later by a saturable core reactor. The bubble pressure was determined by measurement of a dibutyl phthalate manometer using a cathetometer. PREPARATION OF MATERIALS Iron oxide was produced by melting ferric oxide in an inductively heated iron crucible in air. The liquid was quenched by pouring onto an iron plate. Silica was prepared by dehydrating silicic acid at 650°C for 12 hr. RESULTS Before any measurements of the density of a melt were made, the density of distilled water at room temperature was measured bubbling helium and argon. Both gases gave the density as 1.00 ± 0.01 g per cu cm which showed that the density of the manometric fluid (dibutyl phthalate) was not affected by contact with the blowing gas. With the furnace controlled by an on-off temperature controller an attempt was made to measure the density of pure liquid iron oxide by bubbling argon. The furnace atmosphere gas and bubbling gas were dried over magnesium perchlorate and deoxidized over copper turnings at 600°C. It was found that the pressure required to blow a bubble at a given depth increased slowly with time, and thus it was impossible to obtain a unique value for the density of the melt. Inspection of the blowing tube after removal from the furnace showed that rings of dendritic iron had precipitated from the melt onto the immersed part of the tube. This is shown in Fig. l(a) where the various "steps" correspond to different depths of immersion. The precipitation of iron was considered to be due to one or both of two possible causes: i) The composition of the liquid iron oxide is that of the liquidus at the temperature under consideration and can be expressed by the equilibrium

Jan 1, 1968

By M. Murakami, Y. Murakami, O. Kawano

The formation and growth of Guinier-Preston zones in Al-Zn alloys containing 4.4, 6.8, 9.7, and 12.4 at. pct zn have been studied by the X-ray small-angle scattering method. Particular attention was paid to the effects of small amounts of third elements silver, silicon, and magnesium on the formation and growth of G.P. zones. It was noticed that an appreciable number of G.P. zones were formed during the course of rapid cooling and that the size, volume fraction, and number of these G.P. zones were influenced by the existence of the third elements. During subsequent aging it was also found that the addition of both silver and silicon lowered the temperature for the growth of G.P. zones, whereas the addition of magnesium raised it. These results were explained in terms of the mutual interactions among zinc atoms, vacancies, and the third elements. A number of studies on the formation and growth of Guinier-Preston zones in Al-Zn alloys have been reported.1-4 Panseri and Federighii have found that the initial stages of zone growth take place at temperatures as low as around -100°C. For investigation of the mechanism of the initial stages of zone growth, growth studies must be carried out at low temperatures. In order to investigate the possibility of the formation of G.P. zones by the nucleation mechanism or the spinodal decomposition during quenching which was reported by Rundman and Hilliard,5 the examination of the as-quenched structure must be performed. In this paper the investigation of the early stages of the formation and growth were determined by means of the X-ray small-angle scattering method. With this technique, change of X-ray scattering intensities was measured while quenched specimens were heated slowly from liquid-nitrogen temperature to room temperature. At as-quenched state and after heated to room temperature, investigation of zone size, volume fraction, and zone number per unit volume was carried out. Measurements on these specimens yielded information on the early stages of zone formation and growth. Measurements were made also on specimens quenched to and aged at room temperature. From these measurements the previously reported model6 for the later stages of growth is confirmed; namely, the larger zones grow at the expense of smaller ones. Three elements, silver, silicon, and magnesium, were chosen as the third elements for the following reasons: Silver. In the binary A1-Ag alloy the spherical disordered 77' zones were observed immediately after quenching.7 Therefore, in the Al-Zn-Ag alloys, it is suggested that silver atoms might induce cluster formation during quenching. Also, since the migration energy of the zinc atoms was found to be raised by the addition of silver atoms,' silver atoms may have a great effect of the zinc diffusion, especially during low-temperature agings. Silicon. The effects of the addition of silicon atoms were found to be marked, especially at low-tempera-ture aging. In the binary Zn-Si system, no mutual solid solubilities between silicon and zinc9 and no in-termetallic compounds10 are reported to exist. Shashkov and Buynov11 investigated the behavior of silicon atoms in Al-Zn alloys and showed that silicon was not in the G.P. zones. The interaction between silicon atoms and vacancies is strong enough to increase the quenched-in vacancy concentration.* Magnesium. Magnesium atoms are reported to trap quenched-in vacancies and after much longer aging times these trapped vacancies will become free and act as diffusion carriers.13 Therefore at intermediate aging times, the diffusion of zinc atoms in Al-Zn-Mg alloys will be slower than in the binary Al-Zn alloys, whereas at longer times zinc diffusion will become faster. EXPERIMENTAL PROCEDURE The alloys used in this investigation had compositions of 4.4, 6.8, 9.7, and 12.4 at. pct Zn with or without 0.1 and 0.5 at. pct Ag, Si, or Mg. The alloys were prepared from high-purity aluminum, zinc, silver, silicon, and magnesium, with each metal having a purity better than 99.99 pct. The analyzed composition of the specimens is given in Table I. The measurements of the X-ray small-angle scattering were carried out with foils of 0.20 mm thick. The change of the scattering intensity was always measured at the fixed scattering angle of 20 = 2/3 deg. This angle exists nearly on the position of the intensity maximum. The value of the interparticle interference function14 which has large effect in this range of angles may not change abruptly in the case of the spherical shape of small zones. Therefore, from the above considerations, it is concluded that an increase of the intensity measured at this constant angle corresponds to an increase of the average radius and volume fraction of G.P. zones. The specimens were homogenized at 500°, 450°, and 300°C for 1 hr in an air furnace. For the study of the formation and growth at low temperatures, the foil

Jan 1, 1970

By Carl J. McHargue

Mechanical twins were produced in electron-beam melted columbium by high-speed impact at room temperature and by slow or fast compression at -196°C. The composition plane of the twins was { 112} and the shear direction was <111>. Notches in the twin bands often corresponded to traces of {110) of the matrix and appeared to be untwinned regions. Markings within the twin bands were interpreted as resulting from {110} slip in the twins. THERE has been much work in recent years concerning plastic deformation by glide, and the dislocation theory relating to glide has reached a relatively high degree of development. On the other hand, there have been fewer studies of deformation by mechanical twinning, and understanding of this process is far from satisfactory. This method of deformation is of interest for at least two reasons. First, it provides a mechanism in addition to glide for the relief of stresses, and, in the bcc and hexagonal close-packed metals may result in significant amounts of plastic flow. Secondly, there is the possibility that twins may act as barriers for dislocation movement, resulting in pile-ups which could nucleate cracks. As might be expected, the bulk of the literature on mechanical twinning in the bcc metals is concerned with iron. A good summary of the work done prior to 1954 is contained in the book by all.&apos; Recently the refractory bcc metals have become increasingly important. Limited studies have shown that tantalum,2,3 molybdenum,4,5 vanadium,6,7 tungsten,&apos; and columbium9-11 deform by mechanical twinning under some conditions. Alloys of molybdenum with rhenium and tungsten with rhenium show extensive deformation by twinning at room temperature.I2-l4 Most of these studies have dealt primarily with mechanical properties at low temperatures or have shown the existence of twins, and there is only a small amount of information concerning the conditions under which they form. The subject of the present paper is the formation of twins under stress in columbium with a consideration of their morphology. EXPERIMENTAL PROCEDURE The material used for these studies was taken from an ingot of columbium which had been melted twice by the electron-be am-method. The analysis of the ingot was (in ppm): B < 1, C = 10, Fe < 100, The cast ingot contained very large grains, and it was possible to obtain single-crystal prisms which measured from ¼ to 3/4 in. on a side. A few experiments were conducted on polycrystalline plate which was prepared by rolling material from the same ingot at room temperature and annealing at 1000 in a dynamic vacuum of 10-6 mm Hg. This gave a plate in which the grains had an average diameter of 3 mm. After the specimens were cut from the ingot, the six faces were metallographically polished and elec-tropolished to remove all traces of cold work. Most of the observations were made on the surfaces of the deformed specirllens without further treatment. Occasionally, etching after deformation was desirable. In these cases, an etchant of the composition 50 parts H2O, 5 parts HNO3 25 parts HF, and 10 parts H2SO4 was found to delineate the twins very well. Unless considerable care was taken to ensure the removal of all disturbed metal left by the mechanical polishing, etching failed to reveal many of the features discussed in this; paper. The specimen&apos;s were deformed either by impact or slow compression at 77°K (liquid-nitrogen coolant), 198°K (dry ice and acetone coolant), and 298°K. The impact load was delivered by a hammer except in one case where the load was delivered by a bullet. Slow compression was carried out on a hydraulic testing machine equipped with a chamber to hold the coolant. EXPERIMENTAL RESULTS It has been generally believed that the conditions favoring the formation of deformation twins are large grains, low temperature, and impact loading. In fact, Barrett and Bakish2 found twins in tantalum only after impact deformation at 77°K, and Adams, Roberts, and Smallman10 observed twins in columbium only at 20 For these reasons, the initial experiments of this study used impact loading. Hammer blows caused many bands resembling twins in single crystals a.t 77" but not at 198°K. Only a few slip lines were observed on any of the single-crystal specimens of this study—essentially all the deformation occurred by twinning. The appearance of the twins on the as-deformed surface is shown in Fig. 1. Although both Figs. 1(a) and l(b) are photomicrographs of twins taken at the same magnification and from the same crystal, they are startlingly different in appearance. Fig. 1(a) was taken from the crystal face approximately perpendicular to the shear direction, whereas Fig. 1(b) was taken from

Jan 1, 1962

By J. B. Cheatham, J. W. McEver

A laboratory investigation of the behavior of casing subjected to salt loading indicates that it is not economically feasible to design casing for the most severe situations of nonuniform loading. When the annulus is completely filled with cement, casing is subjected to a nearly uniform loading approximately equal to the overburden pressure, and, although the modes of failure may be different, the design of casing to withstand uniform salt pressure can be computed on the same basis as the design of casing to withstand fluid pressure. Failure of casing by nonuniform loading in inadequately cemented washed-out salt sections should be considered a cementing problem rather than a casing design problem. INTRODUCTION Casing failures in salt zones have created an interest in understanding the behavior of casing subjected to salt loading. The designer must know the magnitudes and types of loading to be expected from salt flow and he must be able to calculate the reaction of the casing to these loads. In the laboratory study reported in this paper, short-time experimental measurements of the load required to force steel cylinders into rock salt are used as a basis for computing the salt loading on casing. These results must be considered to be qualitative only since rock salt behaves differently under down-hole and atmospheric conditions and also may vary in strength at different locations. The beneficial effects of (1) cement around casing, (2) a liner cemented inside of casing, and (3) fluid pressure inside of casing in resisting casing failure are considered. ROCK SALT BEHAVIOR UNDER STRESS The effects of such factors as overburden loading, internal fluid pressure, and temperature on the flow of salt around cavities have been studied extensively at The U. of Texas. Brown, et al.1 have concluded that an opening in rock salt can reach a stable equilibrium if the formation stress is less than 3,000 psi and the temperature is less than 300°F. At higher temperatures and pressures an opening in salt can close completely. These results indicate that calculations based upon elastic and plastic equilibrium for an open hole in salt should be applied only at depths less than 3,000 ft. In most oil wells the tem- perature will be less than 300F in the salt sections, therefore no appreciable temperature effects are anticipated. Serata and Gloyna2 have reported an investigation of the structural stability of salt. .They assume that the major principal stress is due to the overburden. Other stresses can be superimposed if additional lateral pressures are known to be acting in a particular region. In the present analysis an isotropic state of stress is assumed to exist in the salt before the hole is drilled, since salt regions are generally at rest. This assumption is partially verified from formation breakdown pressure data taken during squeeze-cementing operations in salt. Experimental measurements of the elastic properties of rock salt indicate a value of 150,000 psi for Young&apos;s modulus and a value of approximately 0.5 for Poisson&apos;s ratio. A value of % for Poison&apos;s ratio with finite Young&apos;s modulus would indicate that the material was incompressible. Values ranging from 2,300 to 5,000 psi have been reporteda for the unconfined compressive strength of salt. These variations may be due to differences in the properties of the salt from different locations or at least partially to differences in testing techniques. Salt is very ductile, even under relatively low confining pressures. For example, in triaxial tests reported by Handin3 strains in excess of 20 to 30 per cent were obtained without fracture. When casing is cemented in a hole through a salt section, the casing must withstand a load from the formation if plastic flow of the salt is prevented. To determine the forces which salt can impose on casing, circular steel rods were forced into Hockley rocksalt with the longitudinal axis of the rods parallel to the surface of the salt. The force required to embed rods 0.2 to I in. in diameter and 1/2 to 1 in. long to a depth equal to the radius of the rods was found to be F/DL =28,700 psi (± 3,700 psi) , .... (1) where D is the diameter, and L is the length of the rod. CASING STRESSES Since an open borehole through salt at depths greater than 3,000 ft will tend to close, cemented casing which prevents closure of the hole will be subjected to a pressure approximately equal to the horizontal formation stress after a sufficiently long time. As a first approximation the horizontal stress can be assumed to be equal to the overburden pressure. This is in agreement with the suggestion by Texter4 that an adequate cement job can prevent plastic flow of salt and result in a pressure on the casing approximately equal to the overburden pressure. He also advocated drilling with fully saturated salt mud

Jan 1, 1965