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By Carle Hayward

IN reheating quenched steel to remove part of the hardness, the softening effect has generally been considered to be a function of temperature and time. The temperature effect is well known, and long before pyrometers were heard of the blacksmith was able to do a good job of tempering, by rule-of-thumb methods and experience in judging temperatures. Modern conditions, which demand steel that will withstand the severest tests, require that the heat treatment he carried out with every possible precaution to secure the best results obtainable. Pyrometers and heat-treatment furnaces of many types are on the market and improvements are continually being made so that it is now possible to regulate the temperature in heat treatment very accurately. There is -still a question regarding the time that the steel should be subjected to treatment. It is customary with all operators to insure the desired tem-pressure throughout the specimen and it is generally supposed that a longer treatment of a hardened steel produces a further softening but there are few published figures showing the exact effect of time of treat-ment at constant temperature. A search of the literature disclosed several brief statements that the tempering effect was a function of both time and temperature, but in no case were any figures given. The opinion is very generally held that the well-known tempering colors are accurate indicators of the degree of tempering. This is disputed by Brearley (The Heat Treatment of Tool Steel, page 102) who states: It has been said that the result would be the same in respect to both hardness and other properties whether the colors were obtained by a shorter heating at a higher temperature or a longer heating at a lower one. This, to say the least, is a very doubtful conclusion, and is certainly not borne out by mechanical tests on oil-hardened and tempered motor car steels, which, after tempering for periods varying from 15 min to 2 hr., show no very great differences. The present investigation had for its object the obtaining of some definite data regarding the effect of time, which might serve as a guide to those engaged in the heat treatment of steel. The Rhode Island Tool Co. cooperated by furnishing the steel and machining the test specimens.

Jan 2, 1917

By Benjamin Smith Lyman

The question of the original extent of the anthracite-beds of Pennsylvania has often been raised; and even discussed with reference to the probability of their present existence under the New Red, a matter of immense practical importance. So high an authority as my revered master, J. P. Lesley, Honorary

Jan 1, 1903

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before break-age, which appears as heat. An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories are compared.

Jan 8, 1950

By Frank L. Nason

During the months of June and July of the present year, the writer made a special geological survey of the mining property of Messrs. Cooper and Hewitt, at Ringwood, New Jersey. Some of the results of this survey are presented to the society through the courtesy of Hon. Abram 8. Hewitt.

Jan 1, 1895

By T. A. Rickard

The question of the original extent of the anthracite-beds of Pennsylvania has often been raised; and even discussed with reference to the probability of their present existence under the New Red, a matter of immense practical importance. So high an authority as my revered master, J. P. Lesley, Honorary

Jan 1, 1903

By Carl Lee

OXYGEN-FREE high-conductivity copper (OFHC brand) that is now being commercially offered for the first time represents a notable achievement in electro-metallurgy and is the outcome of endeavors that have extended over a long period. Its manufacture is novel in that electrolytically refined copper is melted in electric furnaces and cast into vertical water-cooled molds. The ingots show the "pipe" characteristic of sound gas-free metal and microscopic examination even at high magnification reveals no cuprous oxide in the copper. Owing to the patent situation, the United States Metals Refining Co., the producers, cannot at this time divulge the details of manufacture, but the operations are under precise control so that the castings are of great uniformity and the copper contains no residual deoxidant. Figs. 1 and 2 show photographs of cross-sections of a wirebar and a billet, both vertically cast.

Jan 1, 1933

By Robert E. Tally

THE membership of the American Institute of Mining and Metallurgical Engineers is composed largely of technicians, operating engineers, and executives in the mining, metallurgical and petroleum industries. The Institute also has its student, junior and associate membership and its Woman's Auxiliary. Primarily, it is a technical society, devoting itself largely to the encouragement of progress within the industries it represents, and to the discussion and dissemination of facts regarding this progress to its membership. The wisdom of this policy is reflected by the prestige and position which the society has gained, not only .among its members but throughout the entire mining world.

Jan 1, 1932

By A. E. Dwight, A. F. Berndt

Binary and ternary alloys of uranium with transition metals were prepared with U2X stoichiometry. The compounds U2Tc, U2Rh, U2Os, and U2lr were formed by peritectic or peritectoid transformations, and were shown to be isostructural with U2Ru. The lattice constants are presented. Miscibility relationships obtained from the study of ternary alloys are graphically summarized in terms of an area-of-stability plot. The compound U2Re is not isostructural with either U2Ru or U2Mo. A series of compounds with stoichiometry U2X has been prepared in which X is technetium, rhodium, rhenium, osmium, or iridium. The only other U2X compounds, for which X is related to the above transition metals by proximity in the periodic table, are U2Mo and U2Ru. The structure of U2Mo is the tetragonal C11b type (MoSi2 type)1 and U2Ru is monoclinic, with a new structure type.' This investigation was undertaken to determine if any of the above compounds are isostructural with either U2Ru or U2Mo and to find the range of occurrence of these phases. EXPERIMENTAL Alloys were prepared from stoichiometric amounts of electrolytic uranium (99.99 pet pure) and transition metals of 99.5 pet purity (98+ pet pure Tc), by arc melting on a water-cooled copper hearth under an Ar-He atmosphere. Weight losses were negligible. The buttons were homogenized at temperatures between 700o and 800°C (900°C for U2Tc) in evacuated capsules and air-cooled. The X-ray powder specimens were annealed briefly at the temperature of homogenization. Except in the case of the technetium alloy, metallographic examination was used to determine the number of phases present. The radiation hazard involved in handling technetium precluded the use of metallography to examine U2Tc. The temperature and mode of formation of the U2X phases were determined by heating the metallographic specimens to successively higher temperatures, until examination indicated the presence of chilled liquid or a peritectoid transformation. RESULTS The U2X compounds investigated were found to be formed under the following conditions: UzTc unknown U2Ru peritectic 897o ± 3°C U2Rh peritectoid 755o ± 5°C U2Re peritectoid3 below 750°C Uas peritectic4 920°C U2Ir peritectoid 775o ± 5oC Debye-Scherrer patterns for the above U2X phases were made with CuKa radiation (nickel filter). The similarities in the positions and intensities of the strongest lines in the front-reflection region strongly suggested that U2Tc, U2Ru, U2Rh, U2Os, and U21r are isostructural with only minor differences in the unit-cell dimensions. The known lattice constants and intensities of the Debye-Scherrer rings for U2RU2 were used as a guide in order to index the low-angle X-ray reflections of the U2TC, U2Rh, U2Os, and U2Ir powder patterns. Approximate lattice constants for these compounds were thus obtained and were used along with the intensities observed for U2Ru to index the strongest lines in the back-reflection regions. A sin2 2? correction term was included and the lattice constants were refined and standard deviations estimated by least squares. Comparison of observed and calculated values of Q(= 4 sin2?/?2) used in these calculations are given in Table I. In each case when the positions of lines could not be resolved on the films they were not measured. The final lattice constants, with their standard deviations, are given in Table 11, along with the unit-cell volume and X-ray density. The values of the atomic volume5 of the transition ele-

Jan 1, 1965

LOCAL SECTIONS (There are 60 Local Sections in the United States, 4 Foreign ) ADIRONDACK Established June 18, 1952 Paul W Allen, Chairman William Webb, Vice-Chairman Edwin Briggs, Secretary-Treasurer National Lead Company Mac Intyre Development Tahawus, New York Paul W Allen, Section Delegate R G Fleck, Alternate Section Delegate

Jan 1, 1954

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By R. E. Zinkham, R. J. Goodwin

A mathematical study has been made of the amount of support a cement sheath could provide to casing cemented into the earth. Several assumptions were required to make the analysis, but only two of them are limiting: (I) the pipe must be completely surrounded with cement, and (2) any mud filter cake between the cement and formation has the same physical properties as either the cement or formation. The calculations showed that little support would be provided to the pipe before an unsupported cement sheath failed in tension; however, when the cement is confined between the pipe and wellbore and is loaded in compression, the pipe could receive a considerable amount of support. In fact, the theoretical results indicate the lower grades and larger sizes of pipe could have their working pressures doubled when reasonable compressive loads were applied to a surrounding cement sheath. These data are shown in six charts. Other down-hole conditions such as setting the cement under pressure, increased temperature and cement confinement all tend to increase the potential usefulness of the sheath. Because of size limitations, a laboratory program to verify the most important results of this mathematical study would be very difficult. However, small-scale field tests would be practicable. This paper shows that, if a solid cement sheath can be obtained in the field by either primary cementing or by repair after detection of flaws by surveys such as the new cement-bond logs, the use of this approach to reducing pipe costs merits further consideration. INTRODUCTION A modification in casing design practices is proposed which may either reduce the amount and grade of steel required to contain a specified internal pressure or permit the working pressure to be increased for a specified weight and grade of pipe. One of the more important considerations in casing design is its resistance to collapse; however, Bowers' and, more recently, O'Brien and Goins' have shown many casing programs are unnecessarily conservative in this respect, and they have indicated how savings can be made by designing for more realistic down-hole conditions. Earlier, Saye and Richardson howed that pipe costs could be reduced by considering the cement sheath as a part of the casing string when collapse resistance was being calculated. More recently, Rogers4 has raised the question as to whether a cement sheath might be considered in the design for burst resistance of the cemented casing. Calculations have been made for the increased burst resistance a cement sheath would provide for casing in a wellbore, and the results show that a sizable amount of support could be obtained in some instances. These data are presented in addition to a discussion of several other factors that are considered to affect the burst strength of pipe supported by cement. Two types of support are treated: Case I for tensile loading of the unconfined cement sheath, and Case for compressive loading of the confined cement sheath. ANALYTICAL TREATMENT AND RESULTS CASE I—TENSILE STRESSES IN AN UNCONFINED CEMENT SHEATH Conditions like this would most likely occur in a greatly enlarged portion of the hole where the cement was not in immediate contact with either the formation or a thin and hard mud cake. The mathematical analysis for this condition, as shown in the Appendix, rests on the following concepts. Pressure inside a unit length of pipe causes: (1) a tensile or tangential stress to be exerted over the longitudinal cross-sectional areas of the pipe and cement; and (2) an equal amount of strain in both the pipe and cement that is uniformly distributed over the wall thickness of each. This analysis was then used to make several calculations for a cement sheath around 51/2-in. OD pipe. The results are illustrated in Fig. 1, which shows that a tensile stress of 500 psi is imposed on a 5-in. thick sheath when the casing contains a pressure of only 1,450 psi. It also shows that a 10-in. thick sheath would be stressed to 500 psi in tension when the pipe contained a pressure of only 2,350 psi. Alternatively, if the stress analysis is made by means of the Lame thick-wall cylinder theory, the inner fibers of the 10-in. thick sheath will be stressed to 500 psi in tension when the pressure in the pipe is only 990 psi. This, of course, reveals that an unconfined sheath is of little support to the pipe in burst; however, an entirely different result is obtained when the cement is confined between the pipe and formation.

By AIME

Rapid exhaustion of iron ore in Minnesota's Mesabi range has led the Jones & Laughlin Steel Corp. to develop the world's largest open quarry mine for magnetite iron ore, at Star Lake, N. Y. Already contributing more than one eighth of the total iron ore used by the Corporation, the expanding Benson mines are destined to become Jones & Laughlin's important source of ore within the next ten years. In 1947 over 650,000 long tons of high-grade ore was produced. Output this year is expected to reach 800,000 long tons and studies are under way to increase production further. The future of the Benson mines is assured as present indications show large reserves of ore. The property, briefly described in M & M for November 1943, then under

Jan 1, 1948

A tough Conservation Act has been in force in Pennsylvania since January, 1964. Known as the Bituminous Coal Open Pit Mining Conservation Act, it is now under study by other coal producing states, and seems likely to serve as the blueprint for similar legislation elsewhere. It provides for the conservation and improvement of areas of land affected by open pit mining to decrease soil erosion, prevent pollution of rivers and streams, prevent combustion of unmined coal and generally improve the use and enjoyment of such lands. The cost of backfilling may go to as much as 40[c] or more per recovered ton and is cutting deeply into already reduced profit margins brought on by rising labor and equipment costs, static coal prices and less accessible coal. As a result, operators will be forced to seek greater efficiency.

Jan 7, 1965

By John V. Beall

The Glidden Co., a newcomer to the mining industry, will be putting on stream its Lakehurst mine and concentrator this spring. Ilmenite-bearing placer sands will be mined and concentrated in a spanking new combination gravity, magnetic and high-tension separation plant. Glidden, well known as a paint, chemical and food manufacturer, consumes titanium dioxide as pigment in its paint business. The commodity is produced at the company's Adrian D. Joyce Works in Baltimore from ilmenite purchased in India and Australia, The Lakehurst operation, handily located in Ocean County, N. J., will dampen any deficiencies in quantity or price which might occur from foreign suppliers. This objective is no overnight concoction of The Glidden Co., because the move at Lakehurst was preceded by an attempt to start up in Florida. That project was abandoned when it was found that the titanium dioxide values were largely in rutile-a mineral which does not lend itself readily to the digestion process of the Baltimore chemical plant.

Jan 1, 1962

By Ö. Valla, A. Muan, K. Grjotheim

The solid miscibility gap between CaO and "FeO" in the system CaO-"FeO" in contact with metallic iron gradually closes as MnO is added as a third component. On the liquidus surface of the system CaO-"FeO"-MnO, this situation gives rise to a boundary curve which originates in the bounding system CaO-''FeO", proceeds a short distance into the composition triangle of the ternary system, and then vanishes. A new approach has been used to follow the course of this boundary curve. It is shown that the curve vanishes at a much lower temperature and at much lower MnO contents than has been inferred previously. The oxides CaO, "FeO", and MnO together with SiO2 are the major components of the slag phase formed in the basic oxygen process. Hence, the system CaO-"Fe0"-MnO is of considerable technological interest. In addition, the system is theoretically interesting. The three oxides above all have sodium chloride structure. The size differences among the cations are such that in the bounding "binary"* systems CaO-MnO and "FeO"-MnO complete solid-solution series are formed,1,2 whereas in the system CaO-"FeO" there is only limited mutual solubility in the solid state,3 see Fig. 1. Hence, a solid miscibility gap exists in a part of the "ternary"* system Ca0-"Fe0"-Mn0, and a liquidus boundary curve originates at the peritectic point, point a in the insert in Fig. 1, in the system CaO-"FeO", extends a certain distance into the ternary system, and then vanishes. Very little quantitative information on the system Ca0-"Fe0"-Mn0 is available in previous literature. Fischer and Feischer4 sketched isothermal sections at 1600° and 1700°C, and estimated that the vanishing boundary curve extends to approximately 1650°C and a composition of 42 wt pct MnO. The work to be described in the following was aimed at locating experimentally the "vanishing" liquidus boundary curve, determining its end point, and deriving representative isothermal sections below and above the temperature of the end point of this curve. EXPERIMENTAL METHODS The phase relations were determined by the well-known quenching method. (For a description of this method as applied to oxide systems, see the original paper of Shepherd, Rankin, and wright.5) Prereacted oxide mixtures of desired compositions were contained in iron crucibles and heated in a vertical tube furnace in an atmosphere of purified nitrogen. After equilibrium was judged to have been attained, the samples were quenched to room temperature, the phases present were identified by microscopic and X-ray examination, and total iron oxide contents were determined by chemical analysis. "Fisher Certified" reagents (MnCO3, CaCO3, Fe2O3, and Fe) served as starting materials. The calcium carbonate and ferric oxide were heated in air at 400° and 800°C, respectively, for 24 hr prior to use. Manganese oxide was prepared by decomposing the carbonate in a graphite crucible in hydrogen atmosphere at 1000°C. The product was ground under acetone to -100 mesh. The iron powder was used directly without any preparation. Dicalcium ferrite was used as a starting material for some mixtures. It was made by mixing some of the above prepared CaCO3 and Fe2O3 in proportions corresponding to the formula 2CaO. Fe2O3. This mixture was then fired in air for

Jan 1, 1969

By G. R. Fitterer

Trends in slag composition in acid open hearth practice, particularly the variation in iron and manganese oxides during refining, are reviewed. A procedure which is currently being used to control the refining reactions is described and partially explained through slag phase diagram considerations. In addition, the ionic nature of these slags is considered and it is proposed that silica combines with the oxide ion and forms a series of complex silicate ions. The effect of basic oxides such as FeO, MnO, and CaO is apparently additive in furnishing the oxide ion for this purpose. IT is now possible to control192 the refining of steel in an acid open hearth furnace to a surprising degree. This control has been brought about through the knowledge and use of several facts and tests. These are: 1—A planned charge analysis based on a knowledge of the type of fuel, the bath depth, etc. 2—Knowledge and control of rate of fuel input as well as its method of atomization, if any. 3—Determination of the slag fluidity. 4—Bath temperatures (use of the Pt-Pt-Rh thermocouple). 5—Periodic determination of carbon content (use of the Carb-analyzer or Carbometer). Through the use of these control methods, a heat may be made to "melt-in" with or without residual manganese and silicon. The rate of refining or carbon elimination may be controlled accurately, and the desired tapping (or "go-ahead") carbon may be approached at a rapid or slow rate according to preference and type of steel being made. Thus operating time may be predetermined and greatly reduced. Further, all of the refining can be done without any ore or other oxidizing additions, and the heat may be brought to the desired tapping temperature simultaneously with the attainment of the desired carbon analysis. This control procedure is being used in most acid plants in the United States today and has been de- scribed.', ' Although the slag metal relations are sufficiently well known to control the heat as stated, yet it is possible to account for only about two-thirds' of the 0, which must have been used for the elimination of the carbon and other metalloids. Phase diagram studies' of the slags, slag weights, the metal particle theory,' ore additions, limestone additions, etc., may all be taken into consideration; yet, the mechanism of oxidation and source of all the oxygen remain to be explained. This paper reviews some of the principles upon which the control methods were based and proposes other possibilities regarding the unexplained phenomena. Old and New Acid Open Hearth Practice Some of the recent statements in the literature regarding acid open hearth operation are based on old heat data which are not typical of modern American practice. These old heat logs have been responsible for many misconceptions regarding the acid hearth practice and represent heats which do not coincide with modern methods. In recent years, American practice has been altered materially and these changes will be briefly described. Modern American Practice: A typical log of a modern American acid open hearth heat' is shown in Fig. 1 which indicates that the refining time was only two hours, during which the carbon was eliminated rapidly and the bath temperature increased at a fast rate. The manganese and silicon contents of the metal were essentially eliminated and their oxides had become constituent parts of the slag at the "melt-down" period. During the course of the heat, the MnO content of the slag remained practi-

Jan 1, 1954

By J. C. Rengel

Why and how the nuclear industry entered the electric power generation business is discussed in terms that nuclear energy was an undoubtedly additional energy resource and that it had promise of becoming a virtually inexhaustible generating power if breeder reactors could be devised. The growth of nuclear power, its total generation capacity, are related to the need of increasing energy requirements. The use of atomic energy for power generation will grow if it can compete economically with other fuels. The rate of growth, the time scale and direction of technical development is dependent on ore supplies. It is predicted that by 1980, 50% of all new power installations will be nuclear stations. INTRODUCTION Ten years ago, the nuclear industry was virtually unborn, the Atomic Energy Act of 1954 had just been signed, and peaceful applications of atomic power was little more than a phrase. Serious discussion of the practical application of nuclear energy to electric utility installations in the West was highly unlikely. The questions: Why and how did the nuclear industry enter the electric power generation business at all?; What is the predicted growth of nuclear power?; What technological changes do we predict?; How will the above changes affect the utilities? will in part be answered by this paper. WHY NUCLEAR POWER? The only justification for the West as for any other section of the country for atomic power is economics. Whatever energy source will provide the lowest generation cost will prevail; the only electric utilities which have shown an interest in nuclear power are those to whom it means lower generation costs. It is true that the Government sponsored the development of this technology long before there was any evidence of better economics; but a Government must take a very long-range view and it is the only type of organization that can afford to look more than twenty or thirty years into the future. The Government looked at projections such as shown in Fig. 1, which shows various rates of energy consumption, and matched these against estimates of fossil fuel resources. This showed that we will exhaust our low-cost fossil fuel supplies within 75 to 100 years and our total known fuel supplies within 150 to 200 years. The decision to invest in nuclear energy rested, therefore, on two arguments: a) It was undoubtedly an additional energy resource; and b) It has promise of becoming a virtually inex-haustable resource if breeder reactors could be devised if, while generating power, the reactors would produce more fissile materials than they consumed. This decision produced an unexpected bonus: nuclear power became competitive with fossil power much earlier than had been expected and, as shown in Fig. 2, forced the coal industry to take a hard look at its own position. I believe that the drop of coal prices shown here is the direct result of the entry of nuclear power into the energy supply business. At this point, it ought to be explained why and under what conditions nuclear power can be cheaper than fossil power. Fossil fuel cost to the utility is composed of two factors: a) Mining; and b) Transportation. As a result, the cost of fossil fuel to the utilities varies from 126, 106 Btu to 306, 106 Btu and higher. Nuclear energy is highly concentrated and the transportation factor becomes insignificant. Today the cost of nuclear fuel to the utility ranges between 156

Jan 1, 1967

By E. A. Gulbransen, W. S. Wysong

The behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a a Or as an important component in alloys in high temperature Oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a micro-balance study of the following problems: (1) the oxidation behavior in the ternperature range of 25 to 550°C (') the reduction with pure hydrogen Of thin Oxide films formed On tungsten, and (3) the volatility Of thin Oxide films On tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the Oxide to to ratio is greater than one, the oxide is not considered protective, ('1 the meta1 readily Oxidizes at temperatures from 30" to 55o°C (3) the oxides WO² and WO³ are reduced at temperatures as low as 500°C. by hydrogen, and (4) the Oxide WO3 is volatile at temperatures from 800 to 1100°C. Literature The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°c. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides, Schei14 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bed-worth's5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.? They have reported that WO3 is the stable oxide in contact with the metallic substrate up to approximately 600°C while wo³ forms first at 7oo°c. Hagg and Magneli8 have recently reported a study of the lattice structures . observed in the tungsten oxidcs using the X-ray diffraction method. In addition to an a-phase WO3 and a '-phase WO2, they reported the existence of two new phases. A 8' phase, homogeneous between

Jan 1, 1949

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942