Search Documents

By J. R. Bell, W. J. Childs, J. H. Bucher, G. A. Wilber

A technique for determining recrystallization times as short as 0.10 sec was developed utilizing the "Gleeble", a commercially available testing system designed for the study of short-time, high-temperaLure themal and mechanical processes. The procedure consisted of heating a small tensile specimen to a given temperature of hot deformation, loading to a given reduction in area, unloading, delaying various intervals at temperature, and then reloading- to failure. The magnitude of the ultimate load obtained upon reloading decreased with delay lime as recrys-lallization proceeded. The technique was applied to austenite recrystallization in AISI 1010 and AISI 1010 uith 0.02 pct Cb steels. For each steel the reduction in area given the specimen on the first pull was mainlairred at 30 ± 5 pct and recrystallization times deterntined at various temperatures. The results indicaled a significantly slower rate of recrystallization for the columbium-modified composition, suggested the presence of- a recovery stage in the softening process , and indicated a greatly increased softening rate at a temperatuve where significant allotropic transformation to a partially ferritic Structure could occur. In recent years increasing attention has been paid to the fact that the process of recrystallization of austenite deformed at elevated temperatures is far from instantaneous at many practical hot-working temperatures.1-3 This realization has given rise to such terms as hot cold-working1 or warm-working,2 These terms generally describe processes where the recrystallization rate at the temperature of deformation is slow enough to have an appreciable effect on mechanical properties despite a relatively high deformation ternperature. The mechanical properties of interest can be either the properties at the deformation temperature as in hot-workability studies4 or the room-temperature properties after cooling as in the many recent studies of various thermomechanical processes172 where heat treatment and deformation are intentionally combined to give a unique set of room-temperature properties. Because of this interest in processes where the austenite recrystallization kinetics can be an important variable, the development of quantitative methods of following the course of short-time, high-temperature recrystallization has received increasing attention.l,3,5 The experimental methods to date have, in general, relied upon rapidly deforming the austenite, holding at temperature for various brief intervals, quenching as G.A.WILBER and W. J. CHILDS, Members AIME,are Research-Fellow and Professor, respectively, Rensselaer Polytechnic Institute, Troy, N. Y. J. R. BELL and J. H. BUCHER, Member AIME, are Research Engineer and Research Supervisor, respectively, Graham Research Laboratory, Jones & Laughlin Steel Co., Pittsburgh, Pa. Manuscript submitted March 13, 1968. IMD. rapidly as possible, and then using room-temperature measurements to follow the recrystallization process. Although such methods can be successfully applied to certain alloy steels, the existence of the allotropic transformation during cooling of plain-carbon or low-alloy steels tends to obscure the results. Thus, such room-temperature measurements as hardness and X-ray line widths do not correlate well with the extent of austenite recrystallization before quenching,5 and results based on room-temperature microstruc-tural observations are dependent upon the success in correlating the observed structure with the prior aus-tenitic grain structure.1,3,5 The purpose of the present work was to develop a quantitative method for the determination of short-time, high-temperature recrystallization rates, based on measurements made at the temperature of deformation. EXPERIMENTAL TECHNIQUE The basic technique consisted of heating a small tensile specimen to a given temperature of hot deformation, loading to a given reduction in area, unloading, delaying various intervals at temperature, and then reloading to failure. The data were obtained in the form of traces of load and elongation as a function of time. Due to the high deformation temperature, the strain hardening introduced during initial loading was progressively annealed out with holding time after unloading and the loads obtained upon reloading decreased as this softening proceeded. Although the value of the second load at any Consistent point On the load-elongation curve could have been used as a measure of the degree of softening, the most convenient to use was the ultimate load. The softening indicated by the decrease in the second ultimate load with time is essentially a process of annealing of cold-worked material at a high deformation temperature. Although some recovery grain growth may contribute to such a softening process, it is generally considered that the major softening which must take place to achieve complete removal of substantial Strain hardening will occur by the formation of new, stress-free grains. As the results of this work indicate that essentially complete removal of strain hardening did in fact occur. the primary softening process will be attributed to recrystallization, and specific reference made where it appears that other mechanisms may be contributing to the total observed softening. It would, of course, be of interest to attempt to correlate the results of this work with the actual austenite fraction recrystallized as determined by other techniques. This was not attempted in the present work because it would have required running a large number of additional specimens and, as discussed previously, there is limited assurance that the results would accurately reflect the prior austenite fraction recrys-

Jan 1, 1969

By J. S. Kennedy, A. A. Lerew, C. M. Judson, G. L. Simard

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from. these laboratories." These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that, are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren, machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as. the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite. flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the. selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pet Zn for ZnS) ; and the quartz from Klondike, Mo., analyzed as 99.97 pet SiO2. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from S82 supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1952

By G. W. Powell

G. W. Powell (Ohio State University)—Appleton and Bever measured the quantity Es which, for a solid torsion specimen, is basically an average quantity. Es is the amount of energy stored in a solid torsion specimen strained to a surface shear strain of divided by the total number of gram-atoms of alloy in the specimen. It would seem more meaningful and rigorous to deal instead with the quantity which is the energy stored per gram-atom of an alloy uniformly strained to the shear strain . The purpose of this discussion is to demonstrate that as a function of y is readily obtained from the torsion data. radius of the torsion specimen, shear strain at the surface of the torsion specimen density of the alloy, atomic weight of the alloy, and total energy stored in unit length of the torsion specimen. The energy stored in unit length of an elemental tubular section of the torsion specimen is, as given by Appleton and Bever, where E is expressed as calories per gram-atom. The energy stored in unit length of the torsion specimen is

Jan 1, 1963

By Howard Willey

MINING operations of the Charcas unit at present are limited to the Tiro General mine at Charcas, in the State of San Luis Potosi, Mexico. The Tiro General mine was first operated during the Spanish occupation of Mexico for rich silver ores in an oxidized zone along the outcrop of the principal vein. In depth the ore is a complex sulfide with widely varying proportions of sphalerite, argentiferous galena and chalcopyrite; and until recent years, it was economically impossible to carry on mining otherwise than irregularly in sections of the veins richest in galena and chalcopyrite. The advent of selective flotation brought the orebody as a whole within the field of economic interest, and a flotation mill of 650 metric tons daily capacity was constructed in the year 1925. The mining of partly worked-out sections of the mine, as well as the very heavy ground in most of the stopes opened in virgin ore, presented an unusually difficult problem. This -paper describes the so-called "filled top slice" stoping method finally adopted as the standard system.

Jan 1, 1930

By V. F. STANLEY

THERE is not the slightest doubt that the present recoveries of valuable minerals by the Broken Hill mills could be improved, and that further machinery would be installed for the purpose if it could be assured that a high price of metals would be maintained; but concentration, like all other com¬mercial propositions, is a question of profit and loss, and no sensible metallurgist would carry out his work in such a manner as to obtain high recoveries at a financial loss to his company. There is a point in all concentration at which the added money obtained from the higher recovery of minerals is balanced by the extra cost of obtaining the last part of the recovery; a wise metallurgist will be content with his work before his working-expenditure reaches this point. To a casual observer, the work being done by the various Broken Hill mills is identically the same. A closer investigation will show that this is far from being the case, for it is a remarkable fact that, although the larger mines extend over a length of approximately only 2 miles, such a difference in the physical and chemical properties of the ores exists that, from the first reduction downwards, special treatment is necessary in each case, and hardly any two mills are identical in operation. The details of this paper refer directly- to the work of one . particular mill in Broken Hill, for the reason that the ore from each mine presents special difficulties and requires its own special treatment. I have selected the mill referred to because it has been constructed and modified under my supervision.

Sep 1, 1909

By J. Ruben Velasco, Roland B. Mulchay

CANANEA has long been recognized as a remarkable field for geologic study. The copper deposits and rocks of the district have been described by many geologists and engineers, but only the most general correlations have been made between Cananea sedimentary rocks and other known sedimentary sections in the southwestern United States and northern Mexico. The present paper describes the Cananea sediments in greater detail than has been done before and attempts to fit the Cananea sedimentary section more closely into the geologic time table. The lack of well-preserved fossils has made it difficult to date the sediments accurately in geo- logic time, but it is possible to make tentative correlations between the Cananea sediments and the southeastern Arizona sections, based largely upon lithology and general position in the geologic column. It appears that sedimentation at Cananea and Bisbee may have been closely similar during Paleozoic time. Even such generalized correlations, however, may be subject to considerable modification in the future. The present study has led to the recognition of other problems of age and mineralization relationships in the Cananea district. Cananea is located in the north-central part of the state of Sonora, Mexico, at an elevation of 5270 ft. It is about 135 miles northeast of Hermosillo, the state capital, and 25 miles south of the international boundary. By road Cananea is 40 miles from the twin towns of Naco, Ariz., and Naco, Sonora, and about 50 miles from Bisbee, Ariz. It is served by the Nogales-Naco branch of the railroad, F.C. Pacifico, and is connected with Chihuahua and Mexico City by the Aeronaves airline.

Jan 6, 1954

By Bertrand S. Summers

The technologist who has devoted much attention to the foundry-business will perhaps have noticed that the present scientific development of foundry-practice is in a condition similar to that of the steel-business some twenty years ago. In many cases chemistry is looked upon with suspicion, and the old cutand-try-methods are still in vogue, especially in the smaller foundries. The larger works have laboratories and more extensive means for applying science, and have devoted considerable time and attention to the improvement of foundry-practice. This is more especially true in the East, although in the West there are numerous firms devoting considerable attention to improving their metllods through the application of chemistry to work in the iron-foundry. It is hardly necessary to dwell extensively upon the effects of the different metalloids associated with iron, in pig- or castiron, in the way they are given in most text-books. The writer has thought proper to consider more particularly new developments in eupola-practice, particularly those pertinent to the discussion of the physics of cast-iron. In this connection some new ideas which recent practice has developed will be mentioned, and some results of practical tests along the same line will be described. Yet it has been deemed advisable also, by way of introduction, to outline the effects of the metalloids as they are described in most text-books, without going into detail. The question is sometimes asked, What is the most important element governing the quality of cast-iron 'for any particular purpose ? It would seem that right here lies the basis for the greatest difference of opinion. Some twenty years or more ago, silicon was regarded by foundrymen as one of their worst

Jan 1, 1899

By R. S. Barneyback

Not much more is known about concrete today than was known to the Romans. For all the research only better tools have resulted to measure the quality of the materials that go into it." In this paper "some of the materials for lightweight concrete and their characteristics are considered and effort is made to indicate their effect on the end result — a structure of lightweight concrete." Lightweight concrete had noble beginnings. It is believed that the first specification for lightweight concrete was written by the Roman Emperor Hadrian in the early years of his reign, 117-138 AD. Hadrian, was an engineer by trade and an Emperor by adoption. He took considerable interest in the structures sponsored during his reign, even to the point of working out the structural details and preparing working drawings for some of the more prominent works in the vicinity of Rome. In order to reduce the dead weight of the 140 ft diam dome of the Pantheon he specified that the lightweight structural concrete members supporting this concrete and tile composite dome were to be fabricated from a concrete containing pumice and scoria. Still standing after 18 centuries of abuse, this structure has been described as the master effort of a great structural genius, the ultimate achievement of Roman engineering skill.' The Romans were the first to employ many concrete techniques we think of as modem innovations. Some unnamed superintendent noted that when a carefully measured amount of pigs blood was measured into each batch of concrete during mixing, the concrete was more durable and exhibited much better resistance to freezing and thawing climates. He no doubt, attributed this success to the appeasement of one of the gods who in return provided protection for the building containing this sacrificial offering in its walls. It is known today that the blood-entrained air in the concrete tends to make mixtures more workable, resistant to moisture penetration and more resistant to frost damage.

Jan 1, 1964

H. W. Turner, Portland, Ore. (communication to the Secretary*) :—Mr. Brown's paper on the complicated groups of veins exposed in the workings of the Bodie mine forme a valuable contribution to the literature of the structural features of ore-depoeits. It is much to be desired that managers should put into print the results of their observations of the mines under their charge. These observations, as well as data of production, kind of ores, etc., usually accumulate for years, and unless the mining geologists of the Geological Survey happen along before the mine is worked out, such data seldom get into print. About the year 1899 I went through the mines at Bodie with R. C. Turner, then superintendent, and made some notes on the veins and gangue-minerals, and collected some specimens. Mr. Brown refers to crystals of feldspar (albite) found on fragments of quartz on the surface. I collected a number of specimens of these crystals, mostly from Queen Bee hill, and

Jan 1, 1909

By H. D. Kessler, R. J. Van Thyne

Phase diagrams of the titanium-rich portion of the ternary systems from 0 to 10 wt pct Al and 0 to 1 wt pct 0, N, and C were determined. Micrographic analysis of annealed high purity arc melted alloys was the principal method of investigation and was supplemented by X-ray diffraction. TITANIUM-ALUMINUM alloys exhibit excellent properties, particularly for elevated temperature use. For this reason, the Materials Laboratory, Wright Air Development Center, sponsored an investigation of the effect of the interstitially soluble contaminants, oxygen! nitrogen, and carbon, on the Ti-A1 system. Using high purity arc melted alloys and micrographic analysis of annealed samples as the chief method of investigation, titanium-rich partial phase diagrams were determined for the ternary systems. Experimental Procedure Materials: The titanium used in the preparation of the alloys was iodide crystal bar (99.9+ pct pure) produced by the New Jersey Zinc Co. and Foote Mineral Co. The aluminum was obtained from the Aluminum Co. of America in the form of sheet. The given analysis was: Si, 0.0006 pct; Fe, 0.0005; Cu, 0.0022; Mg, 0.0003; Ca, <0.0006; Na, <0.0005; and Al, 99.99. High purity titanium dioxide purchased from the National Lead Co. was used in the preparation of the oxygen-bearing alloys. The spectrographic analysis of this material was as follows: SiO,, 0.07 pct; Fe,O,,, 0.002; A1,0,, <0.001; Sb,O,, <0.002; SnO,,, <0.001; Mg, <::0.001; Cb, <0.01; Cu, 0.0004; Pb, 0.002; Mn, <0.00005; W, <0.01; V, <0.002; Cr, <0.002; Ni, <0.001; and Mo, <0.002. Special spectroscopic graphite rod purchased from the National Carbon Co. was used in the preparation of the Ti-A1-C alloys. Alloy Preparation: Alloy ingots weighing 10 grams were melted in a nonconsumable tungsten electrode arc melting furnace using water-cooled copper hearths and a helium atmosphere. The arc was struck on a tungsten stud in the copper block to minimize contamination from the electrode. Details of the techniques have been reported.&apos;, &apos; Each ingot was inverted and remelted a minimum of four times to insure homogeneity, without opening the furnace. Remelting small control ingots of iodide titanium under similar conditions resulted in no measurable hardness increase, indicating contamination-free melting conditions were used. The alloy charges and resultant ingots were weighed to the nearest milligram. Only small weight losses were obtained upon melting, indicating that the actual compositions were very close to the nominal compositions. Check analyses substantiated this. Oxygen and nitrogen were added during ingot preparation as master alloys. An oxygen master alloy containing 25 wt pct 0 was prepared by melting iodide titanium and pressed titanium dioxide (40 pct 0) powder. The Ti-25 pct 0 alloy is more easily handled during weighing and charging than the pressed TiO, powder. Chemical analysis indicated that titanium-nitride received from an outside source contained large amounts of impurities (2.7 pct Ca). Therefore, a master alloy containing approximately 12 pct N was prepared by melting nitrided sponge titanium. As the sponge melted with difficulty, the alloy was diluted by addition of titanium to lower the melting point. The chemical analysis of the final alloy was 6.69 pct N. Both master alloys are friable and were used as —8 +16 mesh lumps resulting from crushing the ingots. NIelting the Ti-A1-0 and Ti-A1-N compositions five times produced homogeneous ingots. The preparation of homogeneous carbon-bearing alloys caused considerable difficulty. Alloys containing less than 1 pct C were prepared using spectrographic graphite rod, 1/8 in. diameter by 1/8 in. long. However, the graphite did not dissolve even with long melting times and many remelts. The ?/s in. pieces of graphite were used rather than powder because the low density powder is troublesome in arc melting.

Jan 1, 1955

By G. Thodos, R. B. Grieves

A method has been developed For predicting the critical temperatures and critical pressures of binary mixtures of carbon dioxide, hydrogen sulfide, nitrogen, hydrogen, carbon monoxide and oxygen with the normal paraffin hydrocarbons. For carbon-dioxide and hydrogen-sulfide systems, relations are presented that take into account the peculiar behavior of mixtures with closely boiling components, such as carbon dioxide-ethane and hydrogen sulfide-propane mixtures which exhibit minimum critical temperature points. For hydrogen, nitrogen and carbon-monoxide systems, the extreme critical behavior caused by wide differences in pure component properties is established In addition, those fixed gas-paraffin systems which resemble paraffin-paraffin systems are also accounted for. For a mixture of known composition, the pure component critical temperatures, critical pressures and normal boiling points are all that are required to determine its critical point. Graphical relations are presented relating Tc and PC , of the mixture to the pure component properties. From the treatment of 12 carbon-dioxide and hydrogen-sulfide systems reported in the literature (74 mixtures), the expected error lor the critical temperature is approximately 1.5 per cent, and for the critical pressure, approximately 2 per cent. From the treatment of six hydrogen, nitrogen and carbon-monoxide systems reported in the literature (30 mixtures), the expected error for both the critical temperature and critical pressure is approximately 2.5 per cent. The relationships, which have been developed with only normal paraffins as the hydrocarbon components, may be extended to those isoparaffins and olefins which fall within the allowable volatility ranges. INTRODUCTION Many of the fixed gases — carbon dioxide, hydrogen sulfide, nitrogen, hydrogen, carbon monoxide and oxygen — occur in natural mixtures with hydrocarbons. Carbon dioxide and hydrogen sulfide are frequent components of the fluids produced from underground petroleum reservoirs. Nitrogen, carbon dioxide and hydrogen sulfide are present in varying quantities in most natural gases and gas-condensate well effluents. Hydrogen mixtures are of considerable interest in many phases of refining processes of petroleum. The determination of the critical temperatures and critical pressures of such mixtures is of value in vapor-liquid equilibrium studies, for the prediction of the characteristics of underground reservoirs, and for reduced-state correlations of PVT, transport and thermodynamic properties. The accurate estimation of the critical point for binary mixtures is an important initial step toward a complete analysis for the establishment of the critical temperatures and pressures of multi-component mixtures. Methods for predicting the critical temperatures and critical pressures of binary hydrocarbon systems have already been presented in the literature.8 It is possible to apply these existing methods to fixed gas-paraffin mixtures, but due to their unusual critical behavior, values calculated deviate considerably from experimental values. For systems containing trace quantities of the fixed gases, these methods are acceptable; however, for systems containing more than 5 mol per cent of the fixed gases, these utterly fail to produce reasonable critical values. Consequently, in this study a method has been developed for handling such binary mixtures over the entire composition range. CARBON-DIOXIDE AND HYDROGEN-SULFIDE SYSTEMS The critical behavior and the vapor pressure behavior of mixtures of carbon dioxide and hydrogen sulfide with paraffinic hydrocarbons may be quite similar or quite dissimilar to that of paraffin-paraffin mixtures, depending on the volatilities of the components involved. The critical temperature and normal boiling point of carbon dioxide are very close to the corresponding values for ethane, while its critical pressure is considerably higher than that of ethane. The normal boiling point of

By T. Egleston

The treatment of the residues from the manufacture of sulphuric acid which contain small amounts of copper, silver and gold, has attracted considerable attention in Europe. They are successfully treated in several works on the continent, and in as many as twenty establishments in different parts of England. As the process must sooner or later attract attention in this country, I have put together my notes made in three of the most important establishments in Europe. These are the works at Hemixem near Antwerp, of Duisbourg in Westphalia, and of Oker in the Hartz. In the last works only, the ores are produced in the vicinity of the place where they are treated. The works at Duisbourg treat ores which come from the Rio Tinto mines in Spain, which often contain considerable quantities of arsenic. They are roasted in a number of different works along the Rhine for the manufacture of sulphuric acid. They are brought by boat and are landed at the works by steam-cranes. They are carried at once by a double-inclined plane worked by steam to the storagehouses to be kept, until treated. The wagons, after being weighed, are dumped. The ore is assayed at once, the assay-sample being taken from the boat while the ores are being discharged. They are all fine, and contain two to eight per cent. of copper and about sixty per cent. of iron, and a small amount of silver and gold. Their average composition is given below:

Jan 1, 1886

By J. D. Miller, M. Misra

The processing strategy for the effective separation of bitumen from low grade (<l0 weight percent bitumen) Utah tar sands by a hot water process differs significantly from that used for the processing of high grade (> 10 weight percent bitumen) Utah tar sands. Excellent separations (coefficient of separation = 0.9) can be achieved for high grade Utah tar sands by intense hot water digestion followed by a modified froth flotation step. Such a technique is ineffective for low grade tar sands. In order to change the characteristics of the low grade tar sand an attempt was made to enrich the bitumen content of the feed to greater than 10 weight percent by recycle of bitumen concentrate to the digestion stage. However, the quality of the separation was not improved under these circumstances. Similarly feed enrichment by heat treating the low grade feed with recycled concentrate prior to digestion did not improve the separation. More successful separations of low grade Utah tar sands were finally achieved by modification of the viscosity of the low grade bitumen with controlled addition of diluent. These results of the hot water separation tests and variations in the quality of separation are interpreted in terms of the physical properties of the bitumen and the surface bonding forces operative at the bitumen-sand interface.

Jan 1, 1981

By Raja V. Ramani, Ralph W. Barbaro

This paper presents an application of a Mixed Integer Programming (MIP) model to the problem of locating a centralized coal preparation plant and determining the production schedule for the mines. The system used for illustrating model application is hypothetical but realistic. It consists of three mines, two potential preparation plant sites, heavy media processing plant, and one market. The goal is to maximize the total profit of the system while satisfying the coal delivery schedule over a three year period meeting both quantity and quality requirements (ash, sulfur, and heat content). In addition to the base case, four different scenarios are analyzed. These four modifications are: (1) removing the flotation circuit from the preparation plant and sending all of the fines directly to the clean coal, (2) lowering the quality of coal from one of the mines, (3) applying discounts to the unselected site to improve its competitive position, and (4) adding a new mine. A detailed discussion of the base case and the effect of these four alternatives is presented.

Jan 1, 1983

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

The influence which Au, Ag, Sb, Bi, Sn, and Cu have, both individually and collectively, on the activity coefficient of sulfur in liquid lead at 600"C zuas studied by circulating a H2S-Hz gas wlixture over a specific lead alloy until equilibrium was attained. Subsequently, the H2S concentration in the equilibrium gas mixture and sulfur concentration in the condensed phase were deterruined. The elements gold, silver, and antinzony (above 8 at. pct) increased the activity coefficient of sulfur. Bismuth had no apparent effect. Tin (above 3 at. pct) and copper decreased the coefficient. The influence of an individual element, i, on sulfur is best reported as the interaction parameter, riS, which is defined as The values o these first-order interaction zus are: ESzu = —55.0. These interaction parameters are used to predict the activity coefficient of sulfur in six fouv-component alloys and one seven-component alloy. Comparisons are made with direct experimental determinations. INTERACTIONS in dilute solution have been studied by many investigators. Most of the experimental work has been confined to solute-solvent interactions in simple binary systems and solute-solute interactions in ternary systems. Dealy and pehlke"~ have summarized the available literature on activity coefficients at infinite dilution in nonferrous binary alloys and have calculated from published data the values for interaction parameters in dilute nonferrous alloys. Interaction parameters are a convenient means of summarizing the effect of one solute species on another in a given solvent. Only a few investigators have studied interactions of the nonmetallic element sulfur in a metallic solvent. They are as follows: Rosenqvist,~ sulfur in silver; Rosenqvist and Cox,4 sulfur in steel; chipman, sulfur in alloy steels; Alcock and Richardson,% ulfur in copper alloys; Cheng and Alcock,&apos; sulfur in iron, cobalt, and nickel; Cheng and ~lcock,&apos; sulfur in lead and tin. The only reported work on the Pb-S system in the dilute-solution region is that of Cheng and Alcock.&apos; Their investigation involved a study of the solubility of sulfur in liquid lead over the temperature range 500" to 680°C. The results may be summarized by the following relationship: S (dissolved in lead) + Pb(1) = PbS(s) log at. %S = -3388/T + 3.511 Experimentally, it was found that Henry&apos;s law was valid up to the solubility limit of sulfur in lead, i.e., at 600°C up to 0.43 pct. Their investigation did not include the study of sulfur in lead alloys. More accurate calculations could be made in smelting and refining systems if activity coefficients of solute species could be accurately predicted in complex solutions. One of the objectives of this study was to compare the experimental data with the values calculated from the equations derived from models for dilute solutions proposed by wagner9 and Alcock and Richardson. A temperature of 600°C was chosen as the experimental temperature to attain reasonable reaction rates and to minimize volatilization of the condensed phase. EXPERIMENTAL Materials. The Pb, Au, Ag, Sb, Bi, Sn, and Cu used for preparation of the alloys were American Smelting and Refining Co. research-grade materials. All were 99.999+ pct purity except the antimony and tin which were 99.99+ pct. The initial alloys prepared for this study consisted of twenty-one binary alloys, eleven ternary alloys, and one six-component alloy. The constituent elements were mixed for each desired alloy and were placed in a crucible machined from spectrographically pure graphite. The crucible was placed in a vycor tube which was evacuated with a vacuum pump and gettered by titanium sponge at 800°C for 8 to 12 hr. After the gettering was completed, the chamber containing the titanium was sealed and removed. The remaining sample chamber was placed in a tube furnace at 800°C for 2 hr and quenched in cold water. The final operation consisted of homogenization of the alloy for 1 to 2 weeks at a temperature just below the solidus for the individual system. The resulting master alloys were sectioned into small pieces and a random choice made for individual equilibrations. Cobalt sulfide (Cogs8) used to control the gas atmosphere in the circulation system was prepared by passing dried HzS for 24 hr over a Co-S mixture heated to 700°C in a tube furnace. This material was then mixed with cobalt metal to give a two-phase mixture which, when heated in hydrogen to a particular temperature, produced a desired H2S/H2 gas atmosphere in the circulation system. A Cu2S-Cu mixture also used in this study was prepared in a comparable manner. Apparatus for Equilibrium Measurements. The experimental technique of this study required apparatus

Jan 1, 1967

By A. F. Andresen

IN the course of another investigation the lattice parameters were determined for a series of compositions of tin in copper. Ten-gram samples of the alloys were made from spectroscopically pure tin and copper. The metals were weighed and placed in graphite capsules (previously fired at 5500°F) which were then sealed individually in evacuated vycor tubes. The tubes were mounted on a spit, transverse to its axis, which continually rotated the melts in a furnace. After homogenizing, filings were made of one third of each slug by filing off a complete cross section. A 325-mesh sieve was used to obtain the powder for the X-ray determination. The sieved powders were annealed in vacuo at 600°C for 24 hr to remove the cold work, and then quenched. The lattice parameters were determined with a flat-plate back-reflection camera using CuKa radiation (A., = 1.5405A, A,? = - 1.5443A). With this radiation the (331) and (420) reflections appeared close to the focusing region. As reference lines were used the same reflections from pure copper powder, between which the (420) lines of all these alloys are situated. The variation of the systematic error over this angular range was found to be less than the estimated experimental error ±0.0005A which is indicated in Fig. 1 for all but the sample with 8 pct Sn. As a check some of the powders also were examined in a regular Debye-Scherrer camera with the Straumanis film mounting. The parameters were here evaluated by extrapolation against cos2? to ?= 90o. The results are shown in Fig. 1 where the lattice parameters in Angstrom units are plotted as a function of weight percent of tin. The reflection lines for the 8 pct alloy were not clear at first, perhaps due to coring. Several measurements were made after different annealing programs on two separate

Jan 1, 1959

By Amitava Gangulee, Michael B. Bever

The effects of changes in short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions have been investigated. The heats of formation at 273°K of several alloys after two different thermal treatments were measured by liquid metal solution calorimetry. Their electrical resistivities were measured at temperatures ranging from 4° to 773°k. Tensile tests and microhard-ness measurements were carried out at room temperature. An effective short-range order parameter and an effective interaction energy are defined. The measured changes in the properties are interpreted in terms of these quantities. The short-range order parameter is evaluated separately from calorimetric and X-ray data; the results are in fair agreement. Increasing short-range order lowers the resistivity of- the silver-rich Ag-Mg alloys but does not measurably affect the temperature dependence of the resistivity. Short-range order increases the yield stress of these alloys but does not affect the ultimate tensile stress. Changes in the effective short-range order parameter independently obtained from measured changes in the heat of formation, resistivity, and yield stress are in fair agreement. THE thermodynamic, electrical, and mechanical properties of solid solutions have been investigated as functions of composition in many alloy systems, but the effects of configurational variables, such as short-range or long-range order, on these properties have received much less attention. The silver-rich terminal solid solutions in the system Ag-Mg are well-suited for the investigation of the effects of order. The composition of these solid solutions may be varied over a range extending to about 27 at. pct Mg.1 Appreciable short-range ordering is likely to take place in these solid solutions; the degree of short-range order can be varied by suitable thermal treatments. In the alloy Ag3Mg long-range ordering is possible.2 This paper is primarily concerned with the effects of short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions.-The long-range ordering transition is the subject of a concurrent paper.3 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Specimens. Ag-Mg alloys containing up to 26.4 at. pct Mg were prepared by melting 99.99 pct pure Ag (obtained from Baker Chemical Co.) and 99.99 pct pure Mg (obtained from Eastman Chemi- cal Co. or Johnson Mathey & Co.) in graphite crucibles under molten potassium chloride. The solidified ingots were homogenized at 823°K for 10 days in evacuated Vycor capsules. A surface layer 6 in. thick was then removed by machining. The ingots were swaged into rods (2.5 mm diam) which were drawn into wires (1.0 mm diam). The wire specimens were annealed at 773°K for 24 hr in vacuum and either quenched into iced brine or cooled to room temperature over a period of 15 days. The average grain diameter (obtained from the linear intercepts) was about 0.1 mm. 1.2) Calorimetry. The heats of formation of the alloys were measured in a tin solution calorimeter as the difference in the heat effects of alternate additions of samples of an alloy and the mechanical mixture of its component elements. The additions were made from 273°K to the bath at about 623°K. The heat effect on addition of the alloys was approximately 5.5 kcal per g-atom. The procedure and the method of calculation have been described.4 1.3) X-Ray Diffraction. Short-range order parameters of two alloys were calculated from diffuse scattering intensities,&apos; obtained with briquettes made from powdered specimens. A GE-XRD 5 diffractometer with filtered copper radiation was used. The absolute intensities were based on calibrations with paraffin. 1.4) Resistivity Measurements. The electrical resistivities were measured by a potentiometric method in which the potential drop across the specimen was compared with that across a standard resistance. For measurements below room temperature, the specimens were immersed in liquid helium (4°K), liquid nitrogen (78°K), dry ice and trichloroethylene (195°K), or ice and water (273°K). Measurements above room temperature were made on specimens held in a furnace under helium or in vacuum. The resistivity measurements were reproducible to ±0.5 pct or less. 1.5) Mechanical Tests. Tensile tests were carried out at room temperature with a Tinius-Olsen XY elec-tromatic Universal testing machine. Wire specimens (nominal gage length 1 in.) were used. The strain was measured with an extensometer, which had a sensitivity of 4 x 10-5; the strain rate was 10-3 min-1. Microhard-ness measurements were made with a square-pyramid indenter and a 100-g load.11 2) RESULTS AND DISCUSSION All measurements were made on two parallel sets of specimens, one quenched and the other slowly cooled from 773°K. The reported values are the averages of at least three measurements. In the range of magnesium concentration substantially below that of the composition Ag3Mg, quenched alloys have less short-range order than slowly cooled alloys. As the magnesium concentration approaches that of Ag3Mg, slow cooling develops long-range order. Quenching sup-

Jan 1, 1969

By E. M. Cox, A. S. Skapski, N. H. Nachtrieb, M. C. Bachelder

D. T. ROGERS*—The conclusions drawn in this paper have important practical significance to the steelmaker and the metallurgist if, in practice, it is demonstrated that metallic copper in the charge will pick up sulphur from the furnace atmosphere and thus increase the sulphur content of the bath. The problem of residual copper arising out of increasing copper in the scrap available to the industry is, in itself, a matter of concern to the steel maker. If, in addition to the often detrimental effects of high residual copper upon the physical properties of some important steel grades, there is to be a complication of the sulphur problem, then we have a set of conditions that bodes no good for the open hearth melter and the open hearth metallurgist. M. B. BEVER*— Investigations of gas-metal equilibria continue to be of interest, especially as new possibilities for improving experimental techniques emerge. Higher purity of reacting substances, better refractories, improved methods of temperature control and an increased awareness of the pitfalls of high-temperature equilibrium work are

Jan 1, 1950

By Charles Colcock Jones

In any discussion of this very large subject we are confronted at the outset with so many obstacles that at best only a fragmentary and rather disconnected presentation can be made of it, and my hope is that building from the few facts I have to offer a more complete knowledge may be secured. In the whole intermountain and Pacific Coast region, west of Pueblo, Col., and from Canada to Mexico, there is no production of pig iron, and steel production is confined to the manufacture of a small amount of open-hearth steel from scrap. When we consider the area, the resources, and the several centers of population, this condition seems anomalous, even in the face of every counter argument as to cheap water transportation, or other means of transport from the Atlantic Seaboard or from the iron and steel centers of the Middle West. This comatose condition, if such a term may be applied, is certainly not due to a lack of all the essential materials and factors for success in iron and steel smelting, but is rather, I think, due largely to the general fact that it is only within a comparatively few years that the centers of population on the Pacific Coast have attained a size that would entitle them to the position of distributing or freight centers, or that the "back country" has been enough built up to make it sufficiently interesting to the railroads to foster trade from the local centers to the interior points rather than seek to supply such local centers and the interior by a transcontinental haul. "Ore Supply Edwin C. Eckel, in his monumental work on Iron Ores, has but little to say concerning the Pacific Coast deposits. He mentions (p. 269) those of Minaret, Madera County, and the Eagle Mountains, Riverside County, Cal., "perhaps 50 to 100 million tons each;" the deposits in Shasta County, worked for the electric furnace on Pitt River; and

Jan 1, 1916

By James Johnston

Synopsis.—A description of the working of the mills of this company and the metallurgical practice in vogue, by which a remarkably complex silver ore, averaging 54 oz. of silver per ton (run-of-mine ore), is treated to give a 95.66 per cent. extraction. The main features of the processes are: The cyanide amalgamation of the high-grade ore. The cyanide treatment of the low-grade ore, after extremely fine grinding and close classification, in a caustic soda solution. The use of a wet desulphurizing process to break up refractory silver minerals. The substitution of aluminum dust for zinc dust as a precipitant. The recovery and shipment of over 13,000,000 oz. of silver in bullion at 997 to 999 fine since this metallurgy was inaugurated, about 2.5 years ago. On the completion and successful operation of the mill to treat their high-grade ore,&apos; the Nipissing Mining Co., under the general management of R. B. Watson, started a series of investigations of the possible treatment of the low-grade ore by the cyanide process, so that they would be in a position to market only silver bullion. These tests were run in July, 1911, on a large scale, by G. H. Clevenger, on an average mixture of Nipissing ore. The results obtained by a partiai amalgamation followed by cyanide treatment gave an extraction varying from 90 to 93 per cent. and were sufficiently encouraging to warrant Charles Butters, the company&apos;s Consulting Metallurgist, in recommending that the new low-grade ore mill under contemplation should be a cyanide mill, instead of a concentrator. The cost of such a mill, capable of treating 200 tons per day, to obtain a 90 per cent. extraction at a working cost of $3 per ton of ore treated, was estimated at $250,000. In coming to a decision as to which type of mill should be erected, the concentrator, with the subsequent shipping of concentrates to a smeltery,

Jan 1, 1915