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By L. C. Brown, J. S. Kirkaldy

AS part of a program to investigate the diffusive properties of dilute ternary austenites, we have made a determination of the effects of cobalt on the activity of carbon in y iron. Samples of pure iron and Fe-Co alloys were equilibrated at 1000°C in controlled CO-C02 atmospheres, following the procedure of R. P. smith.' The 0.010-in.-thick samples were analyzed for carbon by microcombustion analysis2 to give a set of isoactivity curves. The latter were converted to activity-coefficient (standard state at infinite dilution) plots by combination with Smith's data' for the activity of carbon in pure iron measured in a CO-C02 mixture. Table I shows the composition of the base alloys used, while Fig. 1 shows the experimental results superimposed on a set of curves generated by the relation In the notation of Wagner,' the interaction parameter is the second coefficient on the right, Eq. [I] adequately correlates the experimental points for those alloys which were prepared from electrolytic iron by arc-melting (2,4, and 7 pct Co). The results for the 10 pct Co alloy (supplied by Crucible Steel Co.) do not correlate with the others. In fact, the experimental points for this alloy correspond to an interaction parameter of It is possible that the interaction parameter is a function of concentration for large cobalt additions, but we are inclined to attribute the discrepancy to the presence of a significant amount of aluminum added to this alloy for deoxidation purposes (Table I). Preliminary measurements for the system Fe-C-A1 have indicated an interaction parameter of Which implies that the effect of aluminum in solution on the carbon activity is sixty times greater than the effect of an equal weight percentage of cobalt. These observations cast some doubt on the precision of the results of Chandhok, Hirth, and Dulis who used this same 10 pct alloy for their experiments, obtaining an interaction parameter of E = 2.2. There is considerable doubt as to the activity of a plane Fe-C system. Using a CH4-Ha mixture, Smith obtains cg = 6.1 for the effect of carbon on the activity of carbon in austenite, rather than the value of 8.9 given in Eq. [I]. The use of CHa-Ha mixtures has recently been questioned by Kaufman, Radcliff, and cohens who state that there is some possibility that other hydrocarbons are formed. Fortunately, the determination of the interaction parameter is not sensitive to the coefficient of Nc. For example, using the CHI-H2 results we obtain a value which is almost the same as that obtained using the CO-CO, results. The authors wish to thank Mr. E. J. Dulis of the Crucible Steel Co. of America for supplying us with samples of the 10 pct Co alloy used in their original work. Financial assistance from the American Iron and Steel Institute is gratefully acknowledged.

Jan 1, 1963

By Robert E. Thurmond, E. D. Spaulding, Walter E. Heinrichs

DISCOVERY of a commercial ore deposit has resulted from a program emphasizing geophysical techniques and concentrating upon exploration of alluvial-covered areas. United Geophysical Co. selected these areas as offering the best possibility of success, for here the surface evidence of ore deposits has been hidden from the eyes of prospector and geologist alike. Pima mining district, Pima County, Arizona, was selected for initial exploration. The project was successful in that a commercial ore deposit was discovered and proved through drilling and extensive underground development.

Jan 2, 1954

By Reginald S. Dean

Manganous oxide is readily soluble in concentrated ammonia solutions containing ammonium salts. Lixiviants of ammonia and ammonium carbamate permit ready extraction of manganese from reduced ores and the manganese in such solutions may be precipitated by heating to transform the carbamate to carbonate. THE widespread occurrence of manganese in low grade oxide and carbonate ores not amenable to mechanical concentration has led to extensive investigations of hydrometallurgical methods for producing a pure manganese compound suitable for further treatment. Manganese carbonate is the preferable compound. This product when fully crystalline and of not too fine crystal size is easily filtrable and stable in air. It can be converted to other compounds such as the oxides by heating in air or can be reacted with acids for producing salts. A useful hydrometallurgical process must produce relatively concentrated solutions that can be purified easily, reagents must be cyclically used, and heat requirements must be small. Neither the ammonium sulphate nor sulphur dioxide leaching processes that have been tested extensively fulfill these requirements. Other heretofore proposed processes have obvious limitations and have not been tried on a large scale. The present process is based on the discovery by the writer of a new group of aqueous manganese-ammonia complex solutions highly concentrated in ammonia, which permit rapid solution of manganous oxide to concentrations of 80 to 100 g Mn per liter and from which a fully crystalline, easily filtrable manganese carbonate is precipitated by the addition of carbon dioxide and partial ammonia removal. Although the process may be carried out with many ammonium salts, commercial advantages dictate the use of ammonium carbamate, which is obtained when CO2 is passed into concentrated aqueous solutions of ammonia. If the carbamate is used, the only reagents, ammonia and CO2, are volatile and may therefore be recovered from solutions and residues by heating, thus eliminating washing and extensive evaporation. Impurities are controlled easily as most metal oxides are either insoluble in the lixiviant or fail to precipitate with the manganese carbonate. Others are controlled by sulphide addition. The process has been tested extensively on a small scale on a wide variety of ores, including Three Kids, Artillery Peak, Cuyuna, and Chamberlain, as repre-

Jan 1, 1953

By Reginald S. Dean

Manganous oxide is readily soluble in concentrated ammonia solutions containing ammonium salts. Lixiviants of ammonia and ammonium carbamate permit ready extraction of manganese from reduced ores and the manganese in such solutions may be precipitated by heating to transform the carbamate to carbonate. THE widespread occurrence of manganese in low grade oxide and carbonate ores not amenable to mechanical concentration has led to extensive investigations of hydrometallurgical methods for producing a pure manganese compound suitable for further treatment. Manganese carbonate is the preferable compound. This product when fully crystalline and of not too fine crystal size is easily filtrable and stable in air. It can be converted to other compounds such as the oxides by heating in air or can be reacted with acids for producing salts. A useful hydrometallurgical process must produce relatively concentrated solutions that can be purified easily, reagents must be cyclically used, and heat requirements must be small. Neither the ammonium sulphate nor sulphur dioxide leaching processes that have been tested extensively fulfill these requirements. Other heretofore proposed processes have obvious limitations and have not been tried on a large scale. The present process is based on the discovery by the writer of a new group of aqueous manganese-ammonia complex solutions highly concentrated in ammonia, which permit rapid solution of manganous oxide to concentrations of 80 to 100 g Mn per liter and from which a fully crystalline, easily filtrable manganese carbonate is precipitated by the addition of carbon dioxide and partial ammonia removal. Although the process may be carried out with many ammonium salts, commercial advantages dictate the use of ammonium carbamate, which is obtained when CO2 is passed into concentrated aqueous solutions of ammonia. If the carbamate is used, the only reagents, ammonia and CO2, are volatile and may therefore be recovered from solutions and residues by heating, thus eliminating washing and extensive evaporation. Impurities are controlled easily as most metal oxides are either insoluble in the lixiviant or fail to precipitate with the manganese carbonate. Others are controlled by sulphide addition. The process has been tested extensively on a small scale on a wide variety of ores, including Three Kids, Artillery Peak, Cuyuna, and Chamberlain, as repre-

Jan 1, 1953

THE metal iron has physical and chemical properties which are somewhat different from those of steels, but a knowledge of the pure metal is a useful starting point in studying the behavior of steels. Solid iron exists in two different crystalline forms, called alpha (a) and gamma (?) iron, the former being the ordinary form at room temperature. When heated above the "A2 point," 1400°F. (760°C.), the metal becomes non-magnetic, and at the "As point," 1670°F. (910°C.), it undergoes a change in crystalline form to become gamma iron. In the range 1400 to 1670°F., it is sometimes called beta (0) iron to distinguish it from the magnetic alpha, but the two are identical in crystal structure. When gamma iron is further heated to 2550°F. (1400°C.), it changes into delta (d) iron, which is identical with beta or non-magnetic alpha iron. Pure iron melts (in a hydrogen atmosphere) at 2795°F. (1535°C.); the melting point is generally lowered by alloys or impurities. PROPERTIES OF IRON AT HIGH TEMPERATURES Many of the properties of iron undergo abrupt changes at the transition temperatures. (1) For example, in heating through the As point a sudden shrinkage in volume occurs. Similarly, melting is attended by sharp physical changes such as an increase in volume. Table 27 contains a summary of the measured physical properties of pure iron at several temperatures. Usually the properties change smoothly within the range of stability of a given form, but this is not always the case. For example, the specific heat reaches a sharp maximum at the A2 point although no transformation occurs. Solvent Powers of Liquid Iron. Liquid iron is capable of dissolving most of the other metals and many nonmetallic elements as well. Of the metals which are liquid at the melting point of iron only lead, silver, and bismuth refuse to dissolve to an appreciable extent. The non-metals presumably dissolve by virtue of the formation of an iron compound; for example, sulphur is thought to dissolve as the compound FeS. However, there is no satisfactory method of proving that this

Jan 1, 1944

By John M. Karpinski, David S. Cahn

A new device based on a constant rate of loading has been developed for the compression testing of green and dry pellets. This device has a lower test variation for green pellets than the existing constant deformation rate tester. While the test variations for dry pellets are similar for both types of machine, the new tester is sensitive enough to measure dry pellet deformations of 15 µ in. for cyclic loading studies. In the study discussed here, the compressive load at which a pellet breaks proved to be a normally distributed random variable, and the load-deformation relationship was found to be linear for dry pellets but not for green pellets. The paper emphasizes the need for a standardized test procedure throughout the industry. For many years the green and dry compressive strengths of pellets have been considered as possible criteria of pellet performance during induration. Little attention, however, has been given to standardizing the unfired pellet compressive strength test or to determining the characteristics of this test. The purpose of this study was to compare the constant deformation rate test with constant loading rate

Jan 1, 1969

By K. A. Grange, W. S. Holt, E. T. Tkac

Quantitative knowledge of the time clement involved in austenite transformation in a particular steel provides a sound basis for understanding and planning heat-treatment. Such knowledge is conveniently obtained by measurement of austenite transformation as it occurs at each of a series of temperature levels. The results of these measurements usually are summarized in the form of the now familiar isothermal transformation diagram (I-T diagram, TTT diagram, or S-curve). Although a considerable number of such diagrams already have appeared in the literature, there remain many compositions of commercial importance for which no I-T diagram is available. The diagram for many such steels may be predicted from published data with sufficient accuracy for most practical purposes, but for others no satisfactory prediction can be made because the effect on austenite transformation of one or more of the important alloying elements present is not well enough known. Such a steel is Nitralloy, Type 13s-Modified, which, containing about 1.25 per cent aluminum, differs from any whose I-T diagram has been published. This paper presents results of a study of the isothermal transformation behavior of a sample from a commercial heat of this aluminum-chromium-molybdenum steel, together with pertinent supplementary data including the equilibrium transformation temperatures (Aeaand Ae,), the temperature range of martensite formation, and the end-quench harden-ability. These data are directly applicable to the hcat-treatment of this type of steel and are of interest in revealing some of the fundamental effects of aluminum as an alloying element in steel. Material All specimens were prepared from a 1 1/4 i-in. diam bar forged from a 5 by 5-in. billet from a commercial heat made in an electric arc furnace. The composition of the bar was; C, 0.41 per cent: AIn, 0.57: P, 0.016: S, 0.005: Si, 0.24: Ni, 0.17: Cr, I.j7: Mo, 0.36: All 1.26. The forged bar was normalized from r750°F (95s°C) and then tempered for one hour at rzoo°F (650°C), this tempering treatment having been given to facilitate the machining of specimens. Equilibrium Transformation Temperatures In hypoeutectoid steel the minimum temperature at which austenite is completely stable, Aep, and the maximum temperature at which austenite is completely unstable, Ael, are of great significance in heat-treatment. Since these temperatures are dependent upon com-

Jan 1, 1948

By W. S. Holt, K. A. Grange, E. T. Tkac

Quantitative knowledge of the time clement involved in austenite transformation in a particular steel provides a sound basis for understanding and planning heat-treatment. Such knowledge is conveniently obtained by measurement of austenite transformation as it occurs at each of a series of temperature levels. The results of these measurements usually are summarized in the form of the now familiar isothermal transformation diagram (I-T diagram, TTT diagram, or S-curve). Although a considerable number of such diagrams already have appeared in the literature, there remain many compositions of commercial importance for which no I-T diagram is available. The diagram for many such steels may be predicted from published data with sufficient accuracy for most practical purposes, but for others no satisfactory prediction can be made because the effect on austenite transformation of one or more of the important alloying elements present is not well enough known. Such a steel is Nitralloy, Type 13s-Modified, which, containing about 1.25 per cent aluminum, differs from any whose I-T diagram has been published. This paper presents results of a study of the isothermal transformation behavior of a sample from a commercial heat of this aluminum-chromium-molybdenum steel, together with pertinent supplementary data including the equilibrium transformation temperatures (Aeaand Ae,), the temperature range of martensite formation, and the end-quench harden-ability. These data are directly applicable to the hcat-treatment of this type of steel and are of interest in revealing some of the fundamental effects of aluminum as an alloying element in steel. Material All specimens were prepared from a 1 1/4 i-in. diam bar forged from a 5 by 5-in. billet from a commercial heat made in an electric arc furnace. The composition of the bar was; C, 0.41 per cent: AIn, 0.57: P, 0.016: S, 0.005: Si, 0.24: Ni, 0.17: Cr, I.j7: Mo, 0.36: All 1.26. The forged bar was normalized from r750°F (95s°C) and then tempered for one hour at rzoo°F (650°C), this tempering treatment having been given to facilitate the machining of specimens. Equilibrium Transformation Temperatures In hypoeutectoid steel the minimum temperature at which austenite is completely stable, Aep, and the maximum temperature at which austenite is completely unstable, Ael, are of great significance in heat-treatment. Since these temperatures are dependent upon com-

Jan 1, 1948

By Knut Conradsen

In the study 208 heavy mineral concentrates (pan samples) from Jameson Land, East Greenland, are considered. Each concentrate has been analysed (by spectroscopy) for the content of (approx.) 25 elements. Furthermore the exact sampling position and the geological characteristics of the environment have been registered. In the study is shown how different multivariate methods combined with geological knowledge of the area can be used in the interpretation and classification of the data. Special emphasis is put on the problem of finding reliable expressions for the background level of the element concentrations in the area. This is done by means of severel discrimination procedures. The other main subject is a demonstration of the applicability of isoscore maps - originating from factor analyses - in the evaluation of the co-variability of the data, and thus give another way of classifying the individual samples according to the content of different elements.

Jan 1, 1977

By A. A. Dor

Of the numerous methods that have been tested or considered for the beneficiation of low-grade iron ores, this article deals only with proven flowsheets that are adopted in plants in operation or which have been reliably pilot-plant tested. Several recommended layouts are described and discussed. They illustrate recent trends and embody improvements and new features that have resulted from the experience acquired in the operation of the plants already in service. They have been developed, in the last few years, in the course of designing several iron ore beneficiation plants of various types and sizes. Some of the design features in the layouts which are submitted represent, in some respects, personal views and may not meet the full approval of others in this field. It is hoped that this presentation will provide an opportunity for constructive discussion of the problems involved and of suitable solutions.

Jan 6, 1962

With a mine output as high as 5000 tpd and mill capacity of 7000 tpd, the uranium mining and milling complex owned and operated by Kerr-McGee Nuclear Corp. in the Ambrosia Lake area is the largest in the U.S. and is likely to remain so for some time. Next year, Kerr- McGee expects to have in production another mine in Section 19 of the Ambrosia area-and will begin ore production in 1976 at its new $15-million mine at Church Rock, located northeast of Gallup, N. M., where the company has already completed the shaft work and is in the early stages of project development. Ore from Church Rock will be transported to the company's facilities at Ambrosia Lake for processing. Kerr-McGee's existing eight mines in Ambrosia Lake go to depths of about 800 to 1500 ft to tap the various horizons of uranium-bearing sands in the Westwater Canyon of the Morrison formation.

Jan 8, 1974

By G. E. Johnson

The problem of efficient reclamation of zinc base die cast scrap became interesting early in 1930. Die Cast Metal, as referred to in this paper, is a zinc base alloy with various proportions of aluminum, copper, magnesium, antimony and tin. Many attempts were made to work out some means of reclaiming the discarded die cast metal for re-use as new die cast metal. Difficulties in such reclamation were attributable to contamination by lead and tin from solder, chromium and nickel from electroplated coatings, and iron from iron inserts. This paper relates the experiments that led to the development of a specialized muffle furnace for the treatment of zinc base die cast scrap for the production of zinc oxide and zinc, and describes the development of the muffle furnace and the equipment now used commercially for these purposes. The Eagle-Picher Co. acquired all patent rights' for these developments from the International Smelting and Refining Co. in connection with their purchase of the East Chicago Plant. Zinc Base Serap Situation About 1935, the die cast scrap situation became increasingly acute for scrap dealers. This scrap was accumulating from dismantling automobiles and household appliances which contained die cast parts. Efforts to find an outlet for this type of scrap were intensified. The International Smelting and Refining Co. began to study the possibilities of a commercial process for the recovery of values from die cast scrap. At that time most of the die cast metal reclaimed was melted down in small kettles of from one to five tons capacity, the iron inserts being removed by skimming. The dross was skimmed off and disposed of as a zinc dross. The drossed metal was cast into slabs and was given the trade name "die cast slabs.". Distribution of the products produced by melting die cast scrap in kettles is shown in Table 1. American Process Experiments A method considered for the production of zinc oxide from die cast scrap was an adaption of the standard American Process of zinc oxide manufacture. Thus some die cast scrap was mixed with oxidized zinc materials and charged to Wetherill grates. The zinc oxidized to zinc oxide but, while the aluminum and copper largely remained in the residue, the color of the zinc oxide produced was impaired by copper contamination. As the proportion of die cast scrap was increased, liquation took place; that is, the metal trickled through the charge then solidified in the openings of the grates. French Process Experiments Several hundred tons of die cast scrap were purchased for test purposes and converted into die cast slabs. These slabs were charged into a French Process (horizontal retort) zinc oxide furnace with some electrolytic zinc. A satisfactory grade of zinc oxide was not produced. Distillation in Belgian Retorts It was then decided that, rather than attempt to use scrap die cast metal or scrap zinc for the production of zinc oxide, it would be advisable to redistill the die cast slab metal in a Belgian retort furnace. The opportunity to do so was provided by the closing of the zinc smelter of the Illinois Zinc Co. at Peru, Ill. Arrangements were made for the operation of a Belgian retort furnace for such redistillation purposes. The results of this experiment are summarized in Table 2.

Jan 1, 1950

By P. Niessen, W. C. Winegard, C. J. Beingessner

DURING the last 10 years, several grain-growth studies have been made using zone-refined metals with controlled amounts of solute to elucidate the interaction of solute with moving boundaries. In all these studies, it was more or less implicitly assumed that the alloys used were, after recrystallization and grain growth, homogeneous within the grains with respect to solute and lattice defects. This note deals with observations made on microstructures originating from solidification of dilute alloys and from grain growth. Briefly, the experimental procedure used in these studies was the following: zone-refined cadmium and master alloys were melted and cast in Pyrex under vacuum to produce bars 14 mm in diam and about 150 mm long. These bars were cut into 8-mm-thick slices which were mechanically and chemically polished. The specimens were then deformed 30 pct in compression and given a 1-week anneal at 260°C in argon. After this anneal, a second deformation produced completely recrystallized samples 4 mm thick. The time-temperature controlled anneals were carried out in a bath of silicone oil. After the grain-growth anneal, the specimens were polished in Gil-man's' solution (33 g CrOs, 6 g NazSO, in 100 ml of water). Several etches were used depending on the alloy investigated, but mostly a mixture of concentrated HC1 and HNOj (98:2 vol) was employed. In all the alloys examined, the ease with which substructures could be revealed depended strongly on the crystallographic orientation of the surfaces of the grains. However, very frequently the microstructures to be discussed here etched up over broad areas comprising several grains. Fig. 1 is a micrograph of a Cd-0.05 at. pct Mg alloy annealed for 100 sec at 270°C. Different substructures are seen in this photograph. A denotes the now existing grain boundaries. The well-defined lines and points marked B are the remains of a solidification substructure. The lines are boundaries between cell colonies, and the points are nodes located on regular two-dimensional cells. This cellular structure has the same appearance as that found by weinberg2 for rapidly quenched Zn-Au alloys. The "ghost boundaries", marked C, are very similar in appearance to a grain boundary array in a polycrystalline sample. Repeated polishing and etching showed that all the substructures observed were three-dimensional. To date, the ghost boundaries have been clearly observed in all samples containing 0.005, 0.01, 0.05, and 1 at. pct Mg, and in samples containing 0.01 at. pct Zn. Attempts to outline these ghost boundaries in cadmium alloys containing 0.01 at. pct Ag and Au were only partially successful. In these alloys, parallel lines, having a resemblance to the ghost boundaries in the Cd-Mg and Cd-Zn alloys, were observed, but it was not possible to obtain complete arrays of ghost boundaries which extended over several grains. It is possible that a different etch than that presently employed would reveal the ghost boundaries in the Cd-Au and Cd-Ag alloys as clearly as in the Cd-Zn and Cd-Mg alloys. A close examination of the ghost structure showed that it consisted of linear etch-pit arrays, Fig. 2. The ghost boundaries were resolvable even in grains which showed over-all faceting due to the etching, as seen in the corner of Fig. 2. The general appearance of the ghost structure suggests that it originated during grain growth. This is supported by the observation that the mesh width in the ghost-boundary array generally increased with increasing final grain size. To test whether the ghost structure was formed during the long homogenizing anneal or during the grain-growth anneal, some as-cast samples were deformed and given a grain-growth anneal. This anneal was terminated by air cooling or

Jan 1, 1967

By F. Keller, E. H. Dix, R. W. Graham

Aluminum alloys containing relatively small amounts of magnesium and silicon are of commercial interest because they are readily workable in the annealed form and may be hardened and strengthened by suitable heat treatment. An intermediate temper can be produced in these alloys by quenching after a Solution heat treatment and the alloy in this condition can be formed easily. Artificial aging is required to obtain the maximum mechanical properties but this aging does not cause distortion nor require elaborate heat-treating equipment. The hardening of the alloys after quenching is attributable in part to the retention of the compound Mg²Si in solid solution, while the maximum hardness obtained by subsequent artificial aging is attributed to the fact that the solid solubility of the compound Mg²Si in aluminum decreases with decreasing temperature. Considering the importance of aluminum alloys susceptible to heat treatment, it is surprising how few fundamental investigations have been carried out on the aluminum-magnesium silicide alloys. This paper deals principally with the solid solubility relations of the compound Mg2Si in aluminum and is the sixth paper of a series1 from the laboratories of the Aluminum Co. of America reporting the results of investigations of equilibrium relations in aluminum-base alloys made from high-purity aluminum."

Jan 1, 1931

By Jim Douglas, H. H. Rachford, D. W. Peaceman

The problem of unsteady-state gas flow through porous media has been solved numerically only for the case of linear or radially symmetric reservoirs. A recently introduced numerical method for solving the unsteady-state heat flow equation in two dimensions is applied to the calculation of the depletion of a square region containing a perfect gas. Solutions are presented in graphical form for various values of dimensionless parameters. The solutions are compared with published .solutions for radial reservoirs. I NTR ODUCTION The problem of unsteady-state flow of gas through porous media gives rise to a second-order non-linear partial differential equation for which no analytical solution has been found. Numerical approximations to solutions of the gas flow problem have been obtained by the stepwise solution of an associated difference equation1,2. However, the methods so far developed have required that the reservoir be either linear or radially symmetric. This restriction in shape has been necessary so that only two independent variables be considered, namely, one distance variable and time. In order to deal with reservoirs having more realistic shapes, it is necessary to develop numerical procedures for the solution of the gas flow problem involving two distance variables. A numerical procedure, denoted as the alternating-direction implicit method, for the solution of the heat-flow problem in two dimensions has recently been introduced" By the use of this procedure, approximate solutions have been obtained for heat-flow problems in a square8, and in regions having various non-rectangular boundariesa. Because of the similarity between the equation for heat conduction in solids and the equation for gas flow in porous media, it is reasonable to expect that the alternating-direction implicit method should also be useful for solving the gas flow problem in various two-dimensional regions. Solutions have been calculated for the simplest two-dimensional region, a square reservoir with a single well in the center. While reservoirs of such simple geometry seldom, if ever, exist, the solution of this problem is of some practical importance because it is also the solution of another problem, that of determining the depletion history about an individual well in an infinite uniform reservoir containing wells spaced throughout on a square lattice and producing equally from each well. Finally, it is of interest to compare solutions for a square reservoir with those for a circular reservoir and to determine the effect of the shape of the boundary for that particular case. METHOD OF CALCULATION Basic Differential Equation By combining the equation of continuity, the perfect gas law,

Jan 1, 1956

By John W. Langley

The unsatisfactory character of most, if not all, of the processes for the direct determination of alumina in the presence of iron and phosphoric acid, and the sharpness with which both the iron and phosqhoric acid can be determined, have led chemists to rely mainly

Jan 1, 1892

By M. Hoch

Equations are derived from statistical considerations to represent the activities of each component of an interstitial solution, and of a compound with a wide homogeneity range as a function of composition and temperature, based on the interaction energies between the various components, Eij. The equations are checked on the binary systems Fe-C, Ta-H, and Y-H, the ternary systems Ti-O-H, liquid Fe-C-0, and the compounds TiO, MnO, COO, and YH,. In all cases the present model represents the experimental data well. THE aim of this paper is to derive from statistical considerations the thermodynamic behavior of non-substitutional solid solutions. "Nonsubstitutional solid solution" means either an interstitial solid solution (carbon in iron, oxygen and hydrogen in hexagonal and bcc titanium, and so forth) or deviation from stoichiornetry in compounds (introduction of vacancies—removal of atoms in one or both lattice sites of compounds FeO, MnO, TiO, NbO, YH2). wagnerl and Fowler and Guggenheim considered the theory of compounds with small deviation from stoichiometry; Anderson includes larger deviations from stoichiometry, the defect being present in one component only, as vacancy and interstitial. Rees considers only vacancies in one of the components and introduces various kinds of sites for the component where the defect occurs; the various sites interact with different energies, thus giving isotherms with two or more plateaus. Both Rees and Anderson are mainly occupied in determining the limits of two-phase regions, and the defect interaction energy is determined from the critical point. Darken and Gurry5 gave a brief treatment of carbon solution in iron; Speiser and spretnak calculated the configurational entropy for binary interstitial solid solutions by assuming that each interstitial atom in the solution excludes a certain number of neighboring interstitial sites from occupancy. Use will be made of this concept later. Hoch et al treated transition metal oxides of the NaCl-type structure, and also oxygen solution in titanium.' The main aim was to determine the behavior of the activity of one of the components as a function of the composition in the single-phase region. In the present paper, the various interaction energies are discussed in detail and the similarity between interstitial solid solutions and deviation from stoichiometry in ionic compounds is shown. Both types of systems have in common that at least on one kind of lattice site only one kind of atom occurs; this gives a fixed frame to the system, permitting a much easier statistical treatment than for the substitu-tional solid solutions. (The theory is also applied to ternary systems.) The difference between an interstitial solution and deviation from stoichiometry can be explained as follows. In an interstitial solution in the pure or standard state the host atom or host structure is present alone and all the interstitial sites which are going to be filled when the interstitial atom is introduced are empty. The interstitial solution is now created by introducing atoms into this empty lattice. In the deviation from stoichiometry, both kinds of lattice sites are already occupied in a special fashion (all lattice sites occupied, or the same fraction of lattice sites empty, or one kind completely filled, the other only two-thirds). Deviation from stoichiometry removes atoms from lattice sites, adds them, or removes atoms from one kind of lattice site and introduces them on the other lattice site. Though both cases (interstitial solution and deviation from stoichiometry) lead almost to the same equations, they are treated separately. The treatment given below corresponds to the "regular solution"10 treatment of substitutional solid solutions. Speiser and spretnak's6 treatment is similar to the athermal solution in the substitutional use. a) INTERSTITIAL SOLID SOLUTIONS Theory. It will be assumed that there are N lat-tice sites occupied by the host atom (denoted by 1). Corresponding to those N lattice sites there are N octahedral and EN tetrahedral interstitial sites. If only one kind of interstitial atom is added, this in-

Jan 1, 1964

By D. K. Deardorff, Haruo Kato

D. K. Deardorff and Haruo Kato (U. S. Bureau of Mines)—We wish to refute the 1875" 20°C value that Giessen, et al., report as the transformation temperature of hafnium. Although these authors state that their work along this line will be reported later, we can't leave their value undiscussed, for we believe it to be 125°C too high. Our value of 1750° 20°C, which the authors mention, has been substantiated in our laboratories by the use of three other methods. The first method of substantiation was by heating and cooling curves using a hafnium/tungsten thermocouple, the couple having first been calibrated against a t/Pt-10 pct Rh couple. The second method was by quenching and metallography of dilute Hf-Ta alloys. The third cussion, it may be pointed out that the observations of Rogers referred to large unidirectional strains where the internal cracks or voids appeared only after a strain of 32 pct or more. On the contrary the internal fissures observed, as a result of fatigue cycling, occurred for a total extension of some 5 pct and furthermore followed the directions of the slip zones. Finally, it is not our contention, as implied in Dr. Alden's last paragraph, that the tensile stress is an important factor in crack propagation. Indeed, in connection with the reference to the companion report, special note is made of the fact that "Deformation was apparently concentrated in grains which have a slip plane nearly perpendicular to the specimen axis and thus near the plane of maximum applied shear." This dependence of the growth of fissures on the orientation of the slip planes with respect to the direction of maximum applied shear is clearly shown in work on the torsional cycling of single crystals which has been submitted for publication. method was by heating and cooling curves with W/W-26 pct Re thermocouple. Counting the original resistometric method, four different methods have yielded 1750" 20°C as the transformation temperature of hafnium. All our work on determination of the hafnium transformation temperature has shown that the specimen under test must be quickly heated to and through the transformation temperature if the lowest possible transformation value is to be determined; otherwise a higher value not representative of pure hafnium will result. Speed was emphasized in all methods. In our resistometric work the corresponding voltage, amperage, and temperature readings were taken quickly and the transformation temperature was usually reached within 5 min total heating time. In the thermal analysis work involving Hf/W or W/W-26 pct Re thermocouples the transformation temperature was attained within three minutes total heating time, this time being less because the two variables were

Jan 1, 1963

By C. S. Barrett, D. F. Clifton

THE transformation that occurs in lithium and its solid solutions containing magnesium1,2 is similar in many respects to other diffusionless transformations of the martensitic type. This general similarity makes it desirable to investigate the transformation curves in detail. The current interest in the phenomenon of stabilization in martensitic transformations has created a need for a careful appraisal of possible stabilization effects in both cooling and heating transformations in lithium alloys. The effect of prior heat treatment on the temperature at which transformation begins and the effect of various temperature cycles in partially transformed alloys also merit attention. Limited data on some of these features were presented previously,' but the present studies have been made with improved apparatus, in which erratic fluctuations were smaller than in the earlier work, and include many independent determinations of certain critical observations. Material and Methods Geiger counter X-ray spectrometers were used: a Norelco instrument, original model, and a General Electric XRD-3. The low-temperature specimen holder has been described elsewhere." Specimens 10 mm in diam and 1.5 mm thick were held in firm contact with a copper block which was attached to the lower end of a stainless steel tube that extended up to a reservoir of liquid nitrogen. A heating coil on the tube permitted a controlled temperature gradient along the tube, so that desired temperatures and rates of heating and cooling could be obtained by controlling the heating current. The specimen was surrounded by an atmosphere of evaporated nitrogen in an insulated chamber having double cellophane windows. The temperature of the specimen was read by a thermocouple imbedded in it close to the irradiated area; the specimen could be held at constant temperature within 1°C for long periods. The body-centered cubic 200 reflection near 8 = 26" was used as the index of the amount of b.c.c. material present; occasional checks were made using the most suitable line of the low-temperature phase, the close-packed hexagonal 110 line near 8 = 29". Copper radiation was used throughout. A continuous record was made of the reflected intensities on a strip chart recorder, both when the peak intensity of a line was being followed and when the lines were being scanned at constant temperature. On the continuous recordings of peak intensity, periodic checks were made on the background intensity between the lines, and on the setting of the spectrometer for maximum intensity. The lithium-base solid solution containing 12.4 atomic pct Mg (33.3 wt pct) that had been used previously' was chosen, as it had a transformation range at relatively high temperatures, so as to permit wide temperature cycling within the range. Just prior to use a pellet was cut from the ingot,

Jan 1, 1951

By V. S. Tuman

In the first part of this paper, an estimate is made of the magnitude and extent of the thermal stresses which result from mud circulation. Our study is made for the period of relaxation, i.e., when the drilling operations are terminated and mud circulation is discontinued. In the second part, we have shown how the thermal stress can affect the wave propagation. An example is worked out for a Carbondale sandstone (Illinois basin). It is concluded that, in extreme cases when differential temperature is about 100°F, the travel time will be affected by about 2 microsec/ft. For more refined permeability studies, such corrections would be desirable. MAGNITUDE AND EXTENT OF THERMAL STRESSES RESULTING FROM MUD CIRCULATION When geological beds are penetrated by boreholes, it is observed that the formation temperatures increase with depth; however, the temperature profile varies considerably from place to place. During drilling operations, mud pumped from a pit at atmospheric temperature absorbs heat from the lower beds. As a result, the drilling fluid returning to the surface is at a higher temperature than the surrounding beds. The temperature gradient in a well depends on the rate of mud circulation and other factors; normally, this temperature gradient is smaller than the natural gradient in the formations. (See Fig. 1.) The temperature difference between the mud column and the surrounding beds gives rise to therma1 stresses (which are also important in the phenomenon of fracturing), and it is expected that they will affect the transit time of the sonic front in velocity logging.1 It is evident chat beds near the surface will undergo various cycles and will have a complicated dynamical and thermal-stress history. A limestone bed which is just penetrated will act as a source of heat, warming up the cold mud pumped down a few minutes earlier from the surface pit. The same limestone bed a week later will act as a sink, absorbing heat from the drilling mud which has already warmed up sufficiently to be at a higher temperature than the bed in question. No doubt a large section of the hole will undergo a heat treatment, which will make the calculation of the exact magnitude of the thermal stresses very difficult. In the solution of wellbore thermal equation, it is assumed that the rock around the wellbore is elastic and isotropic, and that the system is radially symmetrical. A complete dynamical solution of the thermal stresses set up at different horizons during the drilling operations would require a comprehensive history of the mud circulation, the surface temperature of the pit and the number of hours in which mud was not circulated. CONDUCTION OF HEAT AND THERMAL EQUATION OF STATE