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By S. A. Falconer

The benefication of non-sulfide or non-metallic minerals by froth flotation has been practiced commercially for at least 30 years. In the pioneer stages of development of this flotation art, most of the promoters investigated were fatty acids or soaps that had been found to float sulfide minerals. When commercial application of froth flotation started to assume importance in the late 1920' s and 1930's, a great deal of fundamental research work was done in the laboratory (11-14, 19, 22, 23, 26, 29, 32). Among other subjects, this work included studies of the relative effectiveness of the different fatty acids and their salts on the flotability of various non-sulfide and non-metallic minerals. The successful present-day use of fatty acid and petroleum sulfonate type promoters results from better understanding of the principles of non-sulfide flotation plus the developnent of effective selectivity modifying agents. Many investigators have contributed to a greater appreciation of the numerous interrelated factors involved in fatty acid and soap flotation of non-sulfide minerals. Of these, mention should be made of recent fundamental studies by Tagart and Arbiter (31); Wolstenholme and Schulman (35); Schulman and Smith (28); Wark and his co-workers(3,4) Du FIietz(l5); and J. Leja(24). According to J. Rogers, K. L. Sutherland and E. E. and I. W. Wark(27), "the basic requirements for a 'collector' in flotation are that it shall form a film over the surface of the mineral to be floated and that this film should be oriented so that hydrocarbon (non-polar) groups form the effective surface." When modified in that way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince (33)that such a film can be produced only if the collector compound contains an active (polar) group to be attracted to the mineral surface, as well as the non-polar group. The commonly used anionic-type promoters for non-sulfide, non-metallic and metallic oxide ores include: 1. Fatty acids, and their soaps and emulsions. 2. Fatty acids residues — "pitches" and "foots." 3. Sulfonated and sulfated fatty acids and so-called "petroleum sulfonates." 4. Paraffin chain salts — sulfonated and sulfated higher alcohols. 5. Cyclic organic acids or salts, such as naph-thenic acid and naphthenates. Certain fatty acids are more effective than others as promoters for particular minerals under certain specified conditions. Some of the more costly fatty acids or collectors of the paraffin chain salt type may give improved selectivity in some instances and are being used commercially in a limited number of operations. Local availability may dictate the choice of the fatty acid used — for example, the use of palmoil fatty acid for flotation of copper carbonate ores in the Belgian Congo. Coconut oil fatty acids have also found limited use.

Jan 1, 1961

By Thomas M. Drown

AT the meeting of the Institute in New York,, in February, 1880,* I described a process of determining sulphur in metallic sulphides, with especial reference to the determination of pyrites in coal. The process, as then described, is as follows : A solution of sodium hydrate, of 1.25 specific gravity, is saturated with bromine. If an excess of bromine is used it must be neutralized by the addition of a :little more sodium hydrate. The pulverized mineral or coal is moistened with 25 c.c. of this solution and heated, then hydrochloric acid is added cautiously to just acid reaction. This operation is repeated with another 25 c.c. of the alkaline solution, and again rendered acid. The mixture should be kept hot. The contents of the beaker or dish are then * Transactions, American Institute of Mining Engineers, vol. viii, p. 569.

Jan 1, 1881

By E. P. Chartkoff, W. P. Sykes

In 1926 one of the authors published researches on the determination and description of the iron-tungsten and iron-molybdenum systems,' including the equilibrium diagrams. In 1929, further work was carried on, including the examination by X-rays, which is recorded here. Meas-urements were made of changes in lattice parameters in the solid solutions. Precipitation from the solid solution and the accompanying changes in hardness were studied as well as the formation of the intermetallic com-pound phases upon sintering a mixture of metal powders. Materials All the specimens were prepared from the same quality of metals and by the same methods as were described in the determination of the constitutional diagrams. The metal powders as mixed and pressed were sintered or fused in a hydrogen atmosphere and subsequently treated as indicated in the titles of the figures. The formation of the iron-rich solutlon in the solid was accomplished by sintering in hydrogen for a period of 20 to 30 hr. at a temperature 25' to 50' C. below the melting point of the eutectic. The tungsten-rich and molybdenum-rich solid solutions of iron were prepared by adding the iron as a solution of iron ammonium oxalate to the oxide of tungsten or molybdenum, followed by a hydrogen reduction. This method results in a homogeneous alloy after sintering the pressed metal powder for 20 to 30 hr. at a temperature slightly below that of the peritectic reaction in the system involved. For X-ray examination the specimens were variously prepared, depending on the nature of the sample and what it was desired to show. For example, the iron containing tungsten or molybdenum in solid solution was cut with a file, the chips were put through bolting cloth, and this powder of filings formed the specimens for comparative study. The

Jan 1, 1930

By G. W. LAAiIBOURNE

FEW mines possess a history of more fascinating interest than the Ontario at Park City, Utah. The famous Bonanza's production record of over $50,000,000; the great extent of its workings; the remarkable character of its mineralization; the fact that recent discoveries have shattered preconceived theories of the geology of the camp practically assuring the half-century old property a future as active and as prosperous as the past make the Ontario one of the unique mines of the world. A mere accounting of the wealth created by this historic property not only exemplifies the great profits

Jan 1, 1925

By Henry B. Estabrooks

As was true with many mining companies, the management of Tennessee Copper Co. followed with interest the successful application of AN-FO as an explosive in coal stripping, construction, open-pit mining, and finally in underground salt mines. Since Tennessee Copper's operations required about 1,250,000 lb of dynamite annually, the potential savings in explosives costs that could be realized by switching to AN-FO could not be ignored. From a cautious start, AN-FO is now being used for stoping, development work and secondary blasting in all mines of Tennessee Copper Co. AN-FO accounts for 80% of the explosives used in such work. Fragmentation, fumes, crew acceptance, and cost savings have been quite attractive without any decrease in safety.

Jan 11, 1962

By Ernest G. Enck

Expanding markets and technological investigations now in progress for commercial production of titanium metal and alloys, as well as expanding uses for the oxide, have resulted in greater production, increased prices, and accelerated search for additional commercial occurrences of titanium minerals. For more than 50 years rutile has been used in moderate quantities in ceramics, in the production of ferrotitanium, as well as nonferrous titanium alloys. During the early 1930's, use of pure titanium dioxide was introduced as an ingredient of coatings for electric welding rods. For technical and economic reasons rutile was soon found to be as good or better for mild steel welding rods, and this use continues to account for a good share of the rutile sales in the U. S.

Aug 1, 1956

By R. L. Loofbourow

Trends in the metal mining industry were definitely down in 1954. With a record in 1953 of $1.8 billion output, the last year dropped to $1.5 billion, the lowest value since 1950. The decrease in iron ore production alone accounted for at least 10 pct of the decline. PROBABLY more than any previous year, political debates of 1954 marked a new high for the mining industry. Lead and zinc prices gave forth with minor rallies producing no real improvements. An anticipated drop in copper prices never came to be. Early in the year arguments for more free trade versus tariffs to restrict imports were voiced eloquently by Charles P. Taft, president, Committee for a National Trade Policy, and Andrew Fletcher, president, St. Joseph Lead Co.

Jan 3, 1955

By Charles S. Barrett, Robert F. Mehl

A study of the structures arising from the decomposition of the ß solid solutions in the Cu-Zn and the Cu-A1 systems is of peculiar interest in the study of the mechanism of precipitation from solid solutions. It is possible in these alloys, by varying the composition within the ß field, to precipitate from the same basic lattice phases having different lattice structures. It has been rather generally assumed heretofore that the type of structure originating from the decomposition of a solid solution— the Widmanstätten structure—-is determined by the lattice structure of the parent solid solution alone. In the first paper of this series1 evidence was advanced which threw doubt upon this hypothesis; but definite proof of the correctness or incorrectness of the hypothesis should be forthcoming from a study of these alloys, for if the structures originating, for example, from the precipitation of the a phase from ß and of the ? phase from the ß in the Cu-Zn system should be shown to be crystallographically different, the hypothesis would necessarily be held as definitely disproved. Furthermore, the newer proposal enunciated in the first paper of this series—that the origin of the Widmanstätten structure lies in a cooperation between the lattice of the parent solid solution and that of the precipitate-—which at present seems the only a1ternative hypothesis, would in such an event be given added weight. The work here reported shows that the Widmanstätten structures originating in the precipitation of the a phase from the ß and in the precipit'at.ion of the y phase from the y in the Cu-Zn system are indeed crystallographically different; and incidentally presents some new descriptive information on the Widmanstätten structure from a more general point, of view.

Jan 1, 1931

By O. T. Marzke, Robert F. Mehl

A study of the structures arising from the decomposition of the ß solid solutions in the Cu-Zn and the Cu-A1 systems is of peculiar interest in the study of the mechanism of precipitation from solid solutions. It is possible in these alloys, by varying the composition within the ß field, to precipitate from the same basic lattice phases having different lattice structures. It has been rather generally assumed heretofore that the type of structure originating from the decomposition of a solid solution— the Widmanstätten structure—-is determined by the lattice structure of the parent solid solution alone. In the first paper of this series1 evidence was advanced which threw doubt upon this hypothesis; but definite proof of the correctness or incorrectness of the hypothesis should be forthcoming from a study of these alloys, for if the structures originating, for example, from the precipitation of the a phase from ß and of the ? phase from the ß in the Cu-Zn system should be shown to be crystallographically different, the hypothesis would necessarily be held as definitely disproved. Furthermore, the newer proposal enunciated in the first paper of this series—that the origin of the Widmanstätten structure lies in a cooperation between the lattice of the parent solid solution and that of the precipitate-—which at present seems the only a1ternative hypothesis, would in such an event be given added weight. The work here reported shows that the Widmanstätten structures originating in the precipitation of the a phase from the ß and in the precipit'at.ion of the y phase from the y in the Cu-Zn system are indeed crystallographically different; and incidentally presents some new descriptive information on the Widmanstätten structure from a more general point, of view.

Jan 1, 1931

By Robert Mehl

A STUDY of the structures arising from the decomposition of the a solid solutions in the Cu-Zn and the Cu-Al systems is of peculiar interest in the study of the mechanism of precipitation from solid solutions. It is possible in these alloys, by varying the composition within the ß field, to precipitate from the same basic lattice phases having different lattice structures. It has been rather generally assumed heretofore that the type of structure originating from the decomposition of a solid solution-the Widmanstätten structure-is determined by the lattice structure of the parent solid solution alone. In the first paper of this series1 evidence was advanced which threw doubt upon this hypothesis; but definite proof of the correctness or incorrectness of the hypothesis should be forthcoming from a study of these alloys, for if the structures originating, for example, from the precipitation of the a phase from ß and of the -y phase from the ß in the Cu-Zn system should be shown to be crystallographically different, the hypothesis would necessarily be held as definitely disproved. Furthermore, the newer proposal enunciated in the first paper of this series-that the origin of the Widmanstätten structure lies in a cooperation between the lattice of the parent solid solution and that of the precipitate-which at present seems the only alternative hypothesis, would in such an event be given added weight. The work here reported shows that the Widmanstätten structures originating in the precipitation of the a phase from the a and in the precipitation of the -y phase from the ß in the Cu-Zn system are indeed crystallographically different; and incidentally presents some new descriptive information on the Widmanstätten structure from a more general point of view.

Jan 1, 1931

By E. E. Duncan, G. Derce

REVIEW of the literature on hydrogen in steels indicates that inadequate consideration has been given to the influence of temperature gradients on segregation of this element. Even when segregation has been taken into account, the interpretation of the data has been seriously handicapped by incomplete understanding of the mechanism by which it occurred. Recognition of a mechanism which will be described as "thermal segregation" appears to rationalize many of the observed effects so well that it will be reported here with some preliminary experimental evidence. The complete quantitative evaluation of the factors controlling the mechanism will require extensive experimentation. The operation of the mechanism can be described in relation to fig. 1, which shows the temperature dependence of the solubility of hydrogen in iron at

Jan 1, 1951

By K. H. Coats, M. H. Terhune

Analysis and example applications have been performed to compare the accuracy and computing speed of alternating-direction explicit and implicit procedures (ADEP and ADIP) in numerical solution of reservoir fluid flow problems. ADIP yields significantly greater accuracy and requires about 60 per cent more computing time than ADEP, not 300 or 500 per cent more as reported elsewhere. l,2 INTRODUCTION Several recent papers 1-3 discuss an alternating-direction explicit difference approximation (ADEP) to the diffusion equation. Example applications of ADEP and ADIP4 were reported to support conclusions that ADEP is comparable in accuracy to ADIP and requires one-fifth to one-third the computing time of ADIP. Applications of ADEP in calculation of two-phase flow in reservoirs was also proposed. 3 This study was performed to compare further the relative merits of ADEP and ADIP in simulation of two-dimensional flow of one and two fluid phases in reservoirs. Since two-phase flow equations are often essentially elliptic rather than parabolic, the efficiency of ADEP in solving the elliptic equation was also examined.

Jan 1, 1967

By S. N. Singh, M. C. Flemings

Results are presented of a detailed study on the combined influences of ingot dendrite am spacing and thermomechanical treatments on the structure and solution kinetics of high --purity cast and worked 7075 alloy. Solution kinetics were found to depend sensitively on ingot dendrite am spacing and on details of therrnomechanical processing, including amount of reduction and extent of&apos; solution treatment before reduction. An approximate analysis is given for rate of solution of nonequilibrium second phase in the cast and worked structres; results of the analysis are compared with experiment. MICROSEGREGATION in high strength aluminum alloys manifests itself as "coring" (composition differences within the primary aluminum-rich phase), and as interdendritic second phase. The mechanism of formation of the microsegregation is understood, and approximate prediction of the amount of second phase is possible for simple binary systems.1,2 When alloy elements or impurities are present in amounts less than their solid solubility at solution temperature, any phases forming from these elements are termed "nonequilibrium" and can be dissolved by appropriate solution treatment. The rate at which the nonequilibrium phases are removed depends sensitively on their spacing (dendrite arm spacing in the cast material, or band spacing in wrought material). When alloy elements or impurities are present in amounts in excess of their solubility at the solution temperature, second phase particles form an "equilibrium" second phase that does not dissolve in heat treatment and may, in fact, coarsen in such treatment. Usual commercial, high strength, wrought aluminum alloys contain nonequilibrium second phases that were not fully dissolved during ingot processing. They also contain equilibrium second phases resulting from impurities present in amounts greater than their solubility. As has been shown by Antes, Lipson, and Rosenthal,3 and will be demonstrated further in a subsequent paper by the authors,4 significant improvements in mechanical properties of high strength alloys can be achieved by reduction or elimination of these second phases. Methods of elimination are 1) to employ high purity materials to minimize amounts of equilibrium second phase, and 2) to employ suitable thermomechanical processing techniques to fully eliminate nonequilibrium second phases. Work reported herein comprises a study of selected thermomechani- cal processing treatments, and of their influence on solution kinetics of wrought high purity 7075 alloy. EXPERIMENTAL PROCEDURE Melting and Casting. The bulk of the work reported was performed on a single ingot of high purity 7075 alloy. The ingot was 4 in. by 4 in. by 8 in. high, uni-directionally solidified following a procedure previously described.5 The mold was heated to 1350°F before pouring the melt. The bottom chill was carbon coated stainless steel. Water was circulated through the chill after the melt was poured. The 7075 alloy was prepared from high purity virgin material (aluminum, zinc, magnesium) and from master alloys (Al-50 pct Cu, A1-15 pct Cr, A1-5 pct Ti). Final measured melt composition (wt pct) was: Zn Mg Cu Cr Ti Fe Si Al 5.70 2.28 1.35 0.18 0.15 <0.002 <0.012 bal Melting was done in a silicon carbide crucible; all tools were coated with zircon wash to minimize iron contamination; degassing was by bubbling chlorine through the melt. che-rmomechanical Treatments. Detailed studies were made on material taken from a location approximately 13 in. from the chill and 51/2 in. from the chill (i.e., from 1 in. thick slices taken between 1 and 2 in. from the chill and between 5 and 6 in. from the chill). Solution treatment was done at 860°F in an air-circulating furnace with a "bottom drop" arrangement to achieve minimum delay time between solution treatment and quench. Samples solution treated in this way were 2 in. by 2 in. by 1 in. Temperature of the quench water was approximately 10°C. Mechanical reduction was by cold rolling. Samples 11/2 and 51/2 in. from the chill were treated for 12 and 24 hr, respectively, before cold rolling. Reduction by cold rolling was then 4/1, 16/1, and 35/1. In each case, several intermediate anneals (1/2 hr at 860°F) were used to permit reaching the final thickness without cracking; two such anneals were used for the 4/1 reduction, five for 16/1, and six for 35/1. After working, materials were again solution treated for various lengths of time from 0 to 48 hr and quenched in water. Structural Measurements. Secondary dendrite arm spacings were measured using procedures previously described.&apos; For each measurement reported, five photomicrographs were first made at X75. Measurements were made of dendrite arm spacings in at least 20 different grains (grain structure was equiaxed). Grain size measurements were made by running a number of random traverses across photomicrographs of the samples and obtaining the mean lineal intercept. Measurement of the volume percent of second phase and porosity was done by quantitative metallography. A two-dimensional systematic point count was used

Jan 1, 1970

By C. W. Sherman, J. Chipman, H. I. Elvander

THE pronounced and usually deleterious effects of sulphur on all ferrous metals and the resultant necessity for its control in metallurgical processes have stimulated many investigations of the system iron-sulphur. The data required for thermodynamic study of the behavior of sulphur in molten iron and steel include the activity and free energy of the dissolved sulphur and its heat of solution. Such data are also of theoretical interest since there is all too little information available concerning solutions of nonmetallic solutes in metallic solvents. It was the purpose of this investigation to attack the problem very directly by a study of equilibrium at several temperatures in the reaction H2 (gas) + S = H2S (gas) [1] K1 = PH2S /PH2 as where the sulphur is present in the liquid iron in amounts up to several percent by weight. Such a method of attack is not new since several careful studies have already been reported. It is planned, however, to extend the study to other metallic solvents and particularly to determine the effects of the various alloying elements on the activity of sulphur in liquid iron. This paper presents the results on molten iron-sulphur alloys containing up to 4 pct sulphur in the temperature range 1530°-1730°C. Literature Review The significant researches on dilute molten solutions of sulphur in iron include those of Chipman

Jan 1, 1951

By Milton E. Wadsworth, Daniel B. Brimhall

Column leach studies of a low-grade porphyry copper ore were made. The technique used involved alternating oxygen absorption and copper leach cycles. The leach solution was displayed from the column with oxygen. The volume of oxygen reacting with the ore was measured with a gas burette. The copper released as a result of exposure to oxygen was correlated with the oxygen uptake. The oxidation rate was found to be dependent on the pH of the solution wetting the particles and was markedly increased by increasing the temperature of the system. Decreasing the particle size of the sample increased the oxidation rate. A material balance on the system indicated 1 mole of oxygen yielded in excess of 1 mole of copper in solution. A discussion of the important parameters is presented and the results are related to dump leaching in general.

Jan 1, 1974

By A. H. Larson, L. G. Twidwell

DURING the roasting of zinc sulfide concentrates and by-product recovery from flue dusts, the zinc sul-fate phase may occur in various stages of the processes. In addition to zinc sulfide, other sulfide phases are usually present such as CdS, PbS, CuzS, and FeS. Consequently, the effect of these sulfides on the thermal decomposition of ZnS04 was investigated. Merck high-purity, anhydrous zinc sulfate was used as the starting material. The sulfate was heated under an argon atmosphere, at a rate of 10°C per min. With the first slight indication of decomposition as determined by gas analysis, the sample was removed from the furnace and allowed to cool. X-ray patterns showed no other phase present. It is estimated that less than 0.05 pct of the ZnS04 decomposed. The metal sulfides were also heated under an argon atmosphere to drive off any adsorbed water. The materials were then sized (-200 to +270 mesh), mixed in predetermined mole ratios, and pressed into pellets. The experimental measurement of the reaction rate consisted of purifying the argon carrier gas, continuous flushing of the heated reacting mixture with argon, and collection and analysis of the SOn product gas. The reaction system was heated to 600°C and al-

Jan 1, 1967

By V. G. Leak, R. A. Swalin

The dilhsion of silver and trace concentrations of tin in liquid silver has been rrzeasured in the temperature range from about 975° to 1350°C. The difBsion dala. fil lhe following equations: fov self-diffusion of silver The ratio of DSn to DAg is found to be about 1.34. The higher diffusivity of tin is interpreted in terms of the coullombic repulsion which results from the fact that tin dissolved in silver has a valence of +3 relative to silver. THE phenomenon of diffusion has been well-described theoretically for hard-sphere gases and solids and found to be in good agreement with experimental data for certain gases and solids. Liquid-diffusion phenomena have not been well described theoretically and there is generally a lack of good experimental data. In this investigation self-diffusion and solute diffusion in liquid silver were studied. Silver was chosen as a solvent for two main reasons. First, silver is a noble metal and the atoms are considered to have a spherically symmetric charge field; hence the liquid may be considered to be a random array of approximate hard spheres. Mercury, gallium, and other lower-melting metals were eliminated from consideration since it appears possible that in their liquid states there is some residual long-range order and directional bonding. Second, silver behaves as a monovalent solvent and, while cadmium, indium, tin, and antimony all have nearly the same atomic size, they have chemical valences relative to that of silver of +1, +2, + 3, and +4, respectively. Slifkin, Lazarus, and coworkers1-5 investigated the diffusion of these solutes in solid silver and found that their diffusion rates increased with an increase of the excess valence of the solute. In the solid state the diffusion-rate increase was calculated to be due to a change in local modulus of the solvent caused by the excess valence of the solute.1"3 For the present investigation it was planned to determine the effect of valence upon solute diffusion in liquid silver. It was deduced that a coulombic repulsion between solute and solvent might be responsible for larger volume fluctuations in the vicinity of the solute thereby enhancing the diffusion of the solute atoms. Tin was the first solute investigated and was chosen for experimental convenience. If an excess-valence diffusion effect exists in the liquid state, the solute tin with its excess valence of + 3 might show a large enough effect to distinguish it from the self-diffusion of silver in silver. The silver self-diffusion data were obviously required as a base line for comparison. In addition silver self-diffusion was investigated with a view toward examining the data in connection with the Sutherland- Einstein: Coheen-Turnbull,7 and swalin8 theories of diffusion in liquids. I) EXPERIMENTAL TECHNIQUES The diffusion coefficients for tin and silver in liquid silver were determined in separate experiments using the capillary-reservoir method of Anderson and saddingtono but following closely the experimental techniques outlined by Ma and Swa1in. The radioactive alloy bath was prepared by plating either tin-113 or silver-110 m isotope* onto 99.999 *Isotopes obtained from Oak Ridge National Laboratory. pct Ag rods.* The silver and isotope were melted *Silver obtained from Cominco Co. and mixed in a graphite crucible under a purified argon atmosphere, then outgassed for capillary filling. Some of the fused-silica capillaries were filled individually as reported by Ma and Swalin, but most were filled in a different manner. A long piece of capillary tubing was sealed off on one end and held in the system so that the open end was just above the surface of the molten alloy. The system was evacuated, the open end submerged into the alloy, and argon was admitted into the system up to atmospheric pressure. The molten alloy was forced up the capillary several inches where it solidified and was subsequently cut into segments of the proper length for diffusion annealing. The apparatus for diffusion annealing was the same as that used for capillary filling except that a Pt—Pt, 10 pct Rh therinocouple was placed in the solvent bath in order to accurately measure the temperature during the run. A diagram of the dif-

Jan 1, 1964

By Arnulf Muan, W. C. Hahn

Activities of "FeO" in "FeO"-MgO solid solutions have been determined in the temperature interval 1100" to 1300"C by equilibrating oxide samples with pure metallic iron in atmospheres of known oxygen partial pressures. The end members "FeO" and MgO form a complete solid solution series. The system shoztls a considerable positive deviation from Raoult&apos;s law. A large amount of data has been accumulated during the past 50 years on stability relations existing among various crystalline and liquid phases in oxide systems of importance in metallurgical processes. By comparison, very little is known about the thermodynamic properties within the various homogeneous phases present in the systems, particularly the crystalline phases. The present paper deals with determination of activities as a function of composition in solid solutions of wüstite ("FeO") and periclase (MgO). Such solid solutions ("Magnesiowustites") have simple sodium chloride structure and are known to be continuous between the end members at elevated temperatures (> 1000°C) and strongly reducing conditions such as prevail in contact with metallic iron. Wiistite has a defect structure in which the ratio of oxygen to iron varies and never has as low a value as 1:1 corresponding to the simplified formula FeO. Within the range of stability of this phase, the composition changes between a maximum oxygen content of approximately 25.6 wt pct (corresponding to the formula FeO.83O) and a minimum oxygen content of approximately 23.2 wt pct (corresponding to the formula Fe0-96O). The activity data to be reported in the present paper are based on using as standard state the wüstite which is in equilibrium with metallic iron at a particular temperature, i.e., "FeO" of minimum oxygen content at each temperature. For sake of simplicity, the formula FeO will be used to represent the wustite phase in the remainder of this paper. Consider the reaction 2 FeO solid solution = 2 Femeta1 + Ozgas in which FeO dissolved in another oxide dissociates to metal and gas. The activity of FeO in the solid solution, relative to "pure FeO" in equilibrium with metallic iron as a standard state, is then expressed as Here Po, and po2 * are the partial pressures of oxygen of the gas phase in equilibrium with metallic iron and the oxide solid solution or "pure FeO", respectively. The equation holds only if the metal phase is essentially pure Fe. The oxide combinations used in the present investigation fulfill this requirement. Magnesia is so much more stable than FeO that for all practical purposes aFe = 1 in the metal phase present in all mixtures used in this investigation. I. EXPERIMENTAL METHOD 1. General Procedure. The experimental method used was analogous to that developed by Foster and Welch1 and used recently by Hahn and Muan.2 It consisted of four steps: a) Determination of the equilibrium between FeO and Fe. b) Determination of d-spacing change with composition in oxide solid solutions (FeO-WO). c) Equilibration of various members of the solid solution series with a metal phase and a gas phase of known oxygen partial pressure. d) Determination of compositions of solid solutions resulting from step (c) by means of data obtained in step (b). 2. Starting Materials. General Aniline and Film Corp. carbonyl iron powder, type HP, was used as the source of metallic iron. A representative analysis was as follows: Fe, 99.6 pct; C, 0.01 to 0.04 pct; 0, 0.1 to 0.3 pct; N, 0.00 to 0.05 pct. Other elements were present as traces only. Wiistite was prepared from "Baker Analyzed" Reagent grade Fe2O3 of reported analysis as follows: Assay (Fe2O3), 98.8 pct; insoluble in HC1, 0.02 pct; not precipitated by NH,OH, 0.02 pct; Zn, 0.003 pct. Production of wüstite was achieved by a two-step

Jan 1, 1962

By M. B. Bever, A. K. Jena

THE heats of formation ?H at 273°K of the compound AgMg as a function of composition have been measured by solution calorimetry.1 The value at the stoichiometric composition is -4.41 kcal per g-atom. From electromotive force measurements2&apos;3 the heat of formation at 773°K of stoichiometric AgMg has been determined as -5.19 kcal per g-atom.4 The combination of these two values results in an unusually high negative temperature coefficient of the heat of formation d?H/dT = ?Cp = -1.6 cal per g-atom-OK. By contrast, published heat contents of the compound AgMg and the component elements above room temperature5 indicate that the temperature coefficient of the heat of formation of AgMg is nearly zero. In this communication calorimetrically measured heats of formation of A.K.JENA,Junior- MemberAIME,andM.B. BEVER,Member AIME, are Staff Member, Division of Sponsored Research, and Professor of Metallurgy, respectively, Massachusetts Institute of Technology, Cambridge, Mass. Manuscript submitted July 1, 1968. IMD AgMg below room temperature are reported and the temperature dependence of the heat of formation is discussed. The heat effects of additions of samples of the compound AgMg containing 50.1 at. pct Mg to liquid tin-rich solutions at 623°K were measured in a solution Calorimeter.6 The heat effects of additions plotted against the average of the atom fractions of solutes in the solution before and after each addition were a linear function of composition from which the heat effect at infinite dilution was obtained, Table I. The calorimeter was calibrated by additions of tin; the heat content (H623°K - H273°K) of tin was taken as 4.08 kcal per g-atom.4 The heat effect at infinite dilution of an addition of where heat of formation of AgMg at T°K, T = temperature from which samples are added (78°, 195°. and 273°K), Xi = atom fraction of i in AgMg, ?Hi = relative partial gram-atomic enthalpy of i in tin-rich solution.

Jan 1, 1969