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By Cuppam Dasarathy

The incidence of liquid inzmiscibility in binar)) indium alloys has been theoretically analyzed on the basis of the Hildebrand-Alott equation. Bedictions of miscibility or otherwise Imve in general been found to agree with those phase diagrams that are already publislzed in the literature. Out of a total of 27 systems, where either the complete phase diagrams are published or liquid immiscible behavior is reported, the Predictions agree with the experimental data in 25 systems, the exceptions being the Te-In and Ni-In systems. According to the equation, liquid immiscibility is also indicated in the binary alloys of indium with K, Rb, Cs, Na, Sr, Ba, Ti, Zr, V. Nb(Cb), Ta, W, U, Re, Ru, Rh, Os, and Ir. RECENT investigations by the author have shown that indium when alloyed with iron, chromium, and cobalt shows liquid immiscible behavior.1"3 The Fe-In phase diagram shows a wide range of compositions where the liquids are immiscible.4,5 No intermediate phases are present in this system. No precise information is available about the extent of liquid immiscibility in the Co-In system. However, it is certain that there is a range of compositions where the liquids are immiscible and that there are two or three intermediate phases,376 in the system. Liquid immiscibility is also strongly indicated in the Cr-In system and no evidence was obtained in the brief investigation to indicate the presence of intermediate Cr-In phases.2 The present paper deals with a theoretical analysis of binary alloys of indium with certain elements of the periodic table and indicates the systems where liquid immiscibility may be expected. The incidence of liquid immiscibility in binary systems has been theoretically examined by many workers and many excellent papers are available on the subject. In this paper, the alloy systems are examined on the basis of the more recent ideas proposed by Mott.7,8 It has been claimed8 that the Mott parameter predicts the incidence of miscibility or otherwise with reasonable accuracy and consistency. BACKGROUND TO MOTT&apos;S APPROACH Hildebrand applied his immiscibility rule for non-polar liquids to various alloy systems.9 The basis of this rule is that the equation for the excess free energy of formation of a liquid solution is rather similar to the theoretical expression for the energy of mixing of a regular solution. He postulated that when the heat of mixing is sufficiently high, separation into liquid phases will occur and the condition for complete CUPPAM DASARATHY is at the Research Centre, British Steel Corporation, (South Wales Group), Port Talbot, Glamorgan, Great Britain. Manuscript submitted March 12, 1969. IMD miscibility was shown as where VA and VB were the atomic volumes of the components A and B, and ?EV the energy of vaporization of the component. The term (?EVA/VA)1/2 was regarded as a measure of the binding energy of the component A and was called the L&apos;solubility parameter" 8A. On this basis immiscibility occurs when 1/2(VA+VB)(bA-bBf > 2RT [2] Apparently, however, there were several inconsistencies in that according to Eq. [2] several systems known to be miscible in the liquid state were predicted as immiscible. MOTT&apos;S ANALYSIS ~ott&apos;" regards that the reason for the inconsistencies arising out of Hildebrand&apos;s equation was largely due to the electrochemical attraction between the two elements, not being considered. Hence, Eqs. [I] and [2] were modified by taking into account the electro-negativities of the two elements XA and XB, and Mott arrived at an equation for immiscibility, i(VA + VB)(6A - aB)2 - 23,Q60n(XA - XBf > 2RT [3j which can be written as i **&£*&* >&apos;*°™- &apos;• HI T being the melting point of the more refractory component of the system. In Eq. [4], the numerator was called the Hildebrand term, the denominator, the electronegativity term, and their ratio, the Mott number. Mott observed that if the Mott number of a given binary system was greater than the maximum number of Pauling bonds which the two metals could form, then liquid immiscibility could be expected. The maximum number of bonds formed by a given metal was considered to be directly related to the number of bonding electrons available, i.e., to its maximum valency. Since the valencies of the elements considered vary from 1 to 6, Mott assumed that if the ratio of the Hildebrand term to the electronegativity term was >6, then immiscibility could be expected. On the contrary, if the ratio is <1, the metals should be miscible. Further, the alloying behavior is not only influenced by the valencies of the two elements but also by the relative atomic sizes that influence the types of packing and hence the coordination number. Mott considers that on average the maximum number of near neighbors of unlike atoms is 6. Thus, on both valency and size factor considerations, Mott concludes that the maximum number of bonds&apos; possible in any system was 6, this being the upper limit of the Mott number for miscibility. In considering the alloying behavior of systems with Mott numbers between 1 and 6, Mott plotted the num-

Jan 1, 1970

By Thomas, J. Elmer

WHEN the price of crude oil was advanced on July 26, 1928, with some 4,000,000 bbl. daily of potential production shut in under proration regulations, and with as much more new production shortly available from semi-proved undrilled reserves, students of the oil industry were made to realize that a new order of things now prevailed in petroleum economics. A new interpretation of the law of supply and demand had taken the place of the archaic method of influencing current production by changing crude price levels. Proration had caused the change. The long period of over-production just experienced, the prospects of a potential over-supply far into the future, had set up certain forces which brought about some fundamental changes. Their cause, effect and future influence can best be developed by a detailed study of the history of the period since war-time regulation

Jan 1, 1928

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Jan 1, 1968

By AIME AIME

T HE 121st meeting of the Institute held in New York City, February 16 to 19, 1920, was a great success despite vicissitudes of weather of unusual severity. On account of tremendous snowstorms, only two members of the Canadian contingent arrived, and several of our members from the west arrived thirty hours late. Two weeks prior to the meeting, the heaviest snowstorm in 34 years wrecked the surface transportation in New York; and it was only by special dispensation that arrangements were effected, with the New York Street Cleaning Department to clear away 39th street in front of this building so that vehicles could reach the curb. The total registration of members and guests was 1138.

Jan 1, 1920

THE solid nonmetallic inclusions that are present to some extent in all commercial steels have been variously designated. In early references they were usually called slag inclusions, and. this terminology is still retained to some extent. On the premise that all nonmetallic matter produced in a metallurgical process is slag, this can be justified. We have come to think of slag, however, in a more restricted sense, and calling these particles slag inclusions is further objectionable because it fosters the erroneous concept that they are actually incorporated portions of furnace slag. Rarely is this true. The term sonims (coined from solid nonmetallic impurities) was proposed many years ago but never came into common use. In general the term "nonmetallic inclusions" seems to be satisfactory and adequate. NATURE AND CONSTITUTION OF NONMETALLIC INCLUSIONS From the standpoint of origin, inclusions fall naturally into two classes: (1) those that occur as a result of reactions taking place in the body of the molten or solidifying metal and (2) those that result from the mechanical incorporation of refractories or other materials with which the steel comes in contact. The former are by far the more numerous and have been called indigenous, natural, or native inclusions. The latter are by their very nature sporadic in occurrence and have been called exogenous, accidental, adventitious, or foreign inclusions. They are often referred to as the "slag stringer" type, though here also the material is not likely to be furnace slag. Substances Found in Inclusions. Nonmetallic inclusions are composed principally of oxides and sulphidea but carbides and nitrides sometimes play an important role. In the case of indigenous inclusions the reactions by which these particles are precipitated from the molten or solidifying steel may be caused by (1) oxidation such as may occur during refining or during tapping and teeming, (2) deoxidation by added alloys, (3) change in equilibrium constants as the steel cools to the freezing temperature, (4) decreased solubility with lower

Jan 1, 1944

Map

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Jan 1, 1967

CYRIL STANLEY SMITH, Chairman CARL E. SWARTZ, Past-Chairman ARTHUR PHILLIPS, Vice-Chairman E. E. SCHUMACHER, Vice-Chairman H. A. MALONEY, Treasurer FRANK. T. SISCO, Secretary 9 West 39th Street, New York, N. 1. Executive Committee 1944 1945 WILLIAM C. ELLIS C. S. BARRETT ALAN MORRIS T. A. WRIGHT KENT R. VAN HORN L. L. WYMAN

Jan 1, 1943

By John W. Cahn, David A. Karlyn, Morris Cohen

The massive B(bcc) — am (fcc) transformation in Cu-Zn alloys has been studied isothermally by pulse-heating the retained ß phase from room temperature to the reaction temperatures. The transformation is found to occur only in the single-phase a region of the equilibrium diagram. The massive growth rate is of the order of 1 cm per sec and is constant at each temperature, usually after a delay time of some milliseconds. The delay time depends on the reaction temperature in C-curve fashion, while the growth rate increases monotonically with temperature over the single-phase range. The absence of isothermal massive transformation in the two-phase region does not arise from slow growth rates at such temperatures, but because the reaction cannot get started there. It is proposed that the massive transjormation initiates at small preexisting a particles which have rejected zinc into the surrounding 0 matrix. Only within the single-phase region can these particles consume the excess zinc during diffusion-controlled growth and thereby accelerate to the steady-state massive growth rate. The onset of massive growth marks the end of the delay time, and the growth rate then becomes interface-controlled. These isothermal transformation characteristics explain why the usual composition range for massive-kinetic studies by quenching is so limited. The same principles can be extended to more complex alloy systems by recognizing that the single-phase region in which the massive transformation can occur may not be stable with respect to phases not participating in the reaction. MASSWE transformations are now recognized as a regular class of solid-state reactions involving no compositional change (like martensitic transformations) and no shear displacements (unlike martensitic transformations). The name was first coined by Greninger1 in 1939 to describe the coarse grains of fcc a solid solution generated via a fast reaction from the parent bcc 0 solid solution in Cu-A1 alloys. However, some 9 years earlier, phillips2 had already described a similar transformation in the Cu-Zn system. The fact that the massive a formed as a single phase during drastic quenching from the 0 region of the equilibrium diagram signified that compositional changes were precluded. and the reaction was presumed to take place as in a one-component polymorphic transition by nucleation and growth. Phillips also observed that the occurrence of the massive transformation in the Cu-Zn system was extremely sensitive to alloy composition. For example. in a Cu-37.3 at. pct Zn alloy. the ß — am (am = massive transformation product) reaction was found to predominate and was not suppressed by iced-brine quenching from the 0 region. whereas at compositions greater than 38.3 at. pct Zn the massive reaction did not appear at all. Knowledge concerning massive transformations has bee11 substantially enhanced over the years by Massalski and his coworkers; an excellent summary of his papers and the current understanding of this type of reaction has been published recently by Barrett and ~assalski." he massive transformation product grows in roughly nodular form. often with irregular boundaries but sometimes with almost planar interfaces. The latter may have simple crys-tallographic indices relative to the 0 matrix. or the indices may be complex just as in the case of mar-tensites.&apos;1 Little is known about the existence of orientation relationships between the massive and parent phases. A striking feature of massive transformations is that the massive units start almost exclusively at grain boundaries of the parent phase and frequently propagate on a broad front across matrix grains and grain boundaries of various orientations. Because of the rapid growth rate, it is thought that the interface motion is controlled. not by long-range diffusion. but by thermally activated atom jumps across the transformation boundary.

Jan 1, 1970

Jan 1, 1968

Jan 1, 1968

By C. D. Thurmond

Jan 1, 1968

Nominating Committee.-On the recommendation of the President, the Board of Directors, at their meeting on Apr. 25,1913, appointed the following Nominating, Committee to nominate officers and directors for next year: John Hays Hammond (Ex-President), Chairman. Robert H. Richards Chairman of Boston Local Section. Richard S. McCaffery, . . . . Chairman of Spokane Local Section. Chester F. Lee Chairman of Puget Sound Local Section. Frederick G. Cottrell, . . . . San Francisco, Cal. Charles W. Goodale Butte, Mont. James W. Maleolmson, . . . . Kansas City, Mo.

Jan 5, 1913

By Robert Pack

INTRODUCTION SOONER or later in the development of any natural resource it becomes highly desirable to know the quantity of this resource in the country as a whole, as well as of the part that is being developed, for the general course and. conduct of the development work must be governed to some extent by the total supply available. An accurate estimate of the quantity of any natural resource is difficult to make; yet if one is diligent enough one can obtain a pretty accurate idea of the quantity of marketable timber, the acreage of tillable land, or the horsepower that may be developed from the streams, for these are things that may be measured. But any attempt to estimate the quantity of some mineral in the ground appears to enter the realm of imagination and it seems that the estimate can be nothing more than a blind guess. It may appear to be especially futile to attempt to determine the quantity of oil and gas that is available in the ground, for these minerals are so vagrant that even if the quantity now available should be known quite exactly, the quantity that will eventually be obtained may be much less, for certain losses in the extraction of both oil and gas are unavoidable, and just what these losses will be cannot be predicted. Though necessarily inaccurate, estimates of such mineral reserves are, however, of distinct value, for they summarize the existing knowledge of the deposits of the mineral and thus enable those who are interested in some industry that depends in one way or another on this mineral to formulate a rational commercial policy. Some time ago, when the price of gasoline suddenly rose in a rather spectacular manner, the writer was one of the U. S. Geological Survey geologists called upon to help to estimate the quantity of oil that could be obtained in the United States, for the fear had become widespread that perhaps the rate of increase in the price of gasoline was a measure of the rate of depletion of the supply of petroleum. It thus became his

Jan 8, 1917

By H. OSBORG

THE patent literature of alloys for the last two decades or so indicates that the number of liatents referring to smaller and smaller percentages of essential alloying constituents is on the increase, whereas the number of patents relating to considerable percentages of alloying additions becomes smaller. The claims regarding physical properties indicate consistently higher and more rigid values and show the possibility of modifying the physical properties by only slight changes in the percentage of minor constituents or by applying different methods - of treatment. Alloys of the same base have been made suitable for a number of different applications by intelligently and rigid- ly controlling their composition, melting, casting, working, and heat-treatments. Other trends indicated in the development of modern alloys are higher corrosion resistance, higher fatigue limits, and "stability" in volume.

Jan 1, 1937