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By N. A. Gokcen, J. Chipman

Aluminum and oxygen dissolved in liquid iron were brought into equilibrium with pure alumina crucibles and atmospheres of known H2O and H2 contents to study the reactions: 1—Al2O3(s) = 2 Al + 3 0; 2—Al2o3(s) + 3H2(g) = 2Al+ 3H2o(g); and 3—H2(9) +O = H2O(g). Aluminum strongly reduces the activity coefficient of oxygen and similarly oxygen reduces that of aluminum. Values of the product [% All" • [% O]3 are much smaller than those found in previous experimental studies and are of the order of magnitude of the calculated values. ALUMINUM is the strongest deoxidizer commonly A used in steelmaking, but the extent to which it removes dissolved oxygen has been debatable. The relationship between aluminum and oxygen has not been determined reliably not only on account of the usual experimental difficulties at high temperatures but also because of uncertainties in the analyses of very small concentrations of oxygen and aluminum. The earliest experimental attempt of Herty and coworkers' was followed by a more systematic study of Wentrup and Hieber.' These authors added aluminum to liquid iron of high oxygen content in an induction furnace and considered that 10 min was sufficient to remove the deoxidation products from the melt. Parts of the melts thus obtained were poured into a copper mold and analyzed for total aluminum and oxygen (soluble plus insoluble forms), assuming that the insoluble parts were in solution at the temperatures from which samples were taken. It is conceivable that the furnace atmosphere in their experiments, consisting of mainly air at 20 mm Hg pressure, was a serious source of continuous oxidation and therefore that their oxygen concentrations were correspondingly high. Scattering of their data was explained to be well within the maximum inaccuracy of 10°C in the temperature measurements and errors of ±0.002 pct each in the oxygen and total aluminum analyses. Maximum and minimum deoxidation values, i.e., values of the product [% All' . [% O] differed by factors of 10 to 15; mean values of 9x10-11 and 7.5x10-9 ere reported at 1600" and 1700°C, respectively. Hilty and Craftsv determined the solubility of oxygen in liquid iron containing aluminum, using a rotating induction furnace. Pure alumina crucibles used in their experiments contained the liquid iron which in turn acted as a container for slags of varying compositions consisting mainly of Al2O3, Fe2O3, and FeO. The furnace was continuously flushed with argon, and additions of aluminum and Fe2O3 were made in the course of each experimental heat. The inner surfaces of their alumina crucibles were covered with a substance other than pure Al2O3, containing both iron oxide and alumina. Although frequent slag additions can change the composition of slag in the liquid iron cup formed by rotation, the inner surface of the crucible must depend upon the transfer of oxygen or aluminum through the liquid iron for any adjustment in composition. It is not clear that their metal was in equilibrium with the crucible wall, but it is clear that it was not in equilibrium with Al2O3. Their deoxidation product, [% A].]" • [% O]3, varied by a factor of more than 50; the average values of 2.8x10- and 1.0x10-7 were selected for temperatures of 1600" and 1700°C, respectively. Aside from the experimental determinations, attempts have been made to calculate the deoxidation constant for aluminum indirectly from thermody-namic data. Schenck4 combined the thermodynamic data for Al2O3 and dissolved oxygen in liquid iron by assuming an ideal solution. His calculated values are 2.0x10-15 and 3.2x10-13 at 1600" and 1700°C, respectively. Later, Chipman5 attempted to correct for the deviation from ideality and derived an expression which led to deoxidation values of 2.0x10-14 and 1.1x10-12 at 1600" and 1700°C, respectively. The errors in these treatments originate mainly from inaccuracies of thermal data and uncertainties regarding the activity coefficients of dissolved oxygen and aluminum. The purpose of this investigation was to study the equilibria represented in the following reactions in the presence of pure alumina: Al2O3(s) = 2Al + 3O K = aAl2.ao3 [1] Al2O3(s) + 3H2(g) = 2Al + 3H2O(g) H2O K2 = aAl2(H2O/H2 ) [2] H2(g) +O = H2O(g) K3 = 1/ao (H2) [3] The experimental method consisted of melting pure electrolytic iron, usually with an initial charge of aluminum, in pure dense alumina crucibles under a controlled atmosphere of H,O and H2 and holding

Jan 1, 1954

By C. F. Floe, N. J. Grant, A. Joukainen

A CCORDING to Guertler,¹ Smith and Hamilton were the first to study the Cu-Ti alloy system, but because of the presence of large amounts of impurities their data are inconclusive. Hensel and Larsen² in 1930 and Kroll³ in 1931 determined the high copper end of the diagram. In 1939 Laves and Wallbaum,4 in a short summary of compound determinations in titanium binary alloys, mentioned the existence of a face-centered cubic compound, Ti2Cu, with 96 atoms per unit cell, and also a compound, TiCu3, which was said to have a deformed hexagonal close-packed structure in which ordering had been observed. The existence of a compound, TiCu, was also found but the crystal structure was not determined. Craighead, Simmons, and Eastwood determined the effect of copper on the allotropic transformation in titanium. The investigation was limited to alloys containing from 0 to 5 pct Cu, using titanium of fairly high impurity content. Experimental Procedure The methods used for determination of the diagram included metallographic examination and X-ray and thermal analyses. The system was first worked out using the higher purity "Process A" sponge titanium and oxygen-free copper. The high titanium region was next determined more accurately using iodide titanium and vacuum-melted, oxygen-free copper. Preparation of Alloys: The alloys were prepared by arc melting under prepurified helium atmos- pheres in water-cooled copper crucibles. The high purity iodide titanium alloys were prepared by melting three compositions along with a specimen of unalloyed titanium in a single charge. A multiple crucible was used which consisted of a copper plate with four cup-like depressions. The unalloyed titanium was melted first and acted as a getter for any oxygen and nitrogen in the melting chamber. Since these elements harden titanium, the hardness of the standard specimen was an index of the highest probable contamination of the alloy melts. The sponge titanium alloy melts weighed from 100 to 200 g each and the iodide titanium melts from 20 to 25 g. In order to insure greater homogeneity most of the alloys were melted, turned, and remelted twice. The larger buttons made from sponge titanium were sectioned or crushed before remelting. These alloys up to 30 pct Cu were further homogenized by forging at 925°C. They forged readily up to 20 pct Cu but numerous cracks were formed in the alloys containing from 20 to 30 pct. Above 30 pct Cu the sponge titanium alloys were homogenized by heating for 200 hr at 850°C under prepurified helium. Similarly, the iodide-grade titanium alloys containing up to 3 pct Cu were homogenized at 1000°C for 24 hr and all others at 880°C for 200 hr.

Jan 1, 1953

By Charles Himrod

In presenting this paper it is not intended to enter into any discussion of the theory of the blast-furnace, but simply to give the results of a number of determinations of CO and CO 2 in furnace gases, and some conclusions arrived at, and the result of an experiment made in hopes of increasing the production of CO 2. In the first table, on page 198, is given the averages of a number of analyses of gases of different furnaces, and in the second, of two stacks of different sizes under varying circumstances. The conclusions arrived at as to what influences the production of CO2 are as follows: lst,. Kind of fuel. Bituminous coal not permitting the formation of as much CO, as coke. 2d. Kind of ores. Rolling-mill cinder being much less favorable to formation of CO2 than hematite ores, magnetites probably less than hematites, but more than cinder. 3d. Length of time of contact of gases with ore. Small furnaces and too rapid driving both waste fuel by riot allowing enough time for conversion of CO into CO2. 4th. The temperature of blast. The hotter the greater the quantity of CO2. 5th. Regularity of passage of stock through the furnace. The hanging and dropping of the stock, however slight, seems to pack it more solidly in the hearth, increases the resistance to the blast, and decreases the quantity of CO2. These are the most common causes noticed which influence the production of CO2, unless we except the one that might be considered the greatest of all, the one that has spoiled so many tons of iron, and the amiability of so many furnacemen, the one most dreaded, the great unknown. It would seem a self-evident proposition that the better the contact of the gases with the ore and the less with the fuel, the greater would be the amount of CO2 produced. To prolong the contact of gas with the ore furnaces are enlarged with advantage, and pains are taken to charge the stock in such a manner as will best promote it. Still, with furnaces of most approved construction and most skilful manipulation, the gases leave the furnace so rich in CO, that not half the heating power of the fuel is obtained, and the highest

James DouGlas, New York, N. Y. (communication to the Secretary*):—In my paper on the Conservation of Natural Resources, I referred to the slow replacement of bee-hive ovens by the by-product ovens as a most notable instance of waste. And I quoted from Mr. Parker's report for 1906 an explanation given by him in accounting for the small production of by-product coke. It was that the market for the by-products of the coke-ovens was so limited that some of the ovens constructed were out of operation. His report on the manufacture of coke in 1908' does not record an improvement, and attributes the strange fact that we alone, of all the industrial peoples, delay the adoption of this cardinal improvement from the continuance of the same almost inexplicable cause. To quote again from his report, he says (p. 241): "The year 1908 was not marked by any notable gain in the construction of byproduct coking plants, though some new work was done. There was a net increase

Jan 1, 1910

By Leonard Klein

Reduction of oxygen-containing copper has always heretofore been brought about with wood poles. This paper reveals the first successful, economical, and Practical substitute for poles: a gaseous reductant, of which the production and plant use are detailed herein. THE art of fire refining of copper, consisting of melting, oxidation, slag removal, and finally reduction with wood poles, has been practiced for many centuries. An authentic record, discussed in detail in De Re Metallica,* mentions that as early as 1200 A.D. workers in this field of metallurgy were already acquainted with and practiced the basic principles of copper purification. Undoubtedly, the art was well developed marly centuries before the first written records began to appear. Notwithstanding the many advantages gained by application of mechanical con. trivances and by the tremendous increase in size of operations over the centuries, the reduction phase of the process has persisted essentially the same to the present time except for a very recent breakthrough. Numerous articles have been published and many patents have been issued on the subject of substitutes for wood poling in the past half century. They have dealt with a variety of gaseous, solid, and liquid reducing agents. But to the knowledge of the writer, no procedure has ever been prosecuted to a complete success on a large operating plant scale with the single exception of gaseous reduction of oxygen-containing copper revealed in detail herein. A natural gas-air reformer with ample capacity for

Jan 1, 1962

By C. Hosten, K. V. S. Sastry, D. J. Kawulok-Englund

Since the last decade the iron ore processing industry has undergone drastic changes from supplying screened and natural ores to manufacturing tailored concentrates and pellets. Increased need for the beneficiation of lower grade iron ore deposits and the increased demand for higher grade concentrates necessitate finer grinding of iron ores before concentration. The normal filtration stations used in the past are experiencing difficulties in dewatering the finely ground concentrates to moisture levels acceptable for balling. In addition to finer grinding, applications of complex beneficiation techniques has decreased the filterability of the concentrates and create problems in filtration of iron ore concentrates. An overview of the filtration literature indicates there are few research reports on the dewatering of iron ore concentrate slurries. There exists a need to understand the principles and mechanisms involved in the filtration of iron ore concentrate slurries with a goal of developing more efficient filtration techniques. This paper presents the results from the first phase of our research program that included the development of a reproducible benchscale filtration technique and the investigation of the filtration behavior of eight iron ore concentrates.

Jan 1, 1984

By A. W. Schlechten, A. H. Larson

Equilibrium H2S/H2 ratios were determined as functions of temperature (500o to 900°C) and composition in a hydrogen-circulation apparatus. Within the composition range studied there exists a two-phase region of "Zr3S4" and "ZrS2". The upper composition limit of this two-phase region is hounded by a disulfide phase and is practically constant over the temperature range investigated. The lower composition limit of this two-phase region is bounded a "Zr3S4 " phase and varies appreciably with tem- perature. The upper composition limit of the homogeneous region of the disulfide phase is not definitely determined, but it appears to he bounded by the stoichiometric composition of ZrS2. The lower composition limit of the homogeneous region of the Zr3S4 phase could not he determined due to the extremely low values of the equilibrium H2S/H2 ratios. Various thermodynamic quantities are evaluated from the data. PUBLISHED free-energy data for the Zr-S system are practically nonexistent. Strotzer, Biltz, and Meisel1 measured the sulfur pressures for the reaction 2ZrS2(s) + S2(g) = ZrS3(s) in the temperature range 783" to 874°C. The average heat of reaction calculated from the temperature dependence of the sulfur pressure is -47 keal. It should be noted, however, that according to these investigators, the two-phase region as determined by sulfur pressure constancy under isothermal conditions extended from approximately ZrS2, 3 to ZrS2.7. From consideration of X-ray data they concluded that the homogeneous regions of the disulfide and trisulfide phases are ZrS1.8-2.0 and ZrS2.8-3.2, respectively. Hahn and coworkers2 have made a structure study of the zirconium sulfide phases. They summarized the zirconium sulfide phases as follows: the compounds ZrS3 and ZrS2 with narrow homogeneous regions, a "Zr3S4" phase with a homogeneous region roughly within the limits of ZrSl.5 and ZrSo.9, the compounds ZrS and Zr4S3, and a "Zr3S2" phase with a homogeneous region within the limits ZrSo.8 and ZrSo.5. It is noted that the compounds ZrS and Zr4S3 are only formed in the gaseous state through sublimation of a phase which has the approximate composition of the compound. This paper describes the determination of the stability of the zirconium sulfide phases by a hydrogen-reduction method in which hydrogen is circulated over the heated sulfide until equilibrium is attained. The resulting H2S-H2 mixture is then analyzed. Partial molar free energies, enthalpies,

Jan 1, 1964

W. L. Saunders, New York, N. Y.:—Mr. Parker's paper, though entitled Conservation of Coal, might also be called the Conservation of Life in the Coal-Mines of the United States. No subject is of greater importance to mining-men at the present time than information from experts as to how to save coal and how to save human lives in mines. That the casualties in the coal-mines should exceed 3,000 in the year 1907 is simply appalling, and that 1,000 men should have been killed in a single year through explosions alone, and that so good an authority as Mr. Parker should say that " a prolific cause " is an "improperly-prepared blast" or "the failure on the part of the miner to undercut his coal," points to the importance of activity not only among mining engineers but also, through experts, by the legislatures of the respective States. There is but little doubt that nearly all the serious coal-mine

Jan 1, 1910

By Charles L. Guettel

The temperature coefficients of electrical resistance of 31 alloys in the nickel-rich corner of the Ni-Cr-Fe system were determined. The results indicate that a range of binary Ni-Cr alloys has lower temperature coefficients than a specific region of Ni-Cr-Fe alloys which has been reported and quoted by others as providing the lowest coefficients in the ternary system. DESIRABLE properties of resistivity and temperature coefficients of resistance have been the basis for the successful commercial application of various Ni-Cr and Ni-Cr-Fe alloys. In particular, low or negligible temperature coefficients of resistance are necessary for wire used in precision wire wound resistors and potentiometers involved in closely controlled electrical and electronic circuitry. Alloys most successfully applied to this purpose basically have not been ternary Ni-Cr-Fe alloys but rather heat-treated Ni-Cr alloys in the region of approximately 73 to 79 pct Ni and 20 pct Cr with significant additions of other elements such as aluminum, silicon, iron, copper, manganese, and cobalt. While the addition elements play a vital role in the nature and control of the temperature-resistance curve of any one of these alloys, the inherent relatively low temperature coefficient of the binary Ni-Cr base composition itself in the approximate region of 80 pct Ni and 20 pct Cr contributes fundamentally to the eventual negligible temperature coefficient obtained with the applied alloys. W. A. Dean 1 has reported mean temperature coefficients (20' to 100oC) of as-cast samples for the Ni-Cr-Fe system, the nickel corner of which is given in Fig. 1. Dean had to use as-cast samples because alloys from a considerable region of the system were unworkable. Dean refers to the work of Hunter and sebast2 who used annealed wire samples to show that, for chromium contents of 10 to 25 pct, the temperature coefficient increases as the iron content is increased at the expense of nickel. Although the data of Hunter and Sebast were limited in the nickel-rich areas to eight samples of 60 to 91 pct Ni with only four samples containing iron, the possibility that no Ni-Cr-Fe alloy has a lower temperature coefficient than certain binary Ni-Cr alloys should have been given serious consideration. However, Dean's work has been referred to by J. S. Marsh,3 who, quoting Dean, states that for the temperature coefficients "the smallest values-about 0.0001 per oC (100 ppm)—were found for alloys containing about 55 pct Ni and 20 pct Cr" (balance iron). A region such as that reported by Dean would be significant to those trying to develop alloys for the applications described. Therefore, a series of three-pound laboratory open-air induction melts of Ni-Cr and Ni-Cr-Fe alloys were melted, conventionally processed to 0.005 in. diam wire, and continuously strand annealed at 1900° F. The basic Ni-Cr compositions, with balances essentially iron other than usual minor impurities, and the corresponding temperature coefficients of resistance and resistivities are given in Table I. The resistivities are approximate and are not to be considered as a basis for relating them to their position of composition in the ternary system. The wire diameters were determined with a micrometer, and not by weight and density measurements which would be required for accurate resistivity values. However,

Jan 1, 1963

By A. W. Gray

Page CRUSHING STRENGTH...................... 659 The Black Dynamometer....................659 A Standardized Procedure for Crushing Strength Tests...... 660 Influence of Height of Test-piece upon Apparent Strength ..... 662 Influence of Packing Pressure and of Packing Time........ 662 Application of the Logarithmic Law...............665 Influence of Amalgamation Variables.............. 665 Influence of Temperature................... 669 The Transition Region Near 70" C............... 671 Influence of Packing Pressure at Various Temperatures ...... 673 Influence of Age upon Alloy and Amalgam........... 676 DIMENSIONAL CHANGES DURING THE HARDENING OF AN AMALGAM .......................... 678 The Black Amalgam Micrometer............... 678 Thermostated Dilatometer Designed by the Author........ 681 Graphical Representation of Reaction Expansions......... 683 The Typical Reaction Expansion Curve ............. 684 Influence of Packing Pressure................. 686 Influence of Trituration Time................. 687 Influence of Temperature................... 688 Influence of Mercury-alloy Ratio................ 689 Influence of Packing Time................... 689 Influence of Annealing the Alloy................ 691 Influence of Size of Alloy Particles...............691 Extension of the Typical Expansion Curve........... 693 Influence of Thermal Softening and of Reamalgamating a Hardened Amalgam.......................... 634 Curves Obtained with a Variety of Dental Alloys ........ 694 Copper Amalgam ...................... 694 PRACTICAL APPLICATIONS OF THE RESULTS.......... 695 Phenomena which reveal chemical and physical processes that probably go on in many alloys at temperatures not far removed from their melting ranges are observable in dental amalgams. These amalgams should. therefore. be of even more interest to the metallographer, the metallurgistl the chemist. and the physicist than to the dentist who uses them for saving decaying teeth. For this reason I am here de-

Jan 1, 1919

By R. F. Marande, R. S. Busk

THE magnesium-aluminum-zinc system contains most of the magnesium-base alloys used commercially, although in practice the ternary, alloys are usually modified by the addition of a small amount [ ] of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the object of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.1 [ ] All alloys reported were made in 15-lb. melts, superheated to 1700°F. for 15 min., cooled to 1400°F. and poured in sand molds. The test bars produced had a ½ in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. CONSTITUTIONAL DATA Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By K. Huessener

Discussion of the paper of K. HUESSENER, presented at the New York. meeting, February, .1916, and printed in Bulletin No. -110, February, 1916, pp. 443 to 474. KARL NIBECKER, Youngstown, O.-It has been contended that the method of measuring the operation of a blast-furnace boiler plant by means of the amount of steam generated per pound of coke used in the blast furnace is not of any value and even that it is quite misleading. It has been found, in the plant with which I am connected, that, in general, a blast furnace will operate during a month so close to average. conditions that the average monthly measure of the plant efficiency is indicated by the number of pounds of steam made per pound of coke put into the furnace, neglecting the amount of iron made and the amount of gas used for heating the stoves. For some time, it has been our custom to keep a record of this figure and use it as a general indicator of the operating practice. In comparing this figure from two different plants we have found some difficulty, due to differing conditions. It is conceivable but not altogether probable that a slight difference in burden, kind of ore or coke, would account for this difference. The method of using the gas, whether washed or unwashed, and the plant arrangement, may affect this number. For several plants on which we have worked up this number, we have found that most of the ordinary running irregularities are eliminated during a run of a month or more and that the number is, therefore, satisfactory. In connection with a plot of the number of pounds of steam generated per pound of coke, we are also plotting the production of the furnaces and the pounds of coke used per ton of production. With these three curves plotted on the same sheet, we believe that the operating man has sufficient information to judge of the efficiency of his plant' for any month.

Jan 5, 1916

By Franklin R. Carpenter, W. P. Headden

TWO notes have already appeared in the Transactions concerning the columbite or tantalite of the Black Hills tin-mines. In vol. xiii., page 232, Prof. Schaeffer speaks of the mineral as tantalite, and concludes by saying that its separation from the tinstone "is a matter which will, I believe, prove puzzling to the wisest metallurgist." He also observes that he is unable to find by analysis in his specimens the least trace of columbic acid. Prof. W. P. Blake, in the same volume, at page 696, says: " Even if it [tantalite or columbite] were present to a considerable amount, it would not injure the tin in smelting. It does not alloy with tin, but carries a small percentage of tin, which would probably be liberated in smelting." He calls the mineral columbite from the fact that a great number of specificgravity tests invariably indicated that it should be so classed. We have made chemical tests as well as specific-gravity tests upon many samples from many different parts of the Hills. Our analyses have always shown the presence of columbic acid, and the specificgravity tests have always indicated columbite, as we have elsewhere shown.* As Prof. Blake has already observed, it is not found in such close association with the tin as to prevent separation by a rough handsorting, but it is usually present with the stream-tin. As Prof. Schaeffer says, it cannot be separated by ordinary concentration; and while, as declared by Prof. Blake, its columbic acid may not unite with the tin in any form, yet its iron and manganese oxides may be reduced, and thus lower the quality of the tin produced, as is also the case when the smelting charge contains wolfram. To determine the effect of columbite in the ordinary potassium cyanide assay, there were assayed at the Dakota School of Mines four samples containing different proportions of columbite. The results, published in the report of the school for 1888, seemed to indi-

Jan 1, 1889

By A. R. Troiano, W. J. Barnett

The existence of a grain size stabilization effect on martensitic type reactions as shown by Scheill in an iron-29 pct nickel alloy and by Troiano and Tokich2 in cobalt prompted a review of other martensitic reactions to determine if this stabilization effect is characteristic of all martensite type reactions. Preliminary work has shown this effect to be present both in the gamma —+ epsilon transformation in an iron-20 pct manganese alloy and the martensite transformation of SAE 4140 and 3 pct Cr-O.40 pct steels. No appreciable effect was found in an SAE 2340 steel. The M, temperature for the gamma —+ epsilon transformation was lowered from 380°F to about room temperature by varying the annealing treatment following cold work as shown in Table I. The effect of austenitic grain size on the M, of three steels is shown in Table 2. M, was deter- mined by the conventional quench-temper method of Greninger and Troiano. In a single crystal the change in external shape concomitant with the homogeneous shear mechanism of the martensite transformation can take place unhindered. In a polycrystalline specimen a restraint of these changes must occur at the grain boundaries. Therefore, the smaller the grain size the greater the shear strain energy necessary for the formation of a martensite crystal. The degree of lowering of M, due to the reduction of grain size is much greater when the change in crystal structure involves only a small energy change, such as face-centered cubic —+ close packed hexagonal (that is, CO and Fe-20 pct manganese alloy). The maximum lowering of M, observed in the steels investigated was 50°F with a change in the ASTM austenitic grain size of 1-2 to 8-9. In comparison, the crystal structure change face-centered cubic —+ body-centered tetragonal involves a considerable energy change. There is little doubt that with much finer grain sizes the increased grain boundary restraint would greatly enhance this stabilization effect. The implications of this phenomenon are multifold. Undoubtedly. under certain conditions it offers a method of stabilizing high temperature phases for room temperature

Jan 1, 1949

By L. O. Bieber, L. H. Martin

DIFFERENT MELTS OF THE same type of nickel and high-nickel alloys, while having almost identical mechanical properties at room temperature, may have widely varying hot malleability. Either the upper limit or burning temperature may vary or a variation in malleability may occur within the temperature limits normally encountered during hot working. Melts which have reduced hot malleability of the latter type, are said to have a "hot short" range. Examination of melting records and chemical analysis of these heats fails in most cases to show the reasons for these variations. In May, 1930, an investigation was started to determine if a quick and accurate method of hot-malleability testing could be developed which would predict the ability of the metal to withstand hot forging and hot rolling by standard mill practices. The results obtained were so satisfactory that from that time on, all melts of nickel and high-nickel alloys produced in the International Nickel Company's Huntington, W. Va. Works have been tested when hot malleabilty was an important factor. To date, over 63,000 commercial melts of Monelt † nickel, Inconel† and other high-nickel alloys have been tested and the test data compared with processing results. As the result of experience gained in over sixteen years, two standard methods of hot malleability testing have been adopted.

Jan 1, 1948

By Ralph Hultgren, Louis A. Carapella

When F. Heuslerl found in 1898 that certain alloys containing only copper, manganese, and tin were ferromagnetic, the discovery excited a great deal of interest and led to numerous investigations. It was early found that tin could be replaced by aluminum, arsenic, antimony, bismuth, or boron without destroying the ferromagnetic nature of the alloys.2 Copper may also be replaced by silver.% All these alloys have come to be known as "Heusler alloys." The aluminum alloys apparently were the most magnetic and have been most extensively investigated. However, no agreement has yet been reached as to the source of the ferromagnetism arising from these nonferromagnetic elements. Absence of reliable quantitative data makes speculation hazardous. The value of much of the earlier work was vitiated by lack of necessary precautions against contamination, and by lack of close control of heat-treatment. It was only recently established that in aluminum Heusler alloys4 the ferromagnetism arose from a single phase, an ordered body-centered-cubic structure. With modern methods of preparation, heat-treatment, and X-ray examination, it is possible to prepare these alloys without contamination, to heat-treat them intellgently, and to determine what phase or phases are present in the finished sample. In the present investigation, a series of pure alloys in the comparatively neglected copper-manganese-tin system have been prepared, which consist of a single, body-centered-cubic structure (the beta phase) and whose compositions vary within wide limits. The magnetic saturation values of these single-phase alloys have been quantitatively determined, so that considerable data on the effect of composition on the ferromagnetism have been made available. In the course of the investigation some information on the extent of the stability of the beta phase and the nature of phases in adjacent regions of the ternary diagram has been accumulated. Anomalies in earlier data. have been explained, and alloys have been prepared that are much more strongly magnetic than any previous Heusler alloys. Previous Work In the original work of F. Heuslerl and coworkers,2 a maximum magnetic saturation value of I = 107 was found at the composition Cu6Mn3Sn, while a value for CusMnAl of I = 443 was early measured. Ross and Gray5 found a second maximum at the composition Cu2MnSn, which was much more magnetic than Heusler's original alloy. F. Heusler6 hen reinvesti-gated the system, confirmed their results,

Jan 1, 1942

By Louis A. Carapella, Ralph Hultgren

When F. Heuslerl found in 1898 that certain alloys containing only copper, manganese, and tin were ferromagnetic, the discovery excited a great deal of interest and led to numerous investigations. It was early found that tin could be replaced by aluminum, arsenic, antimony, bismuth, or boron without destroying the ferromagnetic nature of the alloys.2 Copper may also be replaced by silver.% All these alloys have come to be known as "Heusler alloys." The aluminum alloys apparently were the most magnetic and have been most extensively investigated. However, no agreement has yet been reached as to the source of the ferromagnetism arising from these nonferromagnetic elements. Absence of reliable quantitative data makes speculation hazardous. The value of much of the earlier work was vitiated by lack of necessary precautions against contamination, and by lack of close control of heat-treatment. It was only recently established that in aluminum Heusler alloys4 the ferromagnetism arose from a single phase, an ordered body-centered-cubic structure. With modern methods of preparation, heat-treatment, and X-ray examination, it is possible to prepare these alloys without contamination, to heat-treat them intellgently, and to determine what phase or phases are present in the finished sample. In the present investigation, a series of pure alloys in the comparatively neglected copper-manganese-tin system have been prepared, which consist of a single, body-centered-cubic structure (the beta phase) and whose compositions vary within wide limits. The magnetic saturation values of these single-phase alloys have been quantitatively determined, so that considerable data on the effect of composition on the ferromagnetism have been made available. In the course of the investigation some information on the extent of the stability of the beta phase and the nature of phases in adjacent regions of the ternary diagram has been accumulated. Anomalies in earlier data. have been explained, and alloys have been prepared that are much more strongly magnetic than any previous Heusler alloys. Previous Work In the original work of F. Heuslerl and coworkers,2 a maximum magnetic saturation value of I = 107 was found at the composition Cu6Mn3Sn, while a value for CusMnAl of I = 443 was early measured. Ross and Gray5 found a second maximum at the composition Cu2MnSn, which was much more magnetic than Heusler's original alloy. F. Heusler6 hen reinvesti-gated the system, confirmed their results,

Jan 1, 1942

By H. R. Peiffer

Composite alloys of silver and alumina are shown to resist flow above the melting point of the continuous matrix. The ability to resist flow depends on the fineness of the dispersion and the oxygen content of the silver. It is believed that the oxygen influences very strongly the bond between the molten silver and the finely divided alumina. RECENT needs for materials with high strength and creep resistance at high temperatures initiated mechanical property studies on dispersed phase materials to near the melting point of the continuous matrix material. Results' of these investigations have shown that certain of these materials do have promise for high-temperature applications. Experiments performed on composite materials of silver and alumina by the author have resulted in the discovery of an interesting effect above the melting point of the silver. In these materials the silver was continuous and the alumina very finely divided (Linde B). It was observed that these materials exhibited strength and resistance to flow above the melting point of the silver matrix. The purpose of this paper will be to describe these properties. METHOD OF PREPARATION The materials were prepared by mixing the proper amount of Linde B alumina and high-purity silver oxide. The alumina content was varied from 5 to 20 wt pct alumina in silver in 5 pct steps. The materials were mixed by blending the constituents in an ordinary food blendor using ethyl alcohol as a vehicle. Enough alcohol was added to the powders to form a mixture with the consistency of a thin mud. After blending for about | hr the material was dried and the silver oxide reduced by heating to 450 OC. The material was then pressed at 25 tsi into a -in. billets 3 in. long. EXPERIMENTAL PROCEDURE The specimens were horizontally supported at either end by knife edge supports of cold-rolled steel. This holder was then placed in a "globar" furnace and a chromel-alumel thermocouple placed very close to the specimen recorded its temperature to within 10°C. Each specimen was heated rapidly to 900°C initially. The specimens were held at temperature approximately 30 min and then the temperature was raised 50 deg. The procedure was repeated until deformation was noted. Photographs were made of the specimens at various temperatures and increments of time using a Polaroid Land camera. RESULTS Fig. 1 shows the 5 pct by weight "Linde B" alumina and silver material after reaching 980 °C. Failure occurred after 15 min at this temperature. There were two points of failure and silver collected at them. No additional flow of the molten silver was noted at any other place. Fig. 2 shows a 20 pct by weight "Linde B" alumina in silver specimen. After 30 min at 1400°C, bowing of this material was observed. Other concentrations of alumina were added to

Jan 1, 1961

By Leonard Larson

BEFORE direct or wet smelting of copper concentrate was adopted at the McGill smelter, in November 1932, actual furnace smelting tests had indicated the possibility of smelting between 400 and 500 dry tons of wet concentrate per furnace day. Under calcine smelting practice, solid charge up to 1165 tons per furnace day had been smelted. It was realized that in order to smelt wet tonnage in equivalent amount per furnace day, a higher combustion rate and higher temperatures would be neces-sary within the furnace. The reverberatory furnace considered in the following history of wet-smelting de-velopments is a unit 127 ft. long and 28 ft. 8 in. wide, inside dimensions (Fig. r). This furnace was in operation through all the years from 1934 to date. During 1933, the first complete year of direct or wet smelting, the plant was on a curtailed copper-production basis and the available concentrate tonnage to be smelted was limited. The average coal-firing rate in the reverberatory for that year was 124 tons per furnace day. This rate was lower than the average for years immediately preced-ing under calcine smelting practice. With this coal-firing rate, an average of 391 tons of new metal-bearing material (N.M.B.M.) was smelted per furnace day. The following year, 1934, the coal-firing rate was in-creased to 139 tons and the smelting rate increased to 448 tons N.M.B.M. per fur-nace day. In succeeding years production required that either more tonnage be smelted in the one furnace or an additional furnace be placed in operation. With this situation confronting the smelting depart-ment, it was determined to continue the program of increasing the coal-firing rate and also to intensify the temperature in the smelting zone of the furnace. In order to accomplish this, various improvements were made to aid combustion within the furnace. The burners were enlarged, in-creased primary air was supplied to the burners, and changes were made in the furnace to enlarge and streamline the out-let, thus increasing the furnace draft.

Jan 1, 1940

By Larry Kaufman, Martin Schatz

The effect of pressure on the extension of the ? loop in the FeSi system has been determined by means of metallogvaphic studies and hardness measurements performed on a series of high-purity Fe-Si alloys containing 7.5, 11.0, and 13.9 at. pct Si, respectively. These mensurements, performed at 42 kbar and temperatures up to 1200oC, indicate that the ? loop is expanded to about 10 at. pct Si at 42 kbar as opposed to a maximum extension of 4 at. pct Si at 1 atm. Comparison of the experimental results with thermodynamic predictions of the pressure shifts yields satisfnctory results. DURING the past few years, several studies have been performed in our laboratory1-' in order to determine the effect of high pressure on phase equilibrium in pure iron and iron-base alloys. The purpose of these studies has been to elucidate the effects of high pressure experimentally and to compare the observed results with predicted pressure effects derived on the basis of known thermody-namic and volumetric data at 1 atm. These studies have included work on pure iron2,5,7 as well as Fe-Ni,1,5 Fe-cr,l,5 and Fe-c4-6 alloys. In addition, Tanner and Kulin3 have reported results of pressure studies on two Fe-Si alloys containing 2.0 and 6.25 at. pct Si. At the time of this latter study, no detailed information was available concerning the difference in volume between the a (bcc) and ? (fcc) phases in the Fe-Si system as a function of silicon content. In order to compare their observations with calculated pressure shifts, Tanner and Kulin were forced to assume that silicon had no effect on the difference in volume between a and ? iron. The resulting discrepancy between their calculation of the a/? phase boundary at 42 kbar and the observed results led them to the conclusion that silicon additions probably decrease the difference in volume between a and ? iron. Recently: Cockett and Davis8,9 have reported de- tailed studies of the lattice parameters of a series of Fe-Si alloys at temperatures ranging from 20" to 1150°C. These measurements, performed on alloys in the bcc and fcc range, show that silicon does indeed decrease the difference in volume between a and ? iron. By correcting the calculations of Tanner and Kulin in line with the observed effect of silicon they were able to show improved agreement between computed and observed pressure shifts.' The present measurements were undertaken to provide additional corroboration of this effect, by extending the range of composition, in addition to exploring a situation where large extensions of a ? loop could result in impingement of the ? field with an ordered bcc phase (based on Feo.75Sio.25). I) EXPERIMENTAL PROCEDURES AND RESULTS The alloys investigated were obtained from Dr. F. Kayser of M.I.T. They were prepared at the Ford Scientific Laboratory by vacuum melting electrolytic iron and high-purity silicon. The melts were poured under an argon atmosphere into hot-topped steel molds. Subsequently the ingots were hot-worked down to 1/2-in.-diam rods. Three alloys containing 7.5, 11.0, and 13.9 pct Si were studied. Carbon, regarded as the principal impurity, analyzed at, or below, 0.001 wt pct for all of the alloys. Prior to pressure-temperature treatment, the rod was annealed for 24 hr in vacuum at 1000°C, water-quenched, and subsequently machined into 0.100-in.-diam by 0.100-in.-long specimens. Subsequent to machining, the specimens were again annealed and then examined metallographically. They were found to exhibit a clear coarse-grained ferrite similar to Figs. 10 and 110 of Ref. 1 and Fig. 2 of Ref. 3. Subsequently, specimens of each alloy were equilibrated at 42 kbar at various temperatures in supported piston apparatus.1,3,4,6 Three specimens, one of each alloy, were wrapped in platinum and exposed simultaneously. The pressure-temperature cycle consisted of increasing the pressure from ambient to 42 kbar at 25oC, heating rapidly to the desired temperature, holding for 15 min, and quenching to 100°C, followed by slower cooling to 25°C and pressure release. The temperature was measured with a Pt/Pt-13 pct Rh thermocouple which was not corrected for pressure effects. Subsequently, specimens were examined metallographically and by

Jan 1, 1964