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By S. E. Maddigan

MANY experimental and theoretical investigations have been made on the processes involved in annealing and recrystallization of metals. Most of these, however, have treated the time element as constant and heat-treatments used have been for relatively short times. Aside from the early work by Carpenter and Elam,1 the few that have investigated the effect of time on the processes have usually done so for fairly short time periods. During recent years the growing interest in long-time creep properties of metals and alloys under stress has made increasingly important a better knowledge of the recrystallization during prolonged heating. The recrystallization temperature of 70-30 brass given by Clark and White2 in 1932 was somewhat above 400°F. (204°C.) but under 500° (260°C.), whereas in our laboratory recrystallization has been observed in creep specimens at 204°C, the lowest temperature of Clark and White's range. Since the creep properties are quite different above and below the recrystallization temperature, erroneous conclusions can readily be drawn by the application of short-time recrystallization data to creep problems. It was thus considered of both practical and theoretical value to make long-time annealing studies near the minimum recrystallization temperature. In this way useful additions could be made to data on recrystallization temperatures and, since the reactions in this range are relatively slow, additional insight could be obtained into the factors involved in annealing. Several comprehensive reviews of recrystallization processes have been written,3-5 therefore only a brief review of the generally accepted facts will be given here.

Jan 1, 1940

By Joseph Kaye Wood

A metal is said to be overstrained when it is deformed beyond the elastic limit at a temperature well below the critical range, as in cold working. Quantitatively, overstrain might be considered as that part of the total elastic deformation of the piece of metal, left over after the external load is removed, that added to the permanent deformation due to plastic action will give the total permanent deformation. Ordinarily the effects of this phenomenon, which vary with the internal residual stress probably in accordance with Hooke's law, are more noticeable when the yield point of the metal is exceeded, but they probably also exist to a smaller degree when the load is just large enough to cause the least amount of permanent set. These effects, which we recognize as the result of overstrain, are as follows: 1. An apparent increase of the elastic limit in tension and a decrease of the elastic limit in compression, provided the external load is tensile. The reverse is true when the load is compressive. 2. An elastic after-effeet in which time and temperature are important factors. 3. A state of imperfect elasticity in which Hooke's straight line becomes slightly curved, giving rise to an hysteresis loop. 4. In addition to the apparent increase in the elastic limit, such properties as the hardness, ultimate strength, and resistance to fatigue failure are increased, provided the overstraining has not been carried far enough to make the metal brittle. 5. Correspondingly the ultimate elongation, reduction in area, magnetic quality, ratio of endurance limit (fatigue breaking stress) to elastic limit, and resistance to season cracking (in certain copper alloys) are decreased. The question naturally arises: how do these changes in the properties of a metal resulting from overstrain influence our method of design? The fact that most of the desirable qualities are increased makes overstraining a favorable process, from an engineering standpoint; but on the other hand, the loss of such qualities as perfect elasticity and complete

Jan 1, 1924

By Gunnar Thaning, Goran Mathisson

The iron ores mined by LKAB in the north of Sweden have excellent beneficiation properties. This gives LKAB a favorable position as regards the production of low silica pellets for direct reduction. LKAB has concentrated on developing and marketing grades of pellets for the Midrex-Purofer-HyL process group, i. e., such direct reduction processes carried out in a shaft furnace or a static bed using reformed natural gas as a reducing agent. The paper deals with properties and quality demands of iron ore pellets for such processes. Matters such as the effect of the residual magnetite in the fired pellets on the degree of metallization, the amount and composition of the slag phase in the pellets, the mechanism of the disintegration during reduction, the state of swelling of the pellets during the conditions prevailing in these processes, the importance of the porosity, the improvement of the reducibility and lowering of the sticking tendency of the pellets by small additions of suitable additives, and the influence of the pellet size are discussed. A special test procedure for direct reduction pellets has been elaborated by LKAB. Thus, three metallurgical properties are routinely determined separately, namely reducibility, reduction strength, and sticking. The test methods are described. Finally the present and future LKAB pellets for direct reduction are presented with respect to chemical analyses and metallurgical properties.

Jan 1, 1980

By F. Osmond

When a metal (whether a simple substance, an alloy, or a compound) presents, in each of the smallest parts to which it can be redueed by mechanical division, a constant chemical composition, it is defined as chemically homogeneous. But chemical hombgeneity by no means necessitates mechanical homogeneity. There are no perfectly amorphous metals. Crystalline forces, on the one hand, and tensions or compressions, on the other band, determined by icequalities of temperature in the mass during heating or cooling, give rise in every metal to the formation of geometric elements of structure. These elements may, moreover, assume perfect crystalline forms, with their planes of cleavage; or embryonic crystalline forms, segregated in the midst of. a paste of confused organization; or pseudo-crystalline forms of expansion and contraction, like those produced in the drying of gelatinous precipitates or (most frequently) these different forms associated. 111 either case the adhesions between two adjoining structural elements, respectively homogeneous, may be very different from the interior cohesion of each of these elements. The mechanical properties of this complex aggregate cannot be simple, and, when it is submitted to strains sufficient to produce deformation, the results may be very different according to the type of structure or the manner in which it is affected by the strains. It may be fairly said that a metal does not present a single resistance to tension, or a single resistance to compression, etc., but in fact, at least theoretically, as many resistances to tension, compression, etc., as it may possess coexistent features of structure; only, in any single test, it is the weakest of the resistances involved which makes itself evident. For further explanation, let us imagine a cylinder A B (Fig. I), formed of two similar halves A and B, placed together upon their common base x y. Such a system evidently presents no resistance to axial tension, while it would resist axial compression like a single

Jan 1, 1894

By C. R. Austin

THE paper describes an investigation on the pressure welding of low-carbon steels. The work necessitated a reproducible mechanical means of making the weld and also a test that would indicate the nature and completeness of the union. An apparatus including a high-temperature furnace was devised for making the welds, and the ordinary tensile pulling test 'in correlation with macroscopic and microscopic observations was used as a means of examining the result. Initially it was intended to devise some simple test of weldability, but as the experimental work progressed, it soon became clear that with our limited knowledge of the exact nature of the mechanism of pressure welding it was impossible to interpret our results or to devise a simple test of weldability. Hence it was manifestly necessary first to study the mechanism of such welding and attempt to elucidate the fundamentals underlying the so-called welding of steel by pressing together two metal surfaces. It also became evident that it was necessary to define the term "welding." In many early experiments when, two heated rods were pressed together and then pulled in the cold, very high tensile values were obtained, and yet the fracture took place exactly in the line of junction except for a few small scattered areas. In other words, the' rods pulled apart just as they were before being "stuck" together and had certainly not welded completely, despite the high value indicating the strong cohesive force operating. In this paper, welding has been considered as a form of intimate contact between two metal surfaces, so that the units lose their individual identity and there is no change in physical properties in passing through the weld from one unit to the other. This is defined as "true welding." When true welding has taken place completely over the whole section, the probability is that the rupture in tensile test will occur outside the weld.

Jan 1, 1932

By H. Ries

THE stabilization of a gravel road with soil is a method of treatment developed in recent years by the United States Bureau of Public Roads for the purpose of binding the constituents together better, and maintain-ing a more durable surface. The process consists in adding to the gravel or crushed stone and sand, a soil mortar, so-called, of fine sand, silt and clay, mixed in the proper proportions. The coarse gravel and sand supply structural strength and hardness; the fine sand adds embedment support to the coarse sand; the silt acts as a filler to prevent the granular particles from rocking; while the clay serves not only as a binder but also provides pores minute enough to cause connecting moisture films which are supposed to have high cohesive properties1. It will be recognized that the clay is an important ingredient both when wet and dry, and should not show excessive expansion when wet, nor correspondingly high shrinkage in drying, as otherwise there is danger of unseating the nonplastic particles. Such a stabilized road, although an improvement on one with a floating surface, will in course of time be subject to wear, and become dusty when the clay dries out and breaks up. It has been found that if some salts are added to the road mixture they tend to maintain the soil moisture and prevent dustiness of the road or raveling of the road surface. In addition to this, it is claimed that these dissolved salts cause a thinning of the moisture films on the particles, thus permitting greater compaction of the road mixture, and thereby increasing its density. This fact can be proved by noting the increased compaction which a road mixture shows when certain salts are added to the soil water. Since certain chemical substances such as sodium chloride are electro-lytes, the question arises whether they cannot have some effect on. the qualities of the clay in the soil mortar, and perhaps improve them. In view of the fact that certain salts seem to exert a favorable effect on the road mixture it is desirable that they be held in the road soil as long a time as possible.

Jan 1, 1936

By G. A. Wells

The consumption of barytes in certain paints, polyurethane foams, seamless flooring, glass, brake linings, plastisol gaskets for food containers, and in fluids used for gastrointestinal X-ray examinations relies on the unique properties of barium sulfate. There are no readily available mineral substitutes. Barytes are also the essential raw material for the manufacture of industrially important barium chemicals. High quality barite ore has become scarce throughout the world. Processing ore into quality end products is both capital and energy intensive. These factors have tended to limit availability and increase Prices which have encouraged the use of alternative or competitive materials and restricted market growth.

Jan 1, 1981

By Claus G. Goetzel

SOME of the reactions and procedures upon which modern techniques in the production of metal powders are based were used for 2000 years by the ancients to reduce iron and other metals from their ores. Despite this, however, the art of powder metallurgy is relatively new and probably stems from the introduction of incandescent electric lamp filaments. Attempts to improve upon Edison's carbon filaments led to the production, in order. of metallic filaments of osmium. tantalum.. and finally of tungsten, which ha, replaced the others and is the commercial product of today. These metallic filaments were originally manufactured by the extrusion and sintering of a mixture of the metal or its oxide with a reducing agent which also served as a binder. Further progress in this direction was in the pressing of a small percentage of nickel with the tungsten. The sintering operation was carried out in an atmosphere of hydrogen, at a tem-

Jan 1, 1944

By Curtis L. Graversen, J. H. Hamilton, John C. Nixon, John R. Lewis

RECENTLY there has been much speculation concerning the advantages of using oxygen enriched air or pure oxygen in pyrometallurgical processes. The advantage of using oxygen in the iron blast furnace and elsewhere in ferrous production metallurgy has been given careful consideration and, as a result, several experiments have been tried and a number of papers have recently appeared on this subject.1.2 The use of oxygen in nonferrous smelting likewise poses interesting problems, therefore any experimental data obtained in this area should likewise be of general interest.3 Ashcroft4 in 1933 claimed to have obtained improved results when copper concentrates were roasted in pure oxygen. However, his' paper gives neither data nor experimental details. A few years ago a research program was started in this laboratory which had for its objective the determination of the mechanism of oxidation of metallic sulfides under varying conditions. To date we have studied the oxidation of galena, 5 sphalerite, and chalcocite. It is a well known fact that copper sulfide minerals are oxidized slowly by weathering agents, so that the sulfides of copper which find their way into a tailing pond are gradually changed into watersoluble and acid-soluble compounds. Commercially, the oxidation of copper sulfide minerals is accomplished by roasting them at elevated temperatures in air using a suitable (usually multiple-hearth) roaster. Most copper smelters are equipped with such roasters. In this phase of the study we were especially interested in determining the effect of temperature on: (I) the air oxidation of chalcocite and (2) the oxidation of chalcocite using commercial oxygen. The amount of sulphur removed as sulphur dioxide, the percentages of water-soluble copper, and of acid-soluble copper were determined for the air oxidation tests. In the tests using commercial oxygen, the percentages of sulphur dioxide, water-soluble copper, acid-soluble copper, water-soluble sulphur and acid-soluble sulphur were determined. For these experiments the temperature was varied from 250 to 700°°C. EXPERIMENTAL Preparation of Chalcocite (Cu2S) Natural chalcocite is not pure. Minerals such as bornite, covellite, and chalcopyrite may be present. It was decided, therefore, to prepare some chalcocite in our own laboratory. An intimate mixture of sulphur and finely divided metallic copper in the ratio of 4 g of copper to I g of sulphur was prepared. To this was added a slight excess of

Jan 1, 1948

By Edward R. Mueller

The application of a simple analog computer constructed in a home workshop has registered a 10% to 15% gain in truck productivity at the mammoth Pima mine, located 35 km (22 miles) south of Tucson, Ariz. The newly installed dispatching board enables the truck control foreman to make near-optimum dispatching decisions and to monitor each individual truck, identifying any that are off schedule.

Jan 8, 1977

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally.' Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan,3 show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision; using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by, the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.5 However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: [3fB = 9.20•'./V•Vn- (n-1) • (n+2) /8[1]] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts' as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of, a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsymmetric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat I than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system, of one degree of freedom can be applied: [1E/m[2] fP = 27] Here f, is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: [t~ = 2/f = 7r\/m/E[3]] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson' 1831) [aP = 4 D2.pL•g•h +7rD•y sin a[4]] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, pL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of-the liquid in cm, y the surface tension in dynes per cm and a the supporting angle' or the one required to insure equilibrium, a being smaller than the contact angle ?. Although demonstrated by Poisson, it has not

Jan 1, 1952

By Otis M. Clarke

The Eufaula bauxite-kaolin district in southeastern Alabama is an important source of raw material for the refractory industries in the United States. At the present time, five companies are mining and processing bauxite and kaolin from this district and a sixth company is holding substantial reserves. Mining operations are expanding, but finding new ore reserves is a major problem. The Geological Survey of Alabama sponsored geologic research in the Eufaula district to: (1) investigate the

Jan 1, 1973

By Thomas W. Healy

Particles present in mineral processing systems that are termed ultrafine are those that are small enough to be unaffected by gravity or the flow conditions imposed on the pulp. As such, their interaction with one another and with other larger particles are controlled by specific attractive and repulsive colloidal or surface interactions. Electrostatic repulsion between ultrafines is dominated by surface potential, double layer thickness and specific adsorption potential effects - controlled by pH, salt and complexing ion concentrations. Attraction due to van der Waals interactions must be assessed in terms of bulk and surface coating effects and of particle size and shape. The net effect of attraction and repulsion must finally be related to the average kinetic energy of particles in the real system.

Jan 1, 1979

By J. T. McGrath, G. B. Craig

Tensile tests on aluminum single crystals, grown from the melt, revealed that the yield stress of these crystals was raised as the amount of striation substructure was increased. The number of striation-type boundaries was varied by changing the rate of growth of the crystals. The results are interpreted in terns of a blockage of dislocation movement by striation boundaries. IMPERFECTIONS are known to have a large effect on the mechanical properties of metals. Teghtsoonian and Chalmers 1 studied a block or striation-type substructure in tin and found that the formation of the striations depended upon rate of crystal growth and orientation. They found that the angular misorienta-tion between neighboring striations varied between 15 min and 5 deg. Atwater and chalmers2 investigated striations in tin and lead, and found that purity was another factor which influenced their formation. There was a limiting purity above which the striations were straight and regular. There is little information in the literature concerning how substructures in melt-grown crystals affect strength. washburn3 introduced small-angle boundaries into zinc by a shear process and found a subsequent increase in yield stress which he attributed to the presence of these boundaries. Lauriente and pond4 found the critical resolved shear stress in aluminium crystals grown from the melt, to increase with etch pit density. The etch pits were used as an indication of growth imperfections. In Hibbard's5 work on lineage structure in copper crystals grown from the melt, he tested one crystal containing interlineage boundaries, and found a 50 pct increase in the critical resolved shear stress. Fleischer and Chalmers6, in a recent paper, mention briefly that, in the production of aluminium crystals from the melt when the growth rate was raised from 1.2 to 18 cm per hr, the yield stress increased 50 pct. They felt that the increase in yield stress with rate of growth might be attributed to a higher concentration of impurities in the gage length and also might be affected by the increased number of small-angle boundaries (striations). The present investigation was undertaken to determine the effect of the striation substructure on the strength of aluminum single crystals. EXPERIMENTAL PROCEDURE Aluminum single crystals of 99.9992 purity were grown from the melt using a technique described by Chalmers.7 The growth rate was varied from 0.6 to 20 mm per min, thus producing crystals with varying numbers of striation boundaries. To avoid prior deformation, the crystals were chemically cut to the desired length with a saturated solution of cupric chloride. They were then annealed at 580°C for 24 hr and allowed to cool slowly in the furnace. Finally, the specimens were electropolished using an electrolyte of 5 parts ethyl alcohol and 1 part perchloric acid. Each specimen was approximately 5 in. in length and 0.125 sq in. in cross section. The average orientations of the 5 series of crystals studied are shown on the stereographic projection of Fig. 1. The crystals were strained approximately 2 pct in a soft tensile machine. The strain sensitivity was 3.6 x 10-4 cm over a 5-cm gage length.

Jan 1, 1960

By C. W. Gibbs, E. K. Parks

In 1929 the Standard Oil Company of California commenced the development of a device for obtaining temperatures and pressures in flowing and shut-in wells and of suitable running equipment for such a recorder. Although simple in principle, the recorder has required much experimental work in its development. The various problems have now been solved to such an extent that it is believed that the apparatus affords a sturdy and reliable means for obtaining information regarding depth pressures,—apparatus that may be turned over to a well gang for routine operation. As an example of the rough usage the device will withstand a recent incident may be cited. Owing to failure of the lowering line at the conclusion of a run a recorder was dropped some 6300 ft. through 2 1/2-in. tubing filled with gassy oil. The device was fished out undamaged and with the pressure record intact, although the instrument had been subjected to a pressure greater than 2300 lb. per sq. in. for some 24 hr. after impact at bottom. Description of Recorder The instrument is of the continuous recording loaded spring type (Fig. I). Temperature is not recorded continuously but is obtained by maximum recording thermometers in an auxiliary thermometer well. The entire instrument assembly, from bottom of the recorder to top of the socket, is 6 1/2 ft. long and weighs less than 25 lb. The maximum outside diameter of the recorder shell is 1 1/4in., and all attachments need be no larger. This permits lowering the device inside 2-in. tubing. The operating principle is simple. The well pressure acts upon a piston A resisted by the extension of spring B. The spring deflection is recorded by a stylus C upon paper within the recording drum D. Springs.—To improve accuracy at lower maximum well pressures five interchangeable spring assemblies are used. These have maximum pressure ranges of from 250 to 5000 lb. per sq. in. Piston diameter is the same in all cases, and each spring is designed for a deflection of about 5 in. for maximum pressure loading. A complete spring assembly there-

Jan 1, 1934

By V. R. Degner

The trend in both the metallic and nonmetallic mining industry is toward processing increasingly higher tonnages of lower grade ores, thereby resulting in a growing interest in progressively larger volume individual machines in the flotation circuit. Because of the relatively high cost of large flotation machine development and evaluation, it is important to establish a rational basis by which the existing smaller flotation machine experience can be extrapolated to establish the configuration of the next larger family of flotation machines with a minimum of development modification in the field. This Paper reviews the R&D approach used in translating smaller flotation machine experience to the configuration of a 28.3 m3 (1000 cu ft) induced air machine. Internal cell hydrodynamic principles, which governed this extrapolation, and cell (liquid) surface and froth management considerations will be reviewed, and prototype machine mill tests will be summarized.

Jan 1, 1981

TO metallurgists generally, Arthur S. Dwight is no stranger even to those who do not know him personally. He is one of those contributors to technical progress whose names will go down to posterity because of their being attached to a successful machine or process, such as Dorr, Hardinge, or Marcy, or Wedge, MacDougall, or Herreshoff. The roasting and sintering method and equipment developed by Colonel Dwight and his associate, the late Richard L. Lloyd, may be found in lead smelters throughout the world, and also in many metallurgical works dealing with other ores, including those of iron. It is ordinarily used to desulphurize and agglomerate fine ores for subsequent smelting. Colonel Dwight's citation as James Douglas Medalist reads: "For his contributions to the art of smelting nonferrous ores; and particularly for his pioneer work in developing equipment and technique for sintering such ores and metallurgical products." The medal was awarded at the last Annual Meeting of the A.I.M.E. but unfortunately the medalist was unable to leave Florida at the time to receive it in person.

Jan 1, 1942

IN the early period of steelmaking, ingot structure and segregation were of no practical importance. Crucible melting required very small ingots that gave little segregation, and a small inserted hot top prevented pipe. As larger ingots were poured from bessemer converters and open-hearth furnaces, segrega- [ ] tion, piping, and gas evolution became increasingly important. The techniques of making semikilled and rimmed ingots were developed with little knowledge of the actual mechanism of the process. The first studies of solidification were made by the Brearleysl and Gathmann,2 who used stearine to show the effects of shrinkage and mold shape. Fig 11-1 is a picture of a series of stearine ingots at various stages of solidification. These studies showed that the liquid solidifies at a nearly uniform rate from the sides and bottom of the mold and demonstrated the formation of

Jan 1, 1951

By N. J. Olson, G. W. Toop

A series of equations previously derived for calculating ternary thermodynamic properties using binary data has been applied to the problem of predicting ternary phase diagrams and quaternary excess free energy. The methods are considered to be rigorous for regular ternary and quaternary systerns and empirical for nonregular systems. The equations have been used to predict ternary phase boundaries in the Pb-Sn-Zn system at 926°K and the Ag-Pd-Cu system at 1000ºK. Calculated quaternary excess free-energy values are presented for the Pb-Sn-Cd-Bi system at 773°K. A method for predicting the location of ternary phase boundaries would be a useful supplement to experimental measurements in ternary systems. This has been recognized with the considerable work that has been done to find models to predict or extend thermodynamic properties and phase diagrams in binary and ternary systems1-18 for which direct experimental measurements are limited. With the access to highspeed digital computers and mechanical plotting devices, it is currently rather easy to compare mathematical models with experimental data. The regular-solution model is consistent with systems which exhibit negative heats of mixing, positive heats of mixing, and miscibility gaps, and therefore it is applicable to simple phase diagrams. The purpose of this paper is to illustrate the use of regular-solution equations to predict, empirically, phase equilibria in some types of nonregular ternary systems. Corresponding equations for regular quaternary systems are given and used to calculate empirical quaternary excess free-energy data. METHOD FOR PREDICTING THE LOCATION OF TERNARY PHASE BOUNDARIES USING BINARY DATA Meijerin1,6 has used the regular-solution model to calculate common tangent points to ternary free energy of mixing surfaces and hence to determine phase boundaries in ternary systems involving miscibility gaps. He used the following equation to calculate ternary excess free energy of mixing values: stants characteristic of the binary solutions, and Ni is the mole fraction of component i. An alternate expression which gives for regular solutions as a function of binary values of along composition paths with constant N1/N2, N2lN3, and N1/N3 may also be derived:15 ternary r xs 1 ?c-*n.Ti*.U*. This expression for is more useful for the empirical calculation of ternary excess free-energy values for nonregular systems because actual binary AFXS data may be used in the expression rather than attempting to find suitable constants for Eq. [I]. The results of this feature of Eq. [2] are illustrated in Table I where calculated excess free-energy values for the Ni-Mn-Fe system at 1232°K are compared with experimental data of Smith, Paxton, and McCabe.19 Although regular-solution equations have been shown to give calculated thermodynamic quantities which agree quite well with experiment for single-phase nonregular ternary systems,14,15 care should be exercised in the use of the equations to predict thermo-dynamic properties of multiphase ternary systems in which strong compound formation is suspected. This precaution is consistent with the simple regular-solution model which for negative values of ai_j will indicate a tendency toward compound formation but even for very large negative values of ai-jwill not give multiphase binary or ternary systems involving a distinct stable compound. Hence, calculated ternary free-energy data using Eq. [2] might be expected to vary between being rigorous and poor, in the following order, for ternary systems which are: a) regular solutions, b) nonregular single-phase liquids in which random mixing is nearly realized, c) nonregular single-phase solids, d) nonregular multiphase systems exhibiting miscibility gaps, e) nonregular multiphase systems with binary compounds but no ternary compounds, f) nonregular multiphase systems with highly stable binary and ternary compounds. The calculated data will be expected to be least accurate for the last two cases. The general method adopted in this paper involves two-dimensional plots of ternary activity curves. The principle used is that tie lines indicating two-phase equilibria join conjugate phases a and B for example, for which a1(a) = a1(B), a2(a) = a2(B), and a3(a) = a3(B). Tie lines may be determined by plotting the ternary activities of two components along an isoactivity line for the third component and the unique points where the above equalities hold may be found graphically.

Jan 1, 1970

By P. E. Demmler

Phosphorus combines with copper in various proportions, forming true alloys, some of which are of commercial importance. These materials find wide application as deoxidizers and as a means of introducing phosphorus into other alloys, as in phosphor-bronze. Phosphor-coppers containing 10 and 15 per cent. of phosphorus are the commercial grades that are most generally offered. Each has certain advantages when used in making other alloys. The 10 per cent, grade of phosphor-copper has an advantage over the 15 per cent. in that it has a much lower melting point and can be prepared by certain methods with a much lower loss in phosphorus. The 15 per cent. grade has the advantage of lower freight rates per unit of phosphorus and, by the method to be described, a uniform product can be prepared with practically no loss of phosphorus. Alloys of copper and phosphorus containing any desired percentage of phosphorus lower than 15 per cent. can be prepared by melting together the requisite amounts of copper and 15 per cent. phosphor-copper. Processes for making phosphor-copper may be divided into two classes as follows: (1) Those depending on the smelting of phosphate rock or superphosphate of calcium with copper or copper-bearing materials, and coal or other carbonaceous material; (2) those depending on the direct combination of metallic copper and elemental phosphorus. A number of formulas for preparing phosphor-copper according to the first method have been published. The Metal Industry' gives the following: Superphosphate of calcium, 60 lb.; granulated copper, 30 1b.; finely powdered coal, 10 1b. Similar formulas are given by Brannt2 and others, and detail variations are covered by patents, such as those of L. A. Jeffs3 and H. A. Webster.4 Among the objections to this method of producing phosphor-copper are the large amounts of raw material and resulting slag to be handled, and the difficulty of getting a satisfactory fusion. S. Skowronski5 found that at 1300' C. (2372' F.) it was impossible to get a good fusion

Jan 1, 1921