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By C. E. Shoenfelt

The deepening of the General Crude Oil Company's No. 1 Meyers, NE. NE. SE. of sec. 22, 24S., 36E., in the Cooper area of Lea County, in April, 1934, resulted in the discovery of an oil field of major importance. The discovery well is an old well drilled by Cranfill $ Reynolds and completed in July, 1929, in limestone at 3438 ft. for an initial production of 90,000,000 cu. ft. (estimated) of 'gas. Deepening operations were started early in April, 1934, and cores were taken from the old total depth of 3438 to 3508 ft. A Haliburton test taken through the drill stem at 3439 to 3460 ft. showed 50,000,000 cu. ft. of gas with an increase of 5,000,000 cu. ft. between 3461 and 3474 ft. When completed the well tested 12,000,000 cu. ft. of gas and 5000 bbl. of oil at 3474-3508 feet. The new oil field—the result of this discovery—is between the Eunice and the Jal fields, closer to the productive area of Jal than to that of Eunice but far enough away from both to be considered a separate area. Eventually, all of these pools may be joined together by productive oil wells to form a single unit of large size. They lie in a general northwest-southeast alignment and the intervening areas have not been condemned by dry holes. In the drilling campaign that followed this discovery, 24 wells were drilled, of which 23 were oil wells with combined initial productions of

Jan 1, 1935

The Janet Annenberg Hooker Hall of Geology, Gems and Minerals, located in the National Museum of Natural History, Smithsonian Institution, in Washington DC, opened in September, nine years after initial fundraising efforts were begun. The 1,858-m2 (20,000-sq ft), $16-million hall was mostly funded by private groups and individuals, including $1.7 million from 43 National Mining Associa¬tion (NMA) member companies. Companies that contributed more than $100,000 included Cyprus Amax, Phelps Dodge, Asarco, Homestake Mining, BHP, Caterpillar, Cleveland Cliffs, Exxon Coal and Minerals, Freeport-McMoRan, Newmont Mining and Peabody Holdings. The mining industry's contributions funded a walk-through Mine Gallery. It. features diora¬mas of four mines, as well as numerous specimens associated with the mines. The Mine Gal¬lery demonstrates to the public the importance of mining. The hall was named in honor of Hooker. She contributed $5 million in cash plus the Hooker Yellow Starburst Diamonds to the project. The hall is touted by the Smithsonian as the "most comprehensive earth science complex of its kind." It consists of seven galleries, each devoted to different aspects of gems, minerals and rocks. In addition to the Mine Gal¬lery, the hall contains a collection of gemstones and jewelry pieces, an extensive collection of minerals, a gallery devoted to plate tectonics and a gallery devoted to the moon, meteorites and the solar system. The new hall is a complete makeover of the old and outdated Geology Hall. It was built in the 1960s and finally closed to the public in 1995.

Jan 1, 1997

By H. O. Hofman

THE leading antimony mineral is stibnite. In smelting stibnite ore two processes are available, precipitation and roasting-reduction. The former is suited only for high-grade ores. As low-grade ores are more common than high-grade, roasting-reduction is of greater importance than precipitation. In the roasting process the aim may be to leave the oxidized antimony in the ore, or it may be to volatilize as much of the antimony as possible, collect the volatilized oxide as a rich intermediary product and smelt it for antimony, leaving the gangue poor enough to be considered a waste product. Whichever way the roast is conducted certain difficulties inherent in stibnite are encountered. These are: 1. The low melting point of stibnite which; according to Pelabon,1 is 550°C., according to Wagemann2 540°C., and according to Borgström3 546°C. 2. The ignition temperature: According to Friedrich,4 stibnite, if heated in air, begins to oxidize at 290°C. if the size of a grain is 0.1 mm. in diameter; at 343°, if 0.1 to 0.2 mm.; and 430° if 0.2 mm. 3. The fusibility of a mixture of Sb2S3 and Sb203 which in the form of kermesite (Sb2S3)2.Sb203 melts at 517°C.5 4. The volatility of Sb2S3 and Sb203, for which no numerical data appear to exist, although practical experience has shown that they are volatile at low temperatures.

Jan 1, 1916

By M Freeman

Significant improvements in the metallurgical performance at Pasminco Rosebery Mine have occurred over the last two years. Lead and silver recoveries have increased by more than ten per cent, lead concentrate grades are four per cent higher, zinc recoveries are up 1.5 per cent, and zinc concentrate grades have increased by two per cent. These impressive results have not occurred through the application of some new wonder reagent, but through the application of some fundamental metallurgical principals. The basic premise applied during this study was that to make an effective separation you must first achieve liberation. Therefore, the laboratory and plant studies examined the liberation characteristics within the lead circuit, and the impact of regrinding. The work demonstrated clearly that galena/sphalerite liberation was poor, and significantly impaired plant performance. Further, it was suggested that the application of lead regrinding of the lead scavenger concentrate and the lead first cleaner tailing would not only benefit lead metallurgy, but also improve sphalerite flotation. A similar approach was then applied to the zinc circuit. From these studies, solutions applying simple circuit changes utilising existing equipment were proposed and implemented. Further to the improvements in galena/sphalerite liberation, significant improvements in concentrate quality were achieved by reducing variation within the process. The implementation of changes in work practices negotiated in the Enterprise Agreement, employee contributions and specialist training also made a significant contribution to the unprecedented improvement in the lead and zinc flotation circuit performance. The results of these plant changes are discussed, along with the suggested scope for further improvement.

Jan 1, 2000

By Bryan Morris

Quebrada Blanca (QB) is a copper project located in the semi-arid Andean highlands of northern Chile. The operation is situated 170 km ( 105 miles) southeast of the port of Iquique and 30 km (18 miles) west of the border with Bolivia, at an altitude of about 4300 m (14,000 ft) (Fig. 1). The QB ore body is a secondarily enriched porphyry copper deposit containing reserves of 85 Mt (93 million st) grading 1.3% copper. Underlying the enriched zone is a significant primary ore zone containing several hundred million tons grading about 0.5% copper. In the late 1970s and early 1980s Falconbridge and its affiliates spent $20- $30 million exploring the deposit and conducting feasibility studies. Falconbridge, however, decided not to develop the property. It was returned to its owners, Empresa National de Mineria (ENAMI), a Chilean state mining corporation. In 1988, ENAMI announced its intention to privatize the property through public bidding. Cominco Resources, then 61% owned by Cominco Ltd., examined the property and the extensive data base developed by Falconbridge. In conjunction with its parent company, Cominco Resources submitted a proposal to ENAMI to construct an open- pit mine, with heap leaching and solvent extraction/electrowinning (SX-EW) processing facilities. The plan would use patented heap leaching technology developed by Sociedad MineraPudahuel (SMP), a privately owned Chilean mining company. At that time, a $150-million project that would produce about 45 kt/a (50,000 stpy) of cathode copper was envisaged.

Jan 1, 1993

By C. B. Jordan

LAVES and Wallbaum' have described TiRu and TiOs as having the same structure as TiFe; they had previously described the latter compound as having the CsCl structure. On the other hand, a careful investigation of the structure of TiFe by Duwez and Taylor- ailed to reveal the ordered CsCl structure, finding instead a random arrangement of titanium and iron atoms on the points of a body-centered-cubic space lattice. Consequently, it is not clear whether Laves and Wallbaum proposed the ordered or the disordered structure for TiRu and TiOs. In order to settle this question as to the structural type and to obtain values of the lattice para- meters (thereby completely determining the structures), the present investigation was undertaken. Samples having the compositions TiRu and TiOs were weighed out accurately from iodide titanium supplied by the New Jersey Zinc Co., ruthenium powder from Goldsmith Brothers Smelting & Refining Co., and osmium powder from Wildberg Brothers Smelting & Refining Co. No analysis was made of any of these metals. According to the respective analyses of the suppliers, total impurities amount to less than 0.03 pct in the titanium and to less than 0.5 pct in the osmium. The purity of the ruthenium is not known. The alloys were prepared by arc melting in a furnace of the type described by Schramm, Gordon, and Kaufmann.9 pecimens for X-ray diffraction were obtained by crushing the ingots and passing the resulting powders through a 200 mesh screen. Diffraction patterns were made with a powder

Jan 1, 1956

By Peter M. Anderson

IN recent years many prophets have arisen who hold that gold has outlived its days and that its monetary use is now an anachronism. These prophets include well-known politicians, economists and businessmen. Some of them have called it a joke that metal should be dug up at heavy cost in Africa and elsewhere and shipped to the United States of America only to go underground again at Fort Knox. Others have claimed that all the gold in the world could be sunk in the ocean without anyone being the poorer. The fact that you have invited me to address you on the future of gold may perhaps reflect the fears caused by these various predictions. At present the prophets' taunts show no sign of coming true. The demand for gold is greater than ever before, although stocks held are the largest in history. Nearly all governments have gone to great lengths to suppress any demand that might be made by the public; they have reserved to themselves the right to hold gold and have lost no opportunity of satisfying their own demands. Where the public has been allowed to buy gold, the demand has proved impressively strong. In India the price of gold equals about $82 per fine ounce, having been $90 earlier in the year; in Egypt $65 to $70, after having been $87, and elsewhere it is even higher. In Palestine, for instance, the golden sovereign is traded at about £5, equivalent to $86 per fine ounce, having been nearly £6, equivalent to some $100 per fine ounce, earlier in

Jan 1, 1947

A statistical investigation of folding at Mount Isa disclosed similar patterns in both the shales and the "silica dolomite" zones. Analysis of these patterns yields 3 groups of folds fully developed north plunging folds, fully developed south plunging folds, and flexuresrepresenting stages of development of folds. Interpretation of results indicates that a regional force from a southerly direction was responsible for the folding.The general pattern of shearing is allied to that of folding, with the exception of bedding-plane shearing. Many shears resulted from continued application of force on folds which ruptured after overthrusting. Other shears resulted from rupture of the more incompetent shale members, without associated folding. The shear pattern is consistent with the theory of a regional force from a southerly direction.INTRODUCTIONThe notes on folding and shearing presented in this paper are part of a current study of the structural geology of Mount Isa.FOLDING 1Measurement of FoldsInvestigation of folding underground involved the measurement of plunge, strike and dip of the axial plane, and the order of magnitude of each fold, together with its location and the rock type. The total number of folds measured was 701, of which 411 occurred in shale areas and 290 within the "silica dolomite" zones. All folds measured are located on main levels, from 7 level to 13 level inclusive. The sections of the mine involved are the Black Star, Black Rock and Racecourse. Detailed investigation of folds on the upper levels (4, 5 and 6) has not yet been done, but observations there suggest...

Jan 1, 1961

Manganese ore has been mined from the Peak Hill Gold- field since 1948 and from the Pi'lbaraòGoldfield since 1954, and it is probable that some deposits- In and, near the Phillips River Goldfield will be mined at a future date', There are also several million tons of mariganiferous ;naterial which is too low in manganese. .co.ntent_ for . present requirements. The manganese deposits¦of Western Australia are mostly superficial. They hav' been formed during the Cainozoic Era by supergene enrichment ò6f Precambbrian: manganiferoius sediments, and by deposition from -solution on, or'in caves in, the Cain- ozoic land surface. The manganese in solution was derived from the weathering of Precambrian manganifer.ous s.edimexsts, None of the deposits are of hydrothermal origin, nor are they related to igneous rocks in any war, other than as ultimate source rocks. There is ho evidence-'t.o.:sugge,st that meta- morphism has been responsible for.the emplacement of any deposit. The tenor of the ore varies'aec'ording'to the quantity of gangue in the orebody and- also to the nature of the part- icular ore minerals. The main ore.mine.rals are the oxides pyrolusite and cryptomelane and the 'o'xide-silicate braunite. The main gangue minerals are hematite, limonite and quartz. The deposits of high grade oreò(-above.45 per cent Mn) range in size from 50 tons to many thousands of tons but most of them are in the 500-5,000-tons r .nge .

Jan 1, 1964

Australia as a leading producer of mineral sands has also occupied a leading position in many areas of research'in the processing and applications of these minerals. Research in upgrading ilmenite to produce synthetic rutile has resulted in the develop- ment of many processes, e.g,., Becher, Murso, Chlorine Technology, and ICI processes. Studies on the reducibility of ilmenites, aqueous leaching of reduced ilmenites, Fe-Ti-O system, leachability of natural and treated ilmenites in hydrochloric acid and selective chlorination of iron from ilmenites have been carried out in order to develop and improve the efficiency of the above processes. While research on the processing of zircon sand to produce high purity (99.99% ZrO2 zirconia powder and zirconium chemicals started only recently, research by CSIRO in the early 1970s led to the discovery of the phenomenon of transformation toughening in partially stabilized zirconia (PSZ) ceramics. Australia, with very significant resources of lanthanide-containing ores, pro- duces substantial quantities of monazite each year but research in processing and appli- cations of rare earths was neglected in recent years in this country. However, research to improve processes for the recovery of rare earths is now under way and studies on the production and testing of Nd-B-Fe magnets which are 1.5-2 times stronger than the strongest magnets (Sm-Co) currently available, have also commenced.' An overview of the research in the pro- cessing and applications of mineral sands during the last two decades in Australia and its implications for the industry are pre- sented in the paper.

Jan 1, 1986

By R. D. Pehlke, J. V. Gluck

A study was made of' the effects of up to five additional solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450" to 650°C. The experimental measurements were made in a multielectrode galvanic cell apparatus employing fused LiCl-KCl as the electrolyte. The solute additions included indium, lead, tin, cadmium, copper, silver, antimony, or gold. A range of positice and negative interactiotls with zinc was covered. The experinzer~tal observations were cowlpared with the activity coefficients calculated usitlg either Wagner's first-order Taylor series rnodel or a proposed second-order solution itrteraction model. hi general, the truncated first-order Taylor series proposed by Wagner gaue good results for "dilute" solutions (XBi > 0.90) contaitzing up to six solutes. The second-order model, which includes a second-order cross-interaction term, produced a slight improvement in predictions for solutions with XZn = 0.015 and a significant improvement for solutions with XZn = 0.050 hear the limit of Henry's law region). Seveval of the quaternary solutions studied contained a total solute content of 0.215 mole fraction, and fairly good success was achieved in predicting the activity coefficient 01- zinc. ThE study of thermodynamic interactions between dilute solutes in liquid metallic solutions has occasioned much recent interest. It is useful to recall in this respect that Wagner's well-known expression for the activity coefficient' is a practical application of the problem of representing a given function, i .e., In ?, by means of a sequence of polynomials. No specific physical model of a solution is involved in its use. As suggested by Wagner, a Taylor Series is used to expand In ? about a point of infinite dilution with respect to all solutes. The partial differential coefficients of the series have been termed "interaction parameters". Various authors'-6 have proposed formalisms for parameters, the definitions being designed to meet some specific experimental or physical condition. A usual assumption is that terms above first-order in the Taylor Series may be neglected. In that case, the logarithm of the activity coefficient is expressed as a linear function of solute concentrations. The resulting expression is presumed valid for any number of additional solutes as long as the solution can be regarded as "dilute". This assumption can be termed "the hypothesis of additivity". However, experimental tests of that hypothesis for quaternary or higher-order solutions have been extremely limited. Primarily such tests have been confined to studies of effects of added metallic elements on either the activity of carbon or the solubility of gases in liquid iron.7-13 The only known previous study of an all-metal system is the limited work of Okajima and pehlke14 on the effects of multiple solute additions on the activity of cadmium in liquid lead. The present investigation is a portion of the work to determine the effects of various solute additions on the activity of zinc in dilute solution with molten bismuth in the range 450" to 650C It was shown for such ternary solutions that second-order Taylor Series terms could be evaluated at the same time as first-order terms, with no additional experimentation required. A second-order solution model was described which, under certain conditions, is a rigorous representation of solute activity in a ternary solution. (In the sense employed in this paper, the term "model", as distinguished from "equation", is taken to mean an empirical correlation or formalism, but not a hypothetical physical system per se.) Presumably such a model could be extended to produce a better representation of In ? in solutions of even higher order. The feasibility of a generalized Taylor Series approach to solution interactions and inclusion of second-order terms also has been discussed recently by Lupis and Elliott in independent work concurrent with the present investigation. In addition, they discussed empirical means of estimating certain second -order coefficients.17 The utility of such solution models rests on the ability of a truncated series to represent adequately the experimental facts in multicomponent solutions. Questions that arise include: Do the second-order terms really make a significant contribution? How far away from "dilute" solution may such models be applied? Are the types and varieties of the additional solutes important? among others. In order to provide some answers to these questions, an experimental study was made of the effects of two or more additional solutes on the activity of zinc in dilute solution with molten bismuth. Comparisons were then made with calculated activity coefficients obtained using the previously determined ternary interaction parameters. INTERACTION MODELS As an example of the approach to defining activities in multicomponent solutions, consider the Taylor Series expansion for a quaternary system, i.e., three dilute solutes. Writing terms through second order, the result is:''

Jan 1, 1968

By C. C. Templeton, J. C. Rodgers

A key step in feed water treatment for generating wet steam for thermal oil recovery is the removal of calcium and magnesiunt hardness by cation-exchange series softening. Knowing the solubility of any scale forming salts in brines at elevated temperatures is necessary for fixing the level to which the feed water must be softened. Such calcium sulfate solubility data, previously not available above 392F, were determined by the authors in a flow equilibrium apparatus mud will be reported elsewhere. These data were used to develop a method for predicting the solubility of anhydrite in hot water or steam droplets for saturated steam pressures as high as 2,000 psig (637F). (The calcium sulfate solubility product is represented by a combination of two factors, one reflecting the effects of ionic strength and the other accounting for the effects of complex ion formation in either calcium-magnesium-rich or sulfate-rich brines.) The method is applied to a calcium-magnesium-rich brine If moderately high salinity from a pilot hot-water flood, I nd to several sulfate-rich, low-salinity feed waters and l lowdown (cooled steam droplets) samples from steam s ak operations. The predicted calcium hardness levels corresponding to the calcium sulfate solubilities agreed reasonably well with the results of laboratory solubility determinations run on the field samples. Further testing of the method is needed for brines of other composition classes. Existing field cation exchange softeners in the cases tested are performing adequately since all the samples were found to be undersaturated with respect to calcium sulfate at their operating temperatures. Introduction Prevention of scaling caused by precipitation of calcium sulfate (anhydrite) is of considerable concern in connection with thermal recovery processes using wet steam or hot water. To avoid anhydrite precipitation in a heated system, an engineer must keep the product of the calcium and sulfate concentrations in the water or steam droplets below the value of the solubility product of anhydrite for the temperature and brine composition in question. Usually it is most practical to keep the concentration product lower than the solubility product by keeping calcium low in the presence of high sulfate, or by keeping sulfate low in the presence of high calcium. This can be done by a choice of combinations of natural waters and water treatment processes (such as series cation exchange softening to remove calcium). Until recently, few anhydrite solubility data, particularly for solutions containing other salts, were available for temperatures above 392F (211 psig steam); Marshall, Slusher and Jones' studied the CaS0,-NaCI-H,O system up to 392F and surveyed the work of previous investigators. To model natural brines, one needs to study the solubility of anhydrite in aqueous solutions of sodium chloride, sodium sulfate, calcium chloride, magnesium chloride and their mixtures. Since steam pressures as high as 2,000 psig (637F) may be involved in thermal oil recovery projects, a solubility study was conducted between 482 and 617F.' Discussed in this paper is the application of these data to the prediction of anhydrite precipitation in some practical steam soak and hot-water injection projects. Any simple method for predicting the solubility of an inorganic compound over a wide range of temperatures and solution compositions must be based on some assumptions, and therefore must yield approximate results. On the one hand, natural brines contain too many ionic species for all to be included in a simple scheme; on the other hand, there is no adequate theoretical basis for the exact prediction of solubility in even simple solutions of mixed electrolytes. However, it is possible at a given temperature to base a reasonable prediction scheme on two phenomena:'-' the increase in solubility with increasing total concentrations of all ions (as measured by the ionic strength; see the Appendix), and an increase due to formation of cornplexes between calcium ions and sulfate ions and between sulfate and magnesium ions. Stiff and Davis' developed such a scheme for predicting the solubility of gypsum (CaSO, ¦ 2H,O) in brines at temperatures u~ to 212F. However, for the higher temperaturei of present interest, the stable solid phase is anhydrite (CaSO,). This study involves a two-part method for predicting anhydrite solubility products. First, one predicts a value K, for a given ionic strength I and a given temperature T corresponding to mo./msr, = 1 from data of the CaS0,-NaCI-H,O system. Second, one determines a group of factors F .= F(Ca) • F(Mg) • F(SO,), where the individual factors account for increases in the solubility product due to complex formation by high concentrations, respectively, of calcium, magnesium and sulfate. Combining the two parts, one obtains the solubility product in molalities as

Jan 1, 1969

By B. E. Terkelsen, B. J. Piearcey

A study has been made of the effect of unidirectional solidification on the creep behavior, stress-rupture properties, and thermal shock resistance of four nickel-base superalloys. The alloys Mar-MZOO, B-1900, IN 100, and TRW 1900 show improved rupture ductility and thermal shock resistance when tested with the columnar grains parallel to the major stress axis during test. The relative improvement in creep-rupture properties depends on the intrinsic strength of the alloy, a property which depends on composition, heat-treatnient, and crystallographic orientation. The data clarifies some of the factors affecting the properlies of the cast nickel-base superalloy. COMPONENTS designed for high-temperature use have, in recent years, been fabricated by precision casting techniques using nickel-base alloys developed specifically for use in the conventionally cast condition. This development was a result of both the increasing complexity of the component and the recognition that high-temperature strength was incompatible with workability. The use of castings can be economically favorable, but, more important, the recent complex designs of air-cooled gas turbine blades and vanes in alloys which possess the necessary high-temperature strength cannot be forged. Common modes of failure of high-temperature components are excessive creep, creep rupture, and thermal fatigue. If rupture occurs then the mechanism is usually by inter crystalline cracking along those grain boundaries oriented transverse to the major stress axis. In the stronger alloys, rapid propagation of intercrystalline cracks result in apparent premature failure demonstrated by the absence of third stage creep in a creep-rupture test and low rupture ductility. Tensile ductility shows a similar trend, that is, decreasing ductility with increase in strength. It is not surprising, therefore, that increases in creep strength have only been obtained with a loss in resistance to thermal shock, a property which shows a dependence on tensile ductility. VerSnyder and ~uard' showed that the application of unidirectional solidification to a brittle Ni-Cr-A1 alloy both improved the rupture life of the alloy and increased rupture ductility. Since this casting method results in columnar grains, it appeared that the solution to the lack of ductility in nickel-base alloy components was the elimination of the source of failure, namely the transverse grain boundaries. This concept was recently developed2 to produce cast-to-size gas-turbine blades and vanes consisting entirely of columnar grains oriented parallel to the major stress axis of the component. Not only did the process impart increased rupture life and ductility to the components, but it also increased their resistance to thermal shock. During this development, the effect of unidirectional solidification on the properties of several alloys was investigated. The resulting data allows certain conclusions to be drawn regarding the factors affecting the creep and stress-rupture properties of the cast nickel-base superalloy and also its resistance to thermal shock. Detailed information was obtained on the alloys Mar-MZOO, B-1900, In 100, and TRW 1900. The composition of the alloys studied are shown in Table I. MATERIAL PREPARATION AND TESTING The conventionally cast alloys are cast as +-in.-diam bars in innoculated shell molds under conditions designed to maintain control of grain size. Unidirec-tionally solidified casting were produced in the form of 3-in.-diam ingots. Specimens from the latter were machined such that the axes of the columnar grains were parallel with the axis of the test bar, except in certain cases where the transverse properties of the material were being evaluated. The specimens were tested in an axial loading creep machine.' Temperatures were measured with thermocouples, attached just outside each end of the gage length, to assure uniform temperature along the entire specimen. Chromel/alumel thermocouples were used up to 1800"F and Pt/Pt-10 pct Rh thermocouples above 1800"F. The specimen temperature was recorded and maintained within i2"F throughout the test. Creep extensions were measured automatically with extenso-meters attached to ridges on the specimen and recorded continuously using linear variable differential transformers and multipoint recording equipment. MICROSTRUCTURE The microstructures of transverse sections of the four alloys studied are shown in Figs. 1 and 2. Fig. 1 shows optical micrographs of the alloys, both in the conventionally cast and unidirectionally solidified conditions. Each alloy displays a cored dendritic structure, a distribution of MC carbide, and the presence of the y — y' eutectic constituent.~ In the case of IN 100 and B-1900, Fig. 1 indicates that in these specimens the eutectic is degenerate. That is, it consists only of y' pools indicating that the y constituent has been solutioned during the cooling period after solidification. The major effect of unidirectional solidification on the microstructures of the alloys is a tendency to promote a more dendritic form of MC carbide and an increase in dendrite arm spacing, both effects being a result of the slower solidification rate in the unidirectional solidification technique. V, lec tron micrographs of transverse sections of the four alloys in the two cast conditions are shown in

Jan 1, 1968

By Eugene S. Machlin

A classical theory of solid solutions involving neavest-nergkbor intevactions with both central and linked-central forces between atoms has been developed. It has been found that the theory, where it can be checked quantitatively, is in ageement with experiment. The theory encompasses a description of many diverse pkenomena, such as antiphase shift structures, size effect, relative stabilities of various solutions, lattice para,neters, and order-disorder transitions. In particulav. a quantitative prediction not involving adjustable pavameters is made concevning the deviation of the Au-Cu interatonlic distance in long-range ordered (Ll,) Cu-Au I fronl the average distance based on the distances in pure gold and copper. This prediction, which is in agreement with expel-intent, has not been encompassed by any preuious theory. The theory of order-disorder is fragmentary. That is, no one theory exists that can explain the variety of qualitative phenomena observed. Further, many theories are not in good quantitative agreement with experiment. This subject has been reviewed by Muto and Takagi, Tuttman, and Oriani.3 There exists no doubt that the quasi-chemical approximation is not a complete description and that the inclusion of strain energy using macroscopic elasticity theory concepts leads to results in disagreement with experimenL4 The observation of antiphase domains and ordering systems such as Cu-Pt has led to Brillouin zone treat-ment of the order-disorder transition as opposed to the classical Ising model. The objective of this paper is to demonstrate that it is possible to develop a pairwise approximation model that can explain many of the observed order-disorder phenomena that have puzzled investigators in the past. This theory is based upon an empirical model due to ergmman' for the elastic constants of metals. This model is generalized for multicomponent systems. As will be shown, the theory yields a short-range ordering energy for the disordered solution which differs from the ordering energy calculated from the differences in energy of disordered and long-range ordered solutions. It will be demonstrated that there is no necessary correlation between heats of formation and the tendency to order or between size effect and the tendency to order. Also, the existence of antiphase domains and iso-short-range-order systems that form superlattices (Cu-Pt) is predicted on the basis of the theory. Further, the relative stability of competing superlattices is calculable from the theory. If single-crystal elastic-moduli data are available for the pure components and one superlattice then there exists but one adjustable parameter in the calculation of lattice parameters for both the disordered and ordered solid solutions. In one special case, no adjustable parameters are required and a quantitative prediction is made. For the calculation of energies and partial order, there exists but one additional adjustable parameter, the pair-exchange energy V used in the quasi-chemical approximation (or the Ising model.) However, in these calculations, much more precise values are required for the single-crystal elastic moduli than available if the quantitative uncertainties in the predicted values of the energies are to be sufficiently small. THEORY ~er~man' has developed a model with which he was able to obtain fair agreement with experiment for the relations between the elastic constants for metals. This model which we shall call Bergman's model is a linear combination of his models I and 11. In effect, Bergman, in this model, considers that each interatomic distortion is composed of two components: a classical central force distortion with an associated central force constant and what we shall call a linked-central force distortion with an associated linked central-force constant. The linked-central force distortion component obeys the constraint that the sum of such distortions over all the bonds equals zero. No constraint is imposed on the classical central force distortion component. Bergman' derives the constraint on the linked-central force distortion on the basis of application of Pauling's relation between bond distortion and bond number to metals.ga This assumption is not logically necessary, however, and the Bergman model may be taken as a mathematical model for elastic constants, e.g., a purely empirical model without a physical basis. In the present work, the method of Bergman has been applied to two-component systems (solid solutions). In place of an external strain—which would allow a calculation of the elastic constants for the two-component system—it is considered that internal interatomic distortions exist as a consequence of having three potentially unequal distortion-free interatomic distances and but one "average" interatomic distance. It is assumed that the distortion-free interatomic distances between atoms of the same element are those found in the pure element having the same undistorted crystal structure as the solid solution. The distortion-free interatomic distance between unlike atoms is in general not measurable except in the probably nonexistent

Jan 1, 1967

By Klaus Schwerdtfeger

The equilibria in the Cr-N system have been investigated in the temperature range 1100° to 1310°C by reacting chromium powder with Nz-Hz gas mixtures. The solubility of nitrogen in chromium in equilibrium with chromium subsitvide ("Cr,N") is given by Chromium subnitride is nonstoichiotnetric; its nitrogen content is always less than that corresponding to the formula CrzN. The lattice paranzeters of quenched samples have been measured; c, and a. parameters are found to increase with increasing nitrogen content. The growth rate of the subnitride layer on chromium plates was measured by a thermogravimetric technique, using a silica spring balance. The self-diffu-sivity obtained from the theoretical analysis of the parabolic rate constant is found to decrease with increasing nitrogen content, i.e., with decreasing vacancy concentration in the nitrogen sublattice. The intrinsic nitrogen diffuivity is derived from another series of rate measurements using "CrzN" plates; the intrinsic diffusivity, DN = 3.2 X 10-a cmZ sec-' at 1200 C, is found to be essentially independent of- the subnitride composition. The concentration gradient was measured in a chromium subnitride layer by the X-ray method and found to be consistent with the derived diffusivity value. TWO chromium nitrides are known to exist:' the nonstoichiometric subnitride "CrzN" and the nitride CrN. In the present work the kinetics of the formation of chromium subnitride from chromium and nitrogen have been investigated at 1100" and 1200°C. In additional experiments the relevant equilibria have been measured. The data are used to evaluate the diffusivity of nitrogen in chromium subnitride. Since chromium nitrides are often found in chromium-containing steels, the results are expected to be helpful in the interpretation of the chemical reactions between chromium steels and nitrogen. Equilibria in the Cr-N system have been determined by several investigators.2"3 The rate of nitriding of chromium was measured by Arkharov et a1 .' in ammonia in the temperature range 800" to 1200°C. The parabolic rate law was observed. Due to the undefined nitrogen activity of the ammonia atmosphere, it is dif- ficult to interpret these rate data theoretically. An additional difficulty arises from the fact that the two-layer scale consisting of CrN and "Cr2N" was formed at the temperatures below 1030°C. The rate of nitriding of technical chromium (95 pct) was measured by Zaks in nitrogen at -1 atm in the temperature range 800" to 1300°C. EXPERIMENTAL METHODS The chromium samples were reacted with Nz-HZ gas mixtures in a vertical tube furnace, wound with Pt-10 pct Rh resistance wire. The gas-tight reaction tube was of high-purity recrystallized alumina. In nitrogen solubility measurements the nitrogen content of chromium was determined by the Kjeldahl method, on samples quenched in the cold part of the furnace. The nonstoichiometry of the subnitride and the nitriding rates were measured thermogravimetrically using a sensitive (+0.1 mg) silica spring balance. For the equilibrium measurements samples of 1 g of chromium powder contained in high-purity alumina crucibles were used. In order to remove most of the oxygen and nitrogen impurities from the chromium, the samples were initially annealed in purified hydrogen until a constant weight was obtained. The chromium plates (approximate dimensions 2 by 1 by 0.08 cm) used for the rate measurements were machined from ingots obtained by arc-melting of iodine-processed chromium. According to manufacturers' specifications the purity of the chromium powder was 99.9 pct Cr and that of the iodine-processed chromium 99.99 pct Cr. Our own spectroscopic analysis of the chromium powder yielded 0.02 pct Fe, 0.05 pct Mn, 0.05 pct Si, and 0.02 pct Ti as major impurities with all the other detectable elements below 0.005 pct. The nitrogen partial pressure of the gas phase was controlled by mixing prepurified hydrogen and nitrogen with constant pressure head capillary flowmeters. Oxygen and water vapor were removed from the mixed gas by passing it through columns of platinized asbestos (450°C) and anhydrone. The gas flowed upward in the furnace with flow rates of 300 to 500 cu cm per min (25"~). Gas tightness of the furnace system was ensured by pressure checks at regular intervals. The furnace temperature was controlled electronically in the usual manner. The reported temperatures were measured with a Pt/Pt-10 pct Rh thermocouple and are estimated to be accurate within ±$C The X-ray measurements were made with a Debye-Scherrer camera and a diffractometer using chromium radiation {\Ka = 2.29092A). EQUILIBRIUM MEASUREMENTS The experimental results of the equilibrium measurements are contained in Tables I to In. Fig. 1 shows the solubility of nitrogen in solid chromium in the temperature range 1100" to 1310°C. In Figs.

Jan 1, 1968

By D. R. Parrish, T. M. Geffen, R. A. Morse, G. W. Haynes

Flow tests on small core plugs have indicated that a large amount of gas is trapped and not recovered by water flooding a gas sand. Instead of I to 15 per cent pore space, as is usually assumed, the residual gas saturation is 15 to 50 per cent pore space, and is thus of the same magnitude as residual oil after water flooding oil sands. A thorough investigation was made to ascertain that large amounts of residual gas actually remain in reservoirs after a water flood and that this condition is not merely a laboratory phenomenon. In field experiments, the amount of gas left in a watered-out gas sand was measured by use of a pressure core barrel and the residual gas saturation of two watered-out gas sands was determined by electric log evaluation. In the laboratory, an investigation was made of factors that could possibly cause the value of residual gas saturation as measured on small core plugs to differ from that in the reservoir, and the effect of these factors on the amount of residual gas saturation was studied. The factors studied include flooding rate, static pressure, temperature, sample size and saturation conditions before flooding All evidence established that a relatively high gas saturation is trapped in water flooded gas sands and that this residual gas saturation can be measured in the laboratory by tests on small core plugs. INTRODUCTION There. has been general agreement among engineers that very high recovery of gas could be obtained from natural reservoirs By water displacement. Gas recoveries of 80 to 95 per cent of the original gas in place have become the normal expectation in water drive fields. The assumption of high recovery has been based on: 1. low density and viscosity of gas compared with water; 2. the erroneous assumption that the flow relationship in a gas-liquid system where gas is the displaced phase will be the same as when it is the displacing phase. It has long been recognized that gas can flow at very low gas saturations (in the range of 1 to 15 per cent pore space) in systems where liquid is being displaced by gas. By assuming the reversibility of this process, the conclusion was reached that the residual gas saturation following water flooding of a gas reservoir would be the qame (1 to 15 per cent) as that at which gas first flowed continuously as a displacing phase. Recent laboratory relative permeability Studies have demonstrated that the flow characteristics are very different in gas-liquid systems, depending on whether gas is displacing or being displaced by, a liquid. Also, it has been shown that there is no difference between the flow characteristics of oil and water or gas and water in water wet porous rocks. The residual gas saturation that can be expected following water flooding of a gas reservoir then would be in the same range as the residual oil saturation normally expected after water flooding an oil reservoir! i.e., in the range of 15 to 50 per cent pore space, depending on the rock characteristics. Obviously, such a difference in residual gas saturation means very important differences in recoverable gas reserves from water drive reservoirs. For example, if the original gas saturation in a field were 70 per cent, and the residual gas following flooding were 35 per cent, only half of the gas in place could be recovered by complete water drive, compared to the previously expected 80 to 95 per cent. This is a situation in which complete pressure maintenance could result in very greatly reduced recovery, since straight pressure depletion recoveries from gas reservoirs can approach 80 to 90 per cent. Such a change in thinking must be based on more complete information than a series of small core tests. Hence the work reported herein was undertaken with the objective of determining whether or not residual gas saturations indicated from small core relative permeability tests at atmospheric pressure and room temperature are representative of the residual gas saturations which could be expected after water flood of natural reservoirs. A study was made both through laboratory and fields tests to determine any differences in residual saturation which might be occasioned by differences in pressure, temperature, rate of flooding, and original saturation conditions. Four separate types of laboratory experiments and two field mesurements were made in this investigation. The apparatus and testing methods of each will he discussed individually. LABORATORY EXPERIMENTS, APPARATUS AND PROCEDURE Relative Permeability Tests Steady state flow experiments Here conducted using the Penn State type apparatus. The equipment used has beer (described in a previous publication? "Irreducible" water satu-ration was established in the core' by imposing ,a capillary pressure of 45 psi before simultaneous flow of air and water

Jan 1, 1952

By G. Bhat, J. F. Libsch

lsoembrittlement curves depicting the influence of time and temperature in the range 800' to 1260°F (425' to 680°C) on the development of embrittlement in a commercial chromium alloy steel and a commercial molybdenum alloy steel are presented. Two distinct regions of embrittlement occur in the chromium alloy steel: I—at 800' to 1000°F (425' to 540°C) and 2—in the region just below the lower critical temperature. Embrittlement is most pronounced at 800' to 1000°F, decreasing very rapidly with increasing temperature above this region, only to increase again as the lower critical temperature is approached. The data suggest two distinct modes of embrittlement with possible superposition of the two modes at extended embrittling times in the temperature range 1100° to 1150°F (590' to 620°C). While the molybdenum alloy steel shows little susceptibility to embrittlement at 800' to 1000°F (425' to 540°C), considerable embrittlement may occur just below the lower critical temperature. THE subject of temper embrittlement in alloy steels has received considerable attention in the last few years. Points of view on the mechanism of embrittlement differ, however, resulting in part from the incompleteness of the data developed and in part from the speculation regarding the susceptibility of plain carbon steel to temper embrittlement. Libsch, Powers, and Bhat1 carried out short-time embrittling treatments on an AISI 1050 steel and demonstrated that hardened plain carbon steels are quite susceptible to embrittlement when tempered in the range from 850°F (455°C) to the lower critical temperature. The isoembrittlement diagram,' representing the embrittling characteristics of this steel, is reproduced in Fig. 1. It is evident from the shape of the curves shown that embrittlement in plain carbon steel increases progressively with both temperature and time in the embrittling range. A comparison of the isoembrittlement diagram for AISI 1050 steel with that presented by Jaffe and Buffum' for an SAE 3140 steel shows that up to 930°F (500°C) the isoembrittlement characteristics of the plain carbon steel are similar to those of SAE 3140 steel, although the embrittlement is much more severe in the latter steel. Above 930°F (500°C), the rate of embrittlement in the plain carbon steel increases continuously with increasing temperature; whereas, in the SAE 3140 steel, the embrittlement rapidly decreases. The influence of alloying elements upon embrittlement during tempering thus appears to cause a decrease in embrittlement above the region of maximum embrittlement, i.e., 850" to 1000°F. The question naturally arises as to what effect individual alloying elements have upon the embrittling characteristics of the plain carbon steel. Current knowledge on the influence of alloying elements on temper brittleness may be found in the review papers of Hollomon" and Woodfine. Hollo-mon," from the results of other investigators, has shown that, in general, the amount of embrittlement increases with increasing alloy content (except for molybdenum and possibly tungsten and columbium). Jaffe and Buffum," by a comparison of the embrittlement in a plain carbon steel with that of a SAE 3140 steel postulated that the presence of alloying elements in moderate amounts tends to retard the development of temper brittleness. It is difficult to determine what effect chromium has upon temper brittleness, since most of the information available has been based on the combined effect of other elements with chromium, particularly nickel and manganese. However, Wilten, and recently Jolivet and Vidal,' Vida1, and Woodfine have reported that chromium steels are temper brittle, that the embrittlement is reversible with a maximum rate of embrittlement at approximately 975°F (525"C)," and that the susceptibility increases with increasing amounts of chromium. Taber, Thorlin, and Wallacel" have found a large embrittling effect with increasing chromium content in a medium C-Mn-Ni steel. But Hultgren and Chang," from their experiments conducted on synthetically prepared ternary Fe-C-Cr alloys, could not conclude that these alloys are susceptible to temper embrittlement. However, on addition of manganese or phosphorus, these Fe-C-Cr alloys became susceptible, from which fact they concluded that the embrittlement developed in chromium-bearing Fe-C alloys is due chiefly to the presence of these elements. Considerable data are available to show that molybdenum decreases the susceptibility of steel to temper embrittlement. However, its effectiveness in preventing or decreasing embrittlement appears limited to its presence in small amounts. Vidal" has shown that a plain 2 pct Mo steel was susceptible. Hultgren and Chang" also have shown that molybdenum additions in excess of 2 pct to synthetically prepared Ni-Cr steels did not prevent embrittlement. Jolivet and Vidal' and Lea and Arnold found that molybdenum reduced temper brittleness. Lea and Arnold further stated that molybdenum decreased the rate of embrittlement rather than the total amount of embrittlement, whereas Preece and Carter" have shown that the presence of molybdenum greatly reduces the equilibrium extent of the change at a given temperature but does not appear to influence the rate of embrittlement. There appears to be very little information as to how molybdenum by itself affects the temper brittleness susceptibility of a plain carbon steel.

Jan 1, 1956

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By L. D. Hall, D. R. Mash

The paper presents the results of experiments on the anelastic. behavior of gold, as manifested by grain boundary relaxation. Two grain boundary internal friction peaks are found for 99.9998 pct Au. It is found that the peaks are associated with primary and secondary recrystallization. However, the existence of two discrete peaks cannot be explained on the basis of grain size and shape alone. It is suggested that grain boundary stability, as determined by orientation, plays a role in the observed effects. EVIDENCE for the viscous behavior of grain boundaries in metals has been presented in recent years by several investigators, based upon studies of various anelastic effects, especially internal friction. KG1 has contributed greatly to this field, having put forward a coherent body of evidence for stress relaxation by the viscous intercrystalline flow mechanism. In this connection, he has made extensive use of pure aluminum (99.991 pct) as the test material, although he has also studied other metals and alloys, including pure iron (Puron).² Rotherham, Smith, and Greenough³ have studied the internal friction of pure tin, interpreting their results in a manner similar to that of KG. In view of the importance of such studies in shedding light upon the fundamental structure and behavior of the grain boundaries in pure metals, it appears that the use of a very pure test material which is inert to its environment should provide useful information on anelastic properties and the source of such behavior in pure metals. The present work was carried out on spectrograph-ically pure, 99.9998 pct Au, free of all impurities except for a trace of silver, estimated to be present to the extent of about 0.0002 pct. The term "pure gold" will hereafter refer to this very pure material. Gold of commercial purity, 99.98 pct, was also studied to observe the effects of small amounts of impurities. A pure gold "single crystal" specimen was also tested for comparison. The variation of the internal friction and rigidity modulus as a function of temperature was determined by means of a torsion pendulum apparatus employing extremely low stress amplitudes and a frequency of vibration of the order of 1 cycle per sec. A 12 in. length of 0.031 in. (20 gage) gold wire formed the suspension element. The apparatus was similar to that described by Ke.l The test procedure and the basic requirements to be met for obtaining useful experimental data by this method have been given elsewhere.1,2 It should be made clear that in all of the experiments to be described, the internal friction and rigidity were independent of the amplitude of torsional vibration. The semilog plot of amplitude of vibration vs ordinal number of vibration was a straight line. This was carefully verified for each internal friction measurement. The linear variation shows that the internal friction was independent of stress; i.e., that the specimens were not being cold-worked during testing. The reproducibility of the internal friction curves, which were obtained by cyclic heating and cooling, indicates that the gold was unaffected by its environment during the tests. The measure of internal friction adopted in the present study is the conventional "logarithmic decrement," defined as follows: log. dec. = l/n In A0/An [I] where n is the number of cycles or vibrations; A,, the initial amplitude of vibration; and An, the amplitude after the nth cycle. When the logarithmic decrement is small, the shear modulus, G, of the wire is proportional to the square of the frequency of vibration provided the length and radius of the wire are kept constant. A plot of frequency squared vs temperature gives the following ratio:' This expresses the fraction of the stress which has not been relaxed at a given temperature. Gr and Gv are the relaxed and unrelaxed moduli, respectively. The frequency of vibration in the polycrys-talline specimen is fp, and the frequency of vibration of a single crystal is f8. This latter quantity is obtained simply by extrapolating the linear, low temperature portion of the curve of frequency squared vs temperature for the polycrystalline specimens. The theory of viscous grain boundary stress relaxation as demonstrated by the anelastic behavior of metals has been discussed in detail by Zener4 and need not be reproduced here. Experimental Results Initial measurements of the internal friction of pure gold were carried out on specimens which had been drawn with no intermediate annealing, resulting in a material which had undergone approximately 99 pct reduction of area in final processing. Annealing was then carried out at successively higher temperatures starting at 400°F for 1 hr and proceeding in this manner to as high as 1600°F in 100°F intervals. After each annealing treatment an internal friction and rigidity vs temperature curve was obtained over the range from room temperature to the particular annealing temperature. The resulting internal friction curves did not exhibit well defined maxima (peaks), but rather several fairly flat

Jan 1, 1954

By C. E. Armantrout, J. A. Rowland, D. F. Walsh

THE close-packed-hexagonal structure of mag-J- nesium is converted to a ductile and malleable body-centered-cubic lattice by the addition of lithium in excess of 10 pct. Further, the density of magnesium or magnesium-base alloys is decreased by additions of lithium. The practical possibilities of such alloys as a basis for uniquely light, malleable, and ductile structural materials were pointed out by Dean in 1944' and by Hume-Rothery in 1945.2 It was apparent to these investigators, however, that more complex compositions would be required if strengths sufficient for structural applications were to be developed in these alloys. In a search for strengthening additions, various investigators w have examined a number of the ternary and more complex alloys containing magnesium and lithium. An investigation of the fundamental characteristics of these alloys was undertaken by the Bureau of Mines. The investigation was initiated with a study of the magnesium-rich corner of the equilibrium diagram for the ternary system, Mg-Li-Al. The following data from published investigations of Mg-Li-A1 alloys were available: 1—a description of isothermal sections at 20" and 400°C through the Mg-Li-A1 constitution diagram by F. I. Shamrai;' 2—a diagram by P. D. Frost et al." showing approximate phase relationships at 700°F for a number of the Mg-Li-A1 alloys; and 3—diagrams showing the constitution at 500" and 700°F for the Mg-Li-A1 alloy system published by A. Jones et al.' Where compositions and temperatures permit comparison, these diagrams show disagreement. The 700°F isotherms of Frost and Jones differ only in the placement of the phase boundaries. But Sham-rai's 400°C (752°F) isotherm shows a variation in phases as well as in phase boundaries. Although rigid comparison of these different isothermal sections might not be justifiable, it seems impossible to reconcile Shamrai's construction with the isotherms of Frost or Jones. The isothermal sections presented in this paper were prepared to determine compositions which might be suitable for age hardening and to develop the general slope and placement of the various phase boundaries in the magnesium-rich corner of the diagram. Sections at 375", 200°, and 100°C were selected for investigation. In constructing these sections, the solubility of aluminum in magnesium, as reported by W. L. Fink and L. A. Willey Vn 1948, was used at the binary Mg-A1 boundary and the solubility of lithium in magnesium was obtained from the equilibrium diagram for that system as reported by G. F. Sager and B. J. Nelson" in the same year. The solubility of magnesium in lithium was determined experimentally and conforms in general to data reported by P. Saldau and F. Shamrai." Parameters for AlLi and MgI7A1, were taken from American Society for Testing Materials X-ray diffraction data cards. Experimental Procedures Although the isothermal sections presented in this paper are not unusually complex, the experimental techniques involved in their construction are made extremely difficult by the relatively high vapor pressure of lithium and the great chemical activity of both magnesium and lithium. Because of these characteristics, which make precise control of the composition of equilibrium-treated filings practically impossible, the disappearing phase method was used in preference to the parametric method in conjunction with metallographic studies. The alloys used in this investigation were melted and cast in an atmosphere of helium using a tilting-type furnace which enclosed a steel crucible and mold in a single unit. Each portion of the charge (500 to 600 g) was cleaned carefully just before placing it in the crucible; and the charge, crucible, and entire melting apparatus were evacuated and then washed with grade A helium while preheating to approximately 100°C. The alloys were melted and chill cast in an atmosphere of helium. Alloys prepared in this way were relatively free from inclusions and a fluxing treatment was considered unnecessary. The cylindrical ingots obtained were scalped and then reduced 96 pct in area by direct extrusion, yielding % in. diam rod. Sections of the rod, approximately 3 in. long, were given equilibrium heat treatments and then sampled for metallographic examination, X-ray diffraction study, and chemical analysis. The surface of each equilibrium-treated rod was machined to a depth sufficient to insure removal of contaminated material before samples for chemical analysis or X-ray diffraction study were obtained, and all decisions on microstructure were based on the examination of the central portion of the metallographic specimen. All specimens homogenized at 375°C were analyzed after this equilibrium heat treatment. When the composition of an alloy placed it in a critical area of the 200" or 100°C isothermal section, a check chemical analysis was made on a sample taken from the alloy specimen as-heat-treated at the particular temperature. Standard chemical procedures of gravimetric analysis were used in the determination of magnesium and aluminum; lithium, potassium, and sodium were determined by flame photometer methods

Jan 1, 1956